XICANAS JZAOT--. Conference on Analytical Atomic Spectroscopy with International Participation

Moscaw,USSR July 29 August 4,1990

Abstracts USSR Academy of Sciences XICANAS XI Conference on Analytical Atomic Spectroscopy with International Participation

Moscew,USSR July 28 JUNjust 4,1990

Abstracts e UDC 543.42

XI CAHAS Conference on Analytical Atoaie -Spectroscopy with international participation

COHFEKEHCE ABSTRACTS

Plenary lecture» (Р1Л) Atomic-absorption spectroscopy (AAS) Atomic-emission spectroscopy (ABB) Atoaic laser apactroacopy (ALS) X-Ray apectroacopy (XRS) Miscellaneous spectroscopic techniquea and lata abstracts (HISC)

© V.I.Varnaiaky Institute of Geochemistry *nd Analytioal мм ч-о2_оп?9вп_х CneUtry of the USSR Aead«B} IBB» 5-02-0Q7280-X ^ ^Хвинш, 19*> PREFACE Analytical atonic spectroscopy includes a number of highly important methods of analysis, which play an essential part for analysis of environmental objects, mineral raw materials, metals and alloys, other inorganic substances and materials, different organic substances and biological objects. The theory of the atomic spectroscopy methods is a highly interesting field of research, which is connected with many branches of science. A great number of first class scientists and engineers work in the field of analytical atomic spectroscopy. They know works of one another quite well, often and useful work together, including the conferences, seminars and symposiums. The problems of the development of the theory and practice of the methods are regularly discussed at the Conferences on Analytical Atomic Spectroscopy ( CANAS ). The previous conference toak place in Torun, Poland, in 1988. The present book contains the abstracts of the presentations, contributed to the Conference of the 1990 < Moscow, July 29 - August 4, 1990 ). They were classified according to the sections. There is an x-ray spectroscopy section except the methods of the analytical atomic spectroscopy in the book. This method of analysis has been included in the program of the Conference due to the initiative of the country-organizer. As a rule in the section the abstracts connected with the development of the theory of a method are presented firet, and applied papers are presented thereafter. There is an alphabetic order within the subsection. The number presentation corresponds to its number in the program of the Conference for convenience of use. All the papers are reproduced in the original form, except small linguistic editing. The choice of papers was done by the Organizing Committee. The Editorial Board included E.P. shumilova, Д.В. Volynsky and other collaborators from V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry of the USSR Academy of Sciences, which took over the functions of the base institution of the Conference. We take the chance to extend our gratitude to the administration of the Institute ( Acad. V.L. Barsukov, Prof. B.F. Myasoedov ) and all above mentioned and not mentioned here colleagues.

Professor N.M. Kuz'min Doctor Е.И. Sedykh Conference Vice-chairman Scientific Secretary CONFERENCE COMHITTEE

Acad. Zolotov Yu.A Co-chairman prof. Myasoedov B.F Co-chairman Prof. Kuz'nin N.H Vice-chairman Dr. Sedykh Е.И Scientific Secretary Dr. Belyanin v.B. Prof. Muzgin v.H. Prof. Letokhov V.s. Prof. Karpov vu.A. Or. Ostroumov S.V. Dr. BolBhov H.A. Prof. Киг'тепко N.E. Dr. Baranov S.V. Prof, zil'berstein Kh. Prof. Nedler V.V. Dr. Zaaaraev V.P. Dr. Mogilevsky A.N. Prof. Korovin Vu.I. Prof. Nikolsky A.P. Dr. chekalin N.V. Prof. L'vov B.v. Prof. Ginelfarb F.A. Dr. Koloshnikov v.G.

CONFERENCE SECRETARIAT v.i.vernadsky Institute of eeochemistry and Analytical Chemistry of the USSR Academy of sciences 117975 GSP-i, Kosygin str. 19 Moscow V-334, USSR. Tel. 137-86-56. PLENARY LECTURES

i Х-ВЛХ SPECTHOHBTHY ANALYSIS: ADVANCE AND OUTLOOK PLH-1 FOB IBS DBVSLOHBNT

V.P. Afonin Institute of Geochemistry, Siberian Branch of the USSR Academy of Sciences, Irkutsk, USSR

DM contribution provides an appreciation of present-day state in X-ray spectrometry analysis.Some general features of instruments and theory development are discussed. At present, the following X-ray spectrometry analysis methods (XBF, SHU, PHI, SEHB, TXBP) are available. The 1^ intensity of one of strong lines of characteristic X-ray spectrum of i element to be determined is used as an ana­ lytical signal in XES analysis. The I, dependence on 0^ concentration of the element to be determined is written as: I.* co»s& C^fi, (D

where ?<-function,depending on excitation conditions and chemical composition of the temple analysed. In exciting the analytical signs! by X-ray tube radistien: Г*4Ъс/А ' (2> НъЛ%^/&ь.р1-/и/ £*р In exciting by electron beam:

о The physical and mathematical models,which are used for calculating functions (2) and (5) are discussed in the report. №• possibility of approximation of F-function by eC -correction method is evaluated.

• ATOHIC-EUXSSIOB SPBCTROMBTRY IH SOVIET UHIOIf НЛ-2 V.B.Belyanin, Yu.I.Korovln, V.V.Ifedler Moeoow, USSR

Some aspects of development of spectral analysis CSA) in SU. Statistic and specifity of papers and monographics in SA in SU. Some problems in organisation structure of SA in SU.

Mostly original papers and ideas in SA the last vears. AASA-ETA and related methods of atomisation.new methods, of compensation of interferences,scintillation methods. ESA -arcs and spares sourses.plasmatrons.lCP.combination of chemical and spectroscopy methods.

Laser SA -photoionisation,fluorescences,absorption and emission methods. Application of hollow cathods lamps. Methods of SA with time resolution - analysis of inclusions, analysis of minerals. Some iastrumentation development. Metrology and standard samples. LOOKING IN A BIRDS EYE VIEW AT SOME RECENT AND CURRENT DEVELOPMENTS IN OPTICAL AND X-RAY ATOMIC I h"~J SPECTROSCOPY P.WJ.M. Boumans Philips Research Laboratories P.O. Box 80.000, 5600 JA Eindhoven. The Netherlands

One of the purposes of research in Philips Research Laboratories is to develop "reservoirs of knowledge" filled with the results of fundamental and applied investigations and serving as sources and resources for the development departments of the Product Divisions of the Philips Concern. This entails that part of the research is directed toward the development of science in genera] and is conducted in much the same way as in academic institutions. Research in the field of analytical atomic spectroscopy in the past years is an example of such an academic approach. The results of this work have become known worldwide through publications and lectures, and have contributed to the development of spectroscopy in general. The present lecture will deal with some topics of universal interest, gleaned from recent and current work. An attempt to look in a birds eye view at recent and current work must inevitably be a compromise between a tutorial overview and a critical evaluation. As happens in both history and science, the significance of developments cannot be properly judged at the points that events unroll themselves. Digestion as well as fusion into a broader context are needed before develop­ ments can be assessed in the proper perspective. It is this philosophy which will form the background of this lecture. The author will look partly at his own work, partly at external work, and present some views based on today's insights. In the field of optical atomic spectrometry, topics such as high resolution emission spectroscopy and spectrometers, detection limits under ideal and real-life conditions, analysis and simulation of emission spectra, and, possibly, glow discharges as sources for atomic emission spectroscopy or atom reservoirs for atomic absorption spectroscopy will pass in review. At the point that this abstract is released it is still too early to specify the details of the lecture. Therefore further information is limited here to overall specifications of and references to topics which are likely to be explicitly эг implicitly covered in the lecture, but cannot yet be assumed to belong in the field of common knowledge. The recent explorations of high-resolution emission spectroscopy in connection with the inductively coupled plasma (ICP) may be featured by the following survey of topics covered. (1) Evaluation of the optical and characteristics of spectrometers, in particular eche»je spectrometers, in connection with noise sources [1—3]. (2) Detection limits for flat background ("pure water conditions'): trade-off between (i) the effect of spectral bandwidth on the background radiant flux, which dictates the shot noise component of the relative standard deviation of the background signal (RSDB), and (ii) the effect of spectral bandwidth on the signal-to-background ratio (SBR) Г2]. (3) The contribution of line wings to the background in line-rich spectra [4]. (4) The measurement of the physical widths and shapes of 350 prominent ICP lines of 65 elements [3]. (5) The transfer function which describes the modification of source SBRs by the spectroscopic equipment, in other words, the dependence of SBRs, and therefore detection limits, on the spectral bandwidth and the physical widths of the relevant spectral lines [5—7]. (6) The effect of spectral resolution on analytical performance, in particular the detection limit, in the case of line interference Г7—10]. This question has been quantified by defining the quantity "true detection limit" in such a way that a 'selectivity term" accounts for the reduction in selectivity caused by line interference [9, 10]. (7) The "true detection limit" as a straightforward and unambiguous criterion for line selection in trace analysis [7.10-12].

8 (S) The "true detection limit" as a basis for discussing the benefits of using (i) high resolution spectroscopy. (ii> spectrometers which permit accurate wavelength access ("direct peaking") without requiring curving fitting and peak find routines, and (Hi) chemomethc approaches such as Kalman filters [7.I3J. (9) The measurement of spectra of rare earth elements (REE) at high resolution, the conversion of the spectral data into (pseudo) physically resolved form, and the design of procedures for the application of the stored data to the accurate simulation of effective spectra of REEs for "any" spectral bandwidth [14.15]. This approach has finally resulted in a user- friendly, compiled simulation program on diskette for operation on personal computers, which is featured as an example of possible future electronic publications [16].

In the field of X-ray spectrometry, the bird's eye view will focus on some specific develop­ ments in the following areas: (*) Multilayer analysis using the angular dependence оГХ-гау fluorescence intensities [17]. (2) The application of bent crystals in X-ray spectrometers. (3) X-ray multilayered optics. (4) Wafer analysis. (5) Software developments and automation. (6) Total reflection X-ray fluorescence spectrometry (TXFS) [18].

References 1. P.W.J.M. Boumans and J.J.A.M. Vrakking, Specirochim.Acta 39B, 1239 (19S4). 2. P.W.J.M. Boumans and J.J.A.M. Vrakking. Specirochim.Acta 39B, 1261 (1984). 3. P.W.J.M. Boumans and J.J.A.M, Vrakking, Spectrochim.Acta 41B, 123S (1986). 4. P.W.J.M. Boumans and J.J.A.M. Vrakking, Specirochim.Acta 39B, 1291 (1984). 5. P.WJ.M. Boumans and J.J.A.M. Vrakking, Spearochim.Acta 40B, 1437 (1985). 6. P.WJ.M. Boumans and J.J.A.M, Vrakking, Spectrochim.Acta 42B. 553 (1987). 7. P.W.J.M. Boumans. Specirochim.Acta 44B, 1325 (1989). 8. P.W.J.M. Boumans and J.J.A.M. Vrakking, Spectrochim.Acta 40B. 1085 (1985). 9. P.W.J.M. Boumans and J.J.A.M. Vrakking. Spectrochim.Acta 40B. 1107 (1985). 10. P.W.J.M. Bourn-ins and J.J.A.M. Vrakking, Spectrochim.Acta 42B. 819 (1987). 11. P.W.J.M. Boumans and J.J.A.M. Vrakking, Speclrockim.AcIa 43B, 69 (1988). 12. P.W.J.M. Boumans, J.A. Tielrooy. and F.J.M.J. Maessen, Spectrochim.Acta 43B, 173 (1988). 13. E.H. van Veen and M.T.C. de Loos-Vollebrcgt, 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria. January, 8—14, 1989, Abstract Pl-32, Spectrochim.Acm В (in press). 14. P.W.J.M. Boumans, J.J.A.M. Vrakking, and A.H.M. Heijms, Spectrochim.Acta 43B, 1365 (1988). 15. P.W.J.M. Boumans, He ZhiZhuang. J.J.A.M. Vrakking, J.A. Tielrooy, and F.J.M.J. Maessen, Spectrochim.Acta 44B, 31 (1989). 16. P.WJ.M. Boumans, "The dissemination of the results of scientific research in the era of electronic media", in: "Future Trends in Spectroscopy, eds Paul Boumans, Sidney Kettle, Walter Slavin. and Jeffrey Steinfeld, Specirochim.Acta 44, Golden Jubilee Supplement (1989). 17. D.K.G. de P'.er, X.Ray Spectrom. 18,119 (1989). 18. Total Reflection X-Ray Fluorescence Spectrometry, Proceedings of the Second Workshop on TXRF, Dortmund, F.R.G.. edited by P.W.J.M. Boumans and R. Klockenkamper, Specirochim.Acta 44B, No. 5, 433-549 (1989).

sST- ONE- AND TWO-STEP PROCEDURES IN ATOMIC EMISSION

SPECTROMETRY FOR TRACE ANALYSIS

K. Dittrich Karl - Marx - University Leipzig Section of Chemistry Leipzig, DDR - 7010 German Democratic Republic

Atomic emission spectrometric procedures have a large potential for trace analysis. The power of detection depends on the sample sample introduction technique and on the principle usea for atomisation and excitation. Plasmas mostly used for analysis of solutions are the - inductively coupled plasma ICP - AES - microwave induced plasma MIP - AES - glow discharge plasmas GD - AES particularly a special type of the hollow cathode discharge : the furna"ce ato­ mic nonthermal excitation spectrometry - FANES The sample introduction is very important for trace analysis in mic- rosamples, because the amount analysed is limited.

Direct introduction of solution is possible in ICP - AES by nebulisa- tion, but this technique is low efficient and large sample volumes are needed. In MIP - AES this technique can not be used, because the plasi is very sensitive to a liquid - gas aerosol. Introduction of liquid - gas aerosols into the FANES is impossible, because this technique is WOJ king only at low pressure.

The electrothermal evaporation is highly efficient for sample intro­ duction. For this purpose microvolumes can and must be used. The FANES is a one-step procedure with direct dosing of microvolumes and following electrothermal drying, pyrolysis, and atomisation. There is in ICP - AES such a possibility too, but normally two-step procedures are used in ICP - AES and MIP - AES. This means a electrothermal vapori­ ser ie combined with the ICP or MIP. Different vaporisers and different

10 materials, as carbon and tungsten, can be used. The vaporised material must be transferd into the ICP or MIP, where the complete atomisation and excitation is carried out.

the one-step procedure FANES and the two-step procedures ETV-ICP-AES and ETV-MIP-AES will be compared, particularly for their sensitivity in the determination of different elements. Electrothermal vaporisers can be used also for efficient trapping of some gaseous samples, e.g. hydrides.

Such procedures allow sample enrichment and in special case of hydri­ de technique the efficient sample introduction of large sample volumes. As a consequence of this one- and two-step procedures can be applied by using the mentioned different plasmas. Finally, solid samples can be analysed too. The combination of laser ablation with the ICP-AES or FANES will be discussed. This combination is also a two-step procedure.

II ADVAHCES 1И TRACE ELEMENTAL SPECIATIOH IU EKVIROllMESTAb SAMPLES USIW3 COOTLED I CHROHATOORAPHY-ATCMC SPBCTHMKTRY Lee Ebdon, Simon Branch, Mike Foulkea Plymouth Analytical Chemistry Research Unit, Department of Environmental Soienoes. Polytechnic South West, Drake Circus, Plymouth FLA BAA, U.K. In environmental studies great advances In reoent years have heen made in monitoring trace element pollution and deficiency using the various techniques of analytical atomic spectrometry. It is now acc­ epted that total elemental content only provides partial information and. that the form of the element Is vital when considering questions such as toxicity, mobility and availability. Henoe in recent years there has seen considerable Interest In the quantification of trace metal levels, so called trace metal specfatlon. One of the most pro­ fitable approaches to this problem la to couple the separators' power of chromatography with on-line detection by the sensitive and selec­ tive techniques of atomic spectrometry. Instrumentation for several sueh coupling have been developed in the authors' laboratories and will be described, as will application of GC-AAS, GC-RTP-ABS, HPLC- AAS and HPLC-ICP-HS to a variety of environmental samples. In recent years there has been considerable interest in organo- lead speoles in the environment both as derived from gasoline and from natural processes. Two approaches to monitoring these speoles will be dessrlbed. The first comprises directly coupled gas chroma- tography-atomic absorption spectrometry (GC-AAS). A glass-lined heat­ ed transfer tube connects a oonveational ОС to a glass-lined "T* piece which introduces a small flow of hydrogen. A flame is ignited which atomises the lead for introduction into a heated ceramic tube held in the optical path of an AA instrument. The second approach uses a commercially available GC-microwave induced plasma-atonic emission spectrometry (HIF-ABS) system. The effluent from a capillary column it led via a silica tube to a microwave plasma la a modified

Щ)10 cavity wtoloh is viewed using a computer controlled diode ar­ ray speotrometer. High performance liquid chromatography (НИЛ? la obviously the method of choice for involatile or thermally unstable oompounds.Two HPLC coupled approaches «ill be described, HFLC-AAS and HPLC-induc- tively coupled plasma mass spectrometry (ICF-MS). Both these coup­ lings will be described using an ion-exchange chromatographic sepa­ ration for the speoiatlon of tin in water, sediment and shell-fish. In particular the environmental •ignifioance of monitoring trlbutyl- tin at the parts par trillion level will be demonstrated. The sensitivity, versatility and multi-element capability of ICF- U

,•=» MS are making it one of the techniques growing most rapidly in popu­ larity. It is well suited to coupling with HP1C and a sensitive coup­ ling using a miniaturised Ebdon nebuliser and spray chamber will be described. There is considerable Interest in the forms of arsenic in the environment and in food. One form of arsenic found In food (ar- senobetalne} Is virtually non-toxic. It appears to be the predominant form in fish and present in other animals fed upon fish meal. The results of a dietary study to see if the different forms of arsenic in soils, vegetables, fruits, fish and other foods cause concern when parts of whole diets, on cooking, or digestion, will be described. The use of nitrogen in the plasma to overcome ArCl+ interferences on As* determinations by ICP-MS will be described. In conclusion an attempt will be made to identify the future pos­ sibilities for coupled chromatography-atomic spectrometry and its role in environmental monitoring.

13 NOVEL SOURCES AND DETECTION TECHNIQUES FOR ANALYTICAL | ATOMIC SPECTROMETRY. I НД-6

G. M. Hieftje Indiana University Department ol Chemistry Bloomington, Indana 47405

As the decade of the 1990's dawns, К is appropriate to assess the current status of analytical atomic ipectromatry and to question what, if any, dramatic improvements in instrumentation, technique, and technology might remain. As atom sources, the carbon furnace, the Inductively coupled plasma, the high-voltage spark, and the glow-discharge lamp have proven to be excellent. Similarly, conventional direct-reading spectrometers, slew-scan systems, and, most recently, mass spectrometers have afforded convenience, low limits of detection, and minimal spectral interferences.

Yet, these sources and detection techniques are far from ideal and suffer a number of shortcomings which might be overcome either through evolutionary developments of existing systems or through introduction of entirely new ones. In this presentation, a number of new sources and detection techniques under investigation in our laboratory will be described and compared not only with existing systems but also with an ideal standard for atomic spectrometric analysis.

Among the sources to be considered are a new microwave plasma torch which requires no discharge tube, produces an annular (donut-shaped) plasma and can accept chromatographic effluents or nebulized samples with equal ease. Other sources which will be described are tandem In nature; that Is. they consist of two components. The first such component is optimized for atomlzation of the sample of interest, while the second source Is tailored for excitation or ionization of those atoms. Examples of such combinations Include laser ablation coupled with a microwave-induced plasma (MIP), a glow-discharge lamp combined with a low-pressure MIP, and an ЮР-MIP combination. Novel detection techniques that will be compared and assessed Include those which utilize linear photodtodo arrays, two-dimensional array systems, and mass-spectrometric approaches. Arguments will be presented why such detection approaches very likely will prove superior to classical techniques over the next five-year period. PLASMA SOURCE MASS SPECTROMETRY FOR ELEMENTAL

ANALYSIS

GaryHorlick DepmmeitofCherai5By,UDivroityofAlbata,Edinoiiuiii,AIbott,C«n>da,T602G2

In the list

The use of the glow discharge as a source in mass spectrometry is by no means new and applications predate those ofthelCP by several decades. More recently (during the 197

Critical to the development of GO-MS as a general technique for elemental analysis is UiewicteavaiUb^ty of appropriate totnuneniaaon. Recently a quadrupole bated GO-MS instrumenthas become cornmercialJy available. In addition, it is possible to construct GI>

II sources thai can be interfaced to the same mass spectrometers that are currently used for ICP-MS. In order to carry out a direct comparison of GD-MS and ICP-MS we have developed just such a GD source. It can be bolted onto the interface system of a SCIEX/Perkin Elmer ELAN ICP-MS. Details of the construction of this source and interfacing considerations wilt be presented.

An important first study has been an assessment of the spectral characteristics and complexity of GD mass spectra. As mentioned above, one commercial system uses a high resolution mass spectrometer (a sector instrument) and one (в very recent instrument) a quadrupole mass spectrometer. If GD mass spectra are too complex (i.e. numerous molecular species and clusters) then the analytical effectiveness of GD device quadrupole mass spectrometry instrumentation would be in question. We have measured the GD mass spectra for several samples and will show direct comparisons to ICP mass spectra of the same samples. In addition the basic background spectra for the two techniques will be intercompared. In general» while the nature of the observed species can differ considerably, the overall complexity is comparable between the two sources. Included in this comparison are ICP and GD mass spectra for dry plasmas and mass spectra for identical solid samples introduced into the ICP and the GD using direct sample insertion systems (DSIs). In conclusion, the decade of die 80"s has seen mass spectrometry burst upon the field of elemental analysis and atomic spectrometry primarily through the technique of ICP-MS. In the decade of the 90's a wider range of sources will be adapted, refined and developed for elemental mass spectrometry, the GD device being prominent among the many alternatives.

К HIOH PERFORMANCE SAMPLE DECOMPOSITION METHODS FOR TRACE j ELEMENT ANALYSIS ] НДГ-8

G. Knapp Department for Analytical chemistry, Micro- and ftadiochemistry, Graz University of Technology, Graz, Austria

The requirement for special analytical methods at trace levels becomes increasingly demanding as the elemental content decreases. This is true for all steps of the analysis and also for the decomposition of the sample. Of the numerous methods that have been described in the literature, only a few meet the requirements of modern trace analysis. Three powerful methods will be dieussed in this lecture: - sample decomposion in closed quart* vessels with the High Pressure Asher ж (HPA); - sample decomposition in open and closed vessels by use of micro­ wave oven; - sample decomposition at low temperature by a high-frequency induced oxygen plasma using the Cool Plasma Asher " *CPA 4). The methods will be compared and specific application will be shown.

2.38K.413 17 GRAFhlTb FURNACi. A'CCblC ABSO.iPTIOK аРгС'ИЮЗССРУ (Gl'AAS) РШ-9 | Hi IbVjSS'HGA'i'IOHS 01 RjiACi'lVPH OF SOLIDS

B.V. L'vov Polytocimlcal Institute, Leningrad, US."R

'Ihc graphite furnace technique with the programmable beating and with the possibility of "in situ" determination of metal vapor con­ centration during sample atonization presents the ideal method of thermal analysis. For JO years of Gl'AAS application in analytical chemistry, a lot of experimental data has been accumulated that helped to understand many features of the reactions with, the parti­ cipation of solid substances. In this paper, the mechanisms and the fundamental characteristics of the next typical reactions will be discussed: 'Hiermal dissociation of salts: nitrates, carbonates, etc. 'Ehormnl dissociation of oxides [l]. Reduction of oxides by carbon [2]. On the basis of the theoretical and experimental studies and the literature data, we could show that all these reactions proceed through the gasification of solid reagents irrespective of the vola­ tility of the reaction products, Biis guarantees a high rate of these solid-phase reactions, Theraedynuaical calculations of ap­ pearance temperatures and activation energies for these reactions are in good agreement with the experimental results. Папу of the "mysterious" effects observed in Gl'AAS have been in­ terpreted on this base quantitatively or qualitatively, without using any other theoretical speculations, e.g., the adsorption/ /desorption theory [з]- Besides, the new results ailuiv to recon­ sider some of the traditional ideas on the reactivity of solids accepted in high-temperature chemistry, catalysis and pyrometallurgy.

References

1. L'vov B.V., Fernandez G.H.A.//Zh.Analit. Khim. 1984.V01.39.P.221. 2. L'vov B.V.//Spectrochim.Acta. 1989.Vcl.44B.Nos.il/lS. J. Holcombe J.A., Rayson G.D.//Prog.4nal.At.Speotrosc. 198>. Vol.6. F.225.

II LASER ENHABCED IONIZATION AS A NOVEL I _.„ .„ FLW-10 FHOTON DETECTOR I 1 BW. Smith, P.B.Farnsworth, N.Omenetto Joint Research Centre, environment Institute lepra (Varese), Italy We have evaluated, both theoretically and experimentally, the use of laser enhanced or pnoto-lonlzatlon as a detector of photons. Of particular Interest are the concepts of quantum efflolency and Ion yield as figures of merit for such a detector. Our system consists of an atmospheric pressure oxygen-argon-acetylene flame containing magnesium atonic vapour. One dye laser ( л.р' excites the atoms from the ground state into the 3s3p- P° state, and another laser (Л2), in temporal and spatial coincidence with the first, brings the ex­ cited atoms into the 3s5d- Dg state, from which collisional ionizat­ ion occurs. The experimental set-up allows the simultaneous monitor­ ing of the absorption of <Ц, the resonanoe fluoreaoence and the ion- lzation cignal . The total loss rates out of the P° and Dg levels are calculated from the waveform obtained by time-resolving, with a fast response mleroehannel plate photomultlplier, the resonance fluo­ rescence signal with and without the presence of the second laser. By integrating this signal over the duration of the laser pulse, the fluorescence decrease (dip) Is found to be 83.5$. Naturally, J\,.| need not neoessarily be the first laser but might be provided by some process Induced by It which happens to result in radiation at the magnesium ground state transition. For instance, we have used this Ionization detector to record the spontaneous Rsman spectrum of pure carbon tetrachloride. In this case the first laser is incident upon the CClj and is scanned in wavelength such that the Raman shifted radiation will fall at the ground state magnesium tran­ sition. This light is transferred Into the detector flame, which also contains the seoond laser beam, and is detected by the resulting ion­ ization signal. Based upon these results several conclusions oan be drawn as to now one can approach a unity quantum efficiency for the ionization detector and, possibly, a unity ionization yield, as well.

It RECENT DEVELOPMENTS IB X-RAY FLUORESCENCE SPECTROMETRY РЫМ1 D.F. Sermin Applied Research Laboratories 5.A, Switzerland In recent years developments in X-Ray Fluorescence Spectrometry have been mainly devoted to t - Improvements In instrumental performance - Developments in more sophisticated data treatment. Improvements In instrumental precision This has been devoted to improving wavelength resolution, detection limits» snort term precision, long term stability and the regular reproducibility of the goniometer. The introduction of pseudo crystals (multilayer) for use in the ultra long wavelength range (elements below fluorine in the periodic table) and the development of surface treatment procedures for standard crystals has resulted in improved sensitivity and resolution throughout the range from boron to uranium. Long tern stability has been dramatically improved with the introduction of a sophisticated temperature control, which includes an individual control for each monochromator. A newly designed goniometer utilising moire fringe optically controlled angle positioning has eliminated wear and tear and baeklash, and has an angle reproducibility of better than 0.002* 26, together with a slewing speed greater than 4000° 29/minute. Improved data treatment With suoh a well understood technique as X-Ray Fluorescence Spectrometry and the availability of powerful computers at economic prices make it possible to design software in such a manner, that the instrument operator, independent of his knowledge, will have at his fingertips the full range of XRF techniques. the author will show how a modern 32 bit computer can interact with the operator to simplify the following analytical procedures : - The investigation of line overlap and its correction - The use of a fundamental parameter program to make matrix corrections - A rapid semi-quantitative program for sample classification - Apply an automatic correction for sample dilution, and the correction for loss on ignition (without prior knowledge) when making pearl samples by fusion. The techniques are of course known to the experts in this field and are being used to a greater or lesser extent* With this newly developed software, however, such techniques can be routinely used even by beginners* ATOMIC-ABSORPTION SPECTROSCOPY COMPARABLE STADY ON THE POSSIBILITIES OF THE FLAME- AND ET-AAS IN THE ANALYSES OFHIGH PURITY SUBSTANCES Г~ AA3-1 S.ARPADJAN, I.KARADJOVA, L.JORDANOVA UNIVERSITY OF SOFIA, INSTITUTE FOR HIGH PURITY SUBSTANCES, 1125 SOFIA, BULGARIA

THE ATOMIZATION BEHAVIOUR OF THE CHELATE COMPLEXES OF CD, Си, CO* FE, WN, PB, Nl WITH ЛРВС IN UNCOATED GRAPHITE TUBES. W-IMPREG- NATED TUBES AND L'VOV PLATFORM WAS INVESTIGATED. NO SIGNIFICANT DIFFERENCE WAS OBSERVED IN THE ATOMISATION OF THE DITHIOCARBAMATE COMPLEXES OFTHESE ELEMENTS IF И1ВК, O-XYLENE OR BUTYLACETATE MERE USED AS ORGANIC SOLVENTS.

A MODIFIER EFFECT OF THE ORGANIC CHELATE FORMATION REAGENT A APDC NAS OBSERVED WHEN THE ATOMISATION WAS CARRIED OUT FROM UN- COATED GRAPHITE TUBES STABILIZATION EFFECTS CAN NOT BE ACHIEVED IN THE PRE-ATOMIZATlON STEP IF TUNGSTEN-IMPREGNATED TUBES ARE USED.

DATA COMPARING THE POSSIBILITIES OF THE DIRECT ET-AAS, EX­ TRACTION FLAME AAS AND EXTRACTION ET-AAS FOR ANALYSES OF HIGH PU­ RITY SUBSTANCES ARE PRESENTED. THE LIMIT OF DETECTION, THE REPRO­ DUCIBILITY, THE REPEATABILITY AND THE ANALYSIS TIME OF THE THREE ATOMIC ABSORPTION TECHNIQUES ARE DISCUSSED.

» ATOMIC-ABSORPTIOff SPBCTROPHOTOilETRBS PITTED WITH i «ШОЗтВМХИЬ ATOMIZES DBSIGH AHD АРРЫСАТ10Н I ллз-- Xu.B.Atnashev Ural Electromechanical Plant, Sverdlovsk, USSR Tungsten-ooil atomiser (TCA) application in atomic-absorption spectrometry permitted to design devices «1th small size and «eight, greater efficiency and higher automatization degree. TCA low weight and impulse feeding from a condenser battery ensured atomizer high heating rate (3 z 1Cr K/aee) resulting in absorption peak duration reduction (up to 1-50 msec). Optical and electronic eguipment for measuring peak height and area, capable of identifying lntensivity drift of light sources and non-selective absorption by means of deuterium corrector «ere designed. Autosampler based on new operation principle securing rapid sampling (1-2 sec) without application of microdozator having good repeatability

(Sr«0.02) was worked out [1] . Coil automatic temperature control utilization by way of installing feedback between absorption measuring units and atomizer power source made it possible to enlarge calibration linearity range (up to 3-5 orders of magnitude). Optimal coil size and design «ere selected, atomizing devices with ene and several colls were developed allowing to increase the method efficiency up to 150-200 measurements per hour. Technical requirements for main units mobile atomic-absorption speotrophotometres fitted with TCA designed for running in field conditions were analysed. The device having little dimensions and low weight, less protective gas and energy consumption was designed. Atomie-absorption spaetrophotometre fitted with TCA and graphite furnaces analytioel and consumer characteristic» (taking into acoount TCA features) comparisons were carried out. Method application sphere i.e. industry, agriculture, environmental control, geology, health care were discussed[2] . References

1. Huzgln V.M., Atnashev Yu.B., Korepanov V.E., Pupfshev A.A.// Talanta. 1987.Vol.34. P.197. 2. Atnashev Yu.B.// Zavodskay* Laboratoriya. 1989.Vol.55. P.37.

» SAMPLE INTRODUCTION AND ATOMIZATIQN OF VOLATILE Г~ 1 AA3-3 ORGANQ-METALLIC COMPOUNDS IN FAAS ' '

Gy.BAGDI, J.LAKATD5 and I.LAKATOS Research Laboratory for Mining Chemistry of HAS, Miskolc-Egyetemveros, Hungary

The complexity of the sample introduction and atomization pro­ cess in FAAS still demands further investigations for elucidation of the basic phenomena. The misunderstanding of the experimental findings in analysis of lead in benzine may clearly prove the re­ ality of the that statement [l,2]. The analytical facts that the tetramethyl-lead and tetraethyl-lead present in volatile solvents give different analytical signals and in general the absorbance f;• the mentioned organo-metallic compounds is higher by orders of mag­

nitude than those for inorganic lead components (e.g. Pb(ND,)2> can not be explained simply by the higher volatility or better a ioniza­ tion efficiency of these compounds [2]. The detailed study of the sample introduction has definitely revealed that special circum­ stances rule the process when volatile organo-metallic compounds present in similarly volatile solvents are analysed by FAAS. In contrast to the conventional aerosol-type sample introduction, the absolute amount of the analyte getting into the flame (F ) is in­ dependent of the nebulization efficiency. It was found that F is primary determined by the volatility of the solvents at low uptake rate, while at high uptake rates the distillation process taking place in the nebulization chamber in the deoesive factor. Thus the vapour is enriched in the more volatile component which can be both the analyte or the solvent. As a result the relative amount of the volatile compounds is always higher than the actual corresponding solvent aerosol current. An additional feature of the process is that the sample introduction is basically of vapour form. Conse­ quently, the anBlyte show uniform distribution in the flame and significant aerosol separation could be observed when PbCND-,), and volatile metallo-arganic compounds are simultaneously introduced into the analytical light sources.

Referenoea 1. Dagnall R.M., West T.S.//Talanta. 1964. Vol.11. P.1553-

2. KaflhlKi H.( Yamasoe s.t Oshlma 3.//Anal.Chlm.Acta. 1971. Vol.53. P.95. CALIBRATION CHARACTERISTIC OOHRBCTIOH TAKIHG IH ACCOUHT ИОН-SSLEOTIVE ABSORPTION S.V.Baranov, I.A.Zemskova Scientific and Technical Complex "Soyuztsvetmetavtomatika", Koscow, UISoR For the background correction, different methods are used in atomic sbGorption spectrometry. A deuterium lamp system, the ueeman effect, and the method based on broadening the resonan­ ce line are used, ine last method was proposed by the authors in 1978 [1]. It consists of measurements of absorption at two different values of the atomic absorption factor and is realized by broadening the resonance anelyte emission line of a spectral lamp while feeding it with two pulses of different amplitude. In epite of obvious advantages, the method has a disadvantage caused the dual character of the analytical curve. In the area of large contents, the analytical curve is declined towards the axis of concentration, which causes an ambiguity of interpreta­ tion of an analytical signal because two values of concentration correspond one value of absorption. In the report the results of studies of calibration characteristics are given which have been obtained for 11 elements analysed in flame. It has been shown that the inflection degree of an analytical curve depends on the ratio of the levels of the lamp background emission at two values of resonance line bandwidth (narrow and wide). We have come to a conclusion that the level of background amis - sion in the second operation mode of a spectral lamp should be from 30 to 50 % of the resonance line emission. A new algorithm for calculation of concentrations has bean suggested which ta­ kes into consideration the intensity of the lamp background emission for two values of the line bandwidth. The calibration characteristics obtained according to the algorithm have no roll-overs at large concentrations. 'She method of analytical curve correction has been realized in a 3pektr-5 atomic-absor­ ption spectrometer. Reference 1. Buanov S.V., Zemskova I.A., Satarina G.I. USSR Author's Certificate Но. 77144Т.

25 НЕ* СЛШПЛТННГ МЕТКИ) Ш АТОИ1С ABSORPTIOB SPECTROSCOPY ЛАЗ-5 V.M.Belov, V.A.SuUianov, L.V.Hajorova, Ph.G.Unger Tomsk State University Tomsk, USSR

In atomic absorption spectroscopy (AAS) the connection between mea­ surable missing of flams (S) and concentration of determinate element (C) with oaloulation of prabable errors off the law of Lambert-Ber has the singi

0-1. In (1*) «-» I. B* (1-Й» "kc for 0* Be 1, (1)

where В is portion of diffused light, К is constant. Evidently, that В and К are parameters (1). lbs expression (1) is at the same time the equation for inderected definition of concentrations in «AS and gra­ duated dependence. There is a case of graduated dependence correspondence (•)). It is

natural to propose, that the values T± and 0^ for it iTN are measured with absolute inaccuracies S, and В correspondent^. This vague for­ mulation of the problem for parameters d) definition in general as­ pect is given in [1]. Then, following [1]I

ko Tj * B» (14), - ( t +B» (1_B), ""«tej «• for If l7H, (2) where numbers SJ, T*, (JJ, 0^ oan be measured aai

*[ m Tj-B,, I* m T^tf,,» CJ . C^Bgl Oj m Bj+Bg for it М.Сз)

Plurality of determinate parameters (Kt£), answering the system of

inequalities (2), let ue mark though Л1. Let plurality of indetermi­ nacy Л equal {(K,B)/0a* Be" 1, К» О, (К.ВХ-Л.,} . Shan real value of pa

rameters (K*aB*} of calibrate dependence (1) belongs to plurality of indeterminacy Л , the work with them is analysed in [1] too,

Beferenoe 1. Belov Т.Н., Sukhanov V.A., Unger Ph.G. Reprint И 59. Institute of Oil Chemistry. Tomsk, 1989. 34 p.

И AUTOMATIC GENERATION AND INTRODUCTION OP VOLATILE | " PHASES BY FIOW-INJECTION-ANALYSIS IN ATOMIC ' AA3~6 SPECTROSCOPY

J.R.Castillo, J.M.Mir Department of Analytical Chemistry, University of Zaragozn,Spain Gas phaee is not widely used in spectroscopic instruments. On one hand, technological questions make it difficult to acquire and couple the appropriate devices for gas generation, on the other hand the vo­ latility of many elements and their compounds are unknown. Formation of chelate complexes from transition metals пав been proved as an excellent method to obtain gas phases for these metals to be determined by Atomic Spectroscopy (AS) (1-4). However, synthesis of the chelate complex previous to the Atomic Spectrometry determination, is a limiting faotor to the analytical procedure. The use of PIA, permits the chelate oomplex to be synthesized simply and quickly. 1 mL of analyte injected in the system containing the suitable buffer and chelate reagent, is conducted through 4 m. reaotor.In these conditions, the chelate complex Is synthesized In 30 sec. Given the (insolubility of these compounds in the aqueous phase, the chelate which Is formed may be picked up by a flltrlng system. After 30 seconds this system has been heated up electrically up to the sublimation temperature of the chelate. Combination of both devices let the ohelates to be synthesized and volatilised and the steam generated is oonducted to the atomizer using Nitrogen as carrier gas. The procedure using the PIA technique here described has been de­ veloped for the acetylaoetonate synthesis. It has been applied to the determination of Cobalt in bronzes. The method is being studied now for other chelate agents for Co, Cu, Cr, Al, Fe, Hi, Zn and Mn. References 1. Castillo J.H., Kir J.H., Bendlcho С, Laborda p. // Free. Z. Anal. Cham. 19B8. вв. ЗЭ2. S. 37-40. 2. Wolf W.R. // Anal. Спи». 1976. Vol. 48. P. 1713-1717. 3. Black V., Browner R. // Anal. Chem. 1981. Vol. 53. P. 249-253. 4. Black U.S., Thomas M.B., Browner R.P. // Anal. Chem. 1981.Vol.53. P. 2224-2253.

This work was sponsored by the DGICYT (project PB88-38&) of the Spanish Education and Sciences Department and by the university of Zaragoza (project IH-5).

П ATOMIC ABSORPTION SPECTROMETRY WITH PULSED ATOM1ZATION ЛЛЭ-7 BY A JET-ASSISTED CATHODIC SPUTTERING ATOMIZER

CX. Chakraoarti1, K.L. Headrick1. j.C. Hutlon', P.C. Bends' and M.H. Back2 1. Centre for Analytical Chemistry, Carleton University. Ottawa, Ontario, CANADA 2. Department of Chemistry, University of Ottawa, Ottawa, Ontario, CANADA

A laboratory-built cathodic sputtering atomizer has been developed for the analysis of solution residues. Two important characteristics of this atomizer are: 1) the use of six argon jets directed onto the cathode surface and 2) the independent control of the jet-gas flow rate and the atomizer gas pressure. The use of the argon jets minimizes the ledeposition of sputtered particles onto the cathode surface and thereby greatly enhances the number of ground-state neutral atoms that are transported into the analysis volume. Commercial atomizers constructed to use an argon gas flow for alomization. however, do not provide independent control of the argon gas flow rate and the atomizer gas pressure. The atomizer gas pressure in commercial atomizers increases with increasing argon gas flow rates. Independent control of these two parameters (as in the laboratory-built atomizer) allows the individual optimization of the experimental conditions for each element that is necessary for achieving the maximum possible sensitivity. The optimum conditions for the atomizer in which the aforementioned independent control is possible, to be henceforth called the new atomizer, occur at higher atomizer gas pressures and lower argon gas flow rates than were used in the atomizer, to be called the old atomizer, for which no independent control was possible. In comparing the results obtained using the new atomizer with those obtained using the old atomizer we have found a moderate improvement in the peak-height sensitivity and a substantial improvement in the peak-area sensitivity. The improvement in the peak-helghi sensitivity is due to the fact that it has become possible to use more vigorous sputtering condiiions ai the higher atomizer gas pressures. The improvement in the peak-area sensitivity is due to the combined effects of the improved sputtering conditions and an increased residence time for the atomized sample within the analysis volume because of the lower argon gas flow rate. The independent control also makes it possible to study the individual effects of the atomizer gas pressure and toe gas flow rate on: I) analyte atom transport through (he atomizer, 2) the atomization of the sample from the cathode surface and 3) the electrical discharge characteristics of the atomizer.

Results on characteristic mass, limit of detection and mechanism of atomization obtained with the new atomizer will be presented and compared with those of the old atomizer (1-4]. The important thing to note about the mechanism of aumuzation is mat the use of the new atomizer with its control on the rate of atomization combined with its faster detection system (0.1 ms time constant) has allowed us, for the first tune, to record data points on me rising part of the atomic absorption pulses of the elements, Al, Cr and Mg, which were not possible with the old atomizer, with its lack of control on the rale of atomization combined with its slower detection system (2 ms time constant). 1. C.L. Chakrabarti, K.L. Headrick, J.C. Hutton, B. Marchand and M.H. Back, Speclrochim. Acta, 44B. 385,1989. 2. C.L. Chakrabarti, K.L Headrick, J.C. Hutlon and M.H. Back, Proceedings of XXVI Colloquium Spectroscopicum Internationale, Sofia, Bulgaria, July 2-9,1989. Invited Paper, Vol. VI, pp. 10-20. 3. C.L. Cnakrabani, K.L. Headrick, P.C. BerteU and M.H. Back, J. Anal. At Spectrom., 2. 71.1. 1М.Ч8. 4. C.L. Chakrabarti, K.L. Headrick, J.C. Hutton, Z. Bicheng, P.C. Bertels and M.H. Rack, Anal. Chem. (in press, March 1990 issue). CONTINUOUS AAS TITRATION AS A METHOD TO FOLLOW THE AAS-8 FORMATION AND FLAME ATOMIZATION OF AMIN0-P0LYCAR80XYLIC ACIO COMPLEXES

12 2 S.L.Oavydova , 3.Posts , F.Hussein' 1) Institute of Petrochemical Synthesis, USSR Academy of Sciences, Leninsky pr. 29., USSR. 117071 Moscow V-71 2) Institute of Inorganic and Analytical ChemiBtry, Kossuth University, H-4010 Oebrecen 10, Hungary We elaborated a continuous AAS titration technique Гlj for systematic investigation of the effect of ligands to flame atomization. This method made possible the continuous changing of the ligand to metal ratio in the range of 0-10DD, and the registration nf the absorbance-chang.es by a recorder or a computer. WF applied this method to investigate the interaction between amino-polycarboxylic acids (EOTA, IMOA, MIKOA, HEDTA, NTA. DCTA, OTPA, DDPTA) and the metals of the first transition raw. The AAS titration curves obtained by the above systems can be di­ vided into characteristic sections. At low ligand/metal ratios (0-2) the process end the end point of the complex formation can be easily followed by the significant decrease of absorbance by the breaking point. The breaking points of the titration curve indi­ cated, that the composition of the complexes farmed in the solid aerosol for the majority of the ligands is 1:2 and in a few cases Ы. Vihen the ligands were applied in the form cf their alkali-notal salts, the abscrbance increased continuously from the breaking point till the 50-100 ligand/metal ratio because of physical des- integration effect of the ligand excess. When the excess was over 100-times, the absorbance and atomi- zation of metal complexe become independent of the ligand concent­ ration and remained constant. When we applied the ligand in the form of acid, the absorbance become constant at the value of breaking point. This finding can be explained by the atomizatlon independent from the ligand excess of the complex, caused by the low solubility of the ligand. Refer

I Posta 3., Lakatos J.//Spectrochim.Acta, 356, 1980.P. «01

» MECHANISM OF SELENIUM HYDRIDE ATOMIZATION IN QUARTZ TUBE MS-9 ATOMIZERS I ' J.Dedina Institute of Physiology, Czechoslovak Acadeny of Sciences, Praha 4, fepft

Traditionally, quartz atomizers are considered to break into two diverse kinds: externally heated cells and flame-in-tube atomizers. The mechanism of hydride atomization has been understood much better in flame-in-tube atomizers than in externally heated quartz cellБ [1]- The aln of the present work «as to elucidate the whole process of analyte transfer in heated quartz cells. A "hybrid" hydride atomiser able to work either as a flame-in-tube atomizer or as a heated flameless cell or in several combined modes was designed for this task. Following conclusions have been drawn from the experiments: (i) There is no principal difference between both quart2 tube atomizers - externally heated quartz cells are only oxygen deficient externally heated flane-in-tube atomizers. Hydride atomization takes place in a small cloud of hydrogen radicals located at the entrance to the heated portion of the cell. The decay of analyte free atoms takes place on the whole inner atomizer surface. (ii) The decay is enhanced with temperature. The enhancement is much more pronounced if the surface ie contaminated. (The contamination does not affect the atomlzation efficiency.) (iii) Typically, sensitivity is controlled by the rate of free atom decay. Consequently, an ideal hydride atomizer should be made either of an material inert to free analyte atoms or without surface, (iv) Decayed Se species are volatile; they can be completely reatorn1zed in an additional hydrogen radical cloud downstream in the atomizer. The additional cloud can be formed either by a separate inlet of oxygen to the heated atomizer portion or by a flame lit in the unbeated atomizer section. The decayed Se species cannot be atomized at all in heated atomizer without separate oxygen inlet.

Reference

1. J.Dedina: Frog. Anal. At. Spectroec, 11, 251 (1988).

«• OPTIMIZATION OF DRSTING CONDITIONS AMD ANALYTICAL ГТТ7ТГ APPLICATION OP ELECTROTHERMAL ATOMIZATIOM WITH I INTRODUCING OP SAMPLE DROPS ON THE PREHEATED SURFACE A.A.EmelJanov, V.I.darsukov Tambov Institute of Chemical Engineering, Tambov, USSR The advantages of sample introduction and deposition technigue on­ to a hot surface (furnace., cup, boat or platform) are «ell taiown.How­ ever conventional sample introduction systems that utilize a pneuma­ tic nebulizer decrease and limit the ability of such methods because of its little efficiency of aerosol transport system. These limita­ tions may be easily eliminated by use of conventional sample drops pipetting. Important parameters for optimization of this technigue are the temperature of the furnace in moment and during introduction of the drops ( aerosol deposition ) and time of drying for all decay series and for single drop as well.

She results of a study and optimization of drying conditions его represented. For this purpose the time - dependent measurements of eurfaoe tem­ perature just below the droplet were performed. It has been shown that the temperature falls immediately after the droplet deposits onto the hot surface then it does not remain constant rising only after the process of solvent evaporation ends. Ideally, as it is known,this cooling effect should not been.The peak height and area are depended on initial volume of droplet,and also on initial temperatu­ re and different from nature of solvents.

On bases of obtained heat - transfer single evaporation characte­ ristics or series droplets and in the result of the theoretical analyses of the phenomenon the connections were found to.estimate the time evaporation ( drying ) and temperature of drying. Results are presented for a number of elements in different sample oatrieoes. Sample including waters, surface - active and nature sift- etance have been «laminated and extension of the technigue to other samples will be discussed.

II ESTIMATION 01' THE SAMPLE EVAPORATION AREA bASEb Oil ЛЛЗ-11 STUDIES 0Г POLIDISPERSITY OP LHSf SAMPLE RESIDUE OiJ THE SURFACE 0? ELECTROTHERMAL ATOMIZER

A.A.Eineljanov, V.F.CrigorJev Tambov Institute of Chemical Engineering, Tambov, USSR

A detailed study of morphology and particle size distribution of the dry sample residue on graphite or metal surface used for electro­ thermal atomization is presented. The optical microscopy system has been used to monitor the analyte residue "in situ" on surface as function of analyte concentration and methods of drying. The first of them was trivial (manual drop pipetting); the second - the drop depo­ sition process took place with preliminary heating of the furnace ( up to stationary temperature ). Differences in morphology, size and parameters of distribution not only for methods of drying but also for the nature of substance surface have seen revealed. On the base of experimantal data it has been found that the distributions are of a single-modal nature. The effect is displayed also as shift in the maximal density of particles and as variation in the breadth of the distribution. For the trivial method the results indicated that with increase in concentration the shape of density distribution function remains prac­ tically constant. As It has been found the function of density to a high degree of approximation may be described by the three-parametric gamma-distribution Svenson-Avdeev's type, which for mass distribution of spherical particles, is as:

(b.+3) b, 1 J Pm( r ) « Вт exp (-b2r ) where b^, b-, b, are empirical parameters and В is found from norma­

lization f*fra(r)dr • MQ. This permitted us to receive relationship for estimation a surface area of polydispersed particles esserable of the dry residual:

( 1 )

where Г (X) is gamma function) MQ, p - mass and density of analyte. According to (1} the surface area has been estimated which in a first approximation was presented as an area of sample evaporation. Digital evaluation and other results will be discussed in the re­ port.

SI NEW METHOD OF DIFFERENTIAL ABSORPTION ANALYSIS BASED ON THE FABRI-PEROT PHOTOELASTIC INTERFEROMETER

A.A.Ganeyev, A.D.Timofeyev, Yu.I.Turkin Leningrad State University, Chemical Faculty, Leningrad, USSR Selective differential atomic absorption analysis is greatly im­ proved since creation Zeeman atomic-absorption spectroscopy and other methods in the nlddle of 1970'э. But some problems, as determination elements in drawling layers, are not decided.New method of differenti­ al absorption analysis based on the high stability Fabry-Perot photoe- lastic interferometer is allowed to decide some of these problems. This interferometer consists of crystal and amorphous plates of qu­ artz, pasted together. Dielectric mirrors are plotted on the surfaces of amorphous quartz. Elastic oscillations are exited on own frequency of quartz, that leads to the modulation of the interferometer appara­ tus function. Position of the apparatus function on the wave-length scale is determined by interferometer temperature T(. Changing of the

Tt-leads to displacement of the apparatus function.The value of T; is picked out (for the resonance emission line) from the condition of the equality of amplitude of the first garmonlc Al on the modulation fre­ quency to zero, when the concentration of the absorptive atoms N-0 . Appearance of the absorbanoe gives rise to signal Ai-N. The existence of signal is determinated by Lorentz displacement of the resonance ab­ sorption line. The magnitude Al is calculated as function of interferometer thick­ ness, absorption and emission line widths, modulation amplitude of in­ terferometer, which is determined by amplitude of elastic wave in amorphous quartz. The experimental studies were carried out for meroury, using cells with saturated vapour of mercury, experimental signal Al is determina­ ted as function of oiting parameters for some mercury isotopes and for natural mercury placed in electrodeless discharge lamp.This method was used also for determinating gold in electrothermlo atomisator. The application of the photoelastlc Fabry-Perot interferometer per­ mits with the standart atomic absorption spectrometer to rise selec­ tivity and reduce the limit detection of Cd, Cu, Ag, Zn, Pb and other elements. This method can be used also for isotopical and mole­ cular absorption analysis.

З.Зак.413 ss CONCENTRATION CURVES OF ELECTROTHERMAL ATOMIC ABSORPTION l 1 SPECTROMETRY |АЛЗ-1Э A.Kh,Oilniutdinov,T,M.Abdullina,S.F.Gopbaehov,V,L.Makarov Kazan State University,Kazan,USSR Electrothermal atonic absorption spectroscopy (ET AAS) in a general case includes the following four stages: atonization at a rate of S(t) atoms/s of a sample with the mass m of an analyte , transfer of the atomic vapour in the atomizer volume and the generation of a non stationary absorbing layer Kith the atomic concentration n(t); ir­ radiation of the layer with a line radiation of the same element gives the absorbance Aft) at the atomizer output, wich is transformed into the output electrical signal 041) in the spectrophotometer record­ ing system: atonizetion transfer absorbing recording n > S(t) > n(t) —> A(t) —> U(t) The objective of this work is a detailed analysis of the third neater of this sequence , i.e. the interrelation A»f(n) (concentration curve).In a general case this dependence is also complex:the absorbance value is determined not only by the number of absorbing atoms, but also by inhomoqeneity of their distribution in the atomizer volume , long­ itudinal nonisothermality of a graphite tube and also the spectral characteristics of the used analytical line. In this work the most general expression for the concentration cur­ ves of ET AAS is obtained,taking into account all the features.'esission line-width and its hyperfine structure, the shift of a Voigt profile of the absorption line relative to the emission line and also the gradi­ ents in the atomic and atomizer temperature distributions.The functions A»f(n) are plotted for 25 elements most frequently analysed by AAA as applied to STPF conditions.This required re-evaluation of the available data bank on the hypefine structure of the analytical lines . Such general consideration has allowed one to introduce and calculate the following informative parameters of the concentration curves: linearity region,low and high characteristic concentrations determining the ope­ ration range of the atomic absorbtion method,curvature and sensitivity. The changes of the concentration curves in the sequential introduc­ tion of the above speotral characteristics and their stability to possible variations of the determining parameters are considered . The dependence of absorbance on the degree of inhomogeneity of the atomic distribution and on the degree of longitudinal nonisothenality of the atomizer has been analysed.lt is shown that a typical longitudinal con­ centration and temperature inhomogeneities of graphite furnaces result in lowering the slope of the concentration curves by as much as lOji . However, the dependence of A on the inhonogeneity of the atonic distri­ bution over the cross section has been found much more significant. м SPECTRAL SHADOW FILMING - A NEW METHOD OF INVESTIGATION OF THE ELECTROTHERMAL ATOMIZATION PROCESSES ЛАЗ-14 A.Kh.Gilmutdinov, U.A.Zakharov.A.V.Voloshin Kazan State University,Kazan,USSR An analysis of recent numerous investigations shows that the elec­ trothermal atoiiization (ETA) from the graphite surface is a complex systen of rival processes simultaneously proceeding in the gaseous phase, on the surface and in the atomizer body . Therefore , a reliable interpretation of the electrothermal atomization processes is possible only by a multichannel test . For this purpose a number of alternative methods, including non-optic methods: mass-spectrometry, X-ray analysis, electron microscopy,etc.,is widely used. A new method of getting more information of the atomic absorption test is suggested,which is based on spectral shadow filming,having its specific merits. The main point of this method is to obtain an image of the atomizer internal space in the light of the analytical line of the element under study and to record the shadow picture caused by absorption vapour . An electrodeless discharge lamp is used as an irradiating light source,and a slitless monochromator is used to separate the required wavelength. Possibilities.The method allows one to register simultaneously: lHhe distribution of the atoms ( molecules ) of the analyte in the cross section of a graphite tube : 2)the dynamics of these distributions in tiie(with a resolution of~ O.Ols); 3)time dependence of the temperature of the atomizer wall and platform. Illustrations. The absorbance signal at atomization of lOng Al { Я - Зев.впт нгои the atomizer wall and visualize*1on of this process by spectral shadow filming are shown in Fig. (a) Incensing the intensity of atomizer wall emission allows one to judge about wall temperature variation. Al molecules distribution,registered at a maximum absorption at X - £55 nn when atomizer temperature is steady is shown in Fig.(b). Different emissions of the atomizer wall and platform , indicative of their temperature difference, is illustrated in Fig.(c).

(*) The variation in the formation of Al atoms' (a) and moleculee'Cb) absorption layer and the luminescence of the atomizer wall and platform (c). (c) (a.) Interpretation. It is obvious from the given data that the distribu­ tion or Ai atoms and molecules in the atomizer volume has the following characteristic features: atoms are distributed mainly in wall-proximate areas.while Al molecules have a marked localization in the axially- proximate parts of the tube. Similar investigations have been carried out on * number of other elements , having considerably different physical and chemical properties. The obtained enables data one to make eneral conclusions concerning the orocesses of electrothermal atomiza- fIon in graphite furnaces.

9- nTRTTni» ПГСФТЙН1ГГЯДФТПИ flff RRWBinTnPV ТЛТЛМТГМФС! UV - •, АЛЯ-15! лкпЛ.1ЛЛЯ< WTnmrrti«AAllVUbc ' пттпоVA4VB" -A/iwnVT.vixi ttWJJ* J.M«UU? J utTflHW Air?U imrairnA4WBJ. W шслвптгп^DaVIUllUпO

H.N. Gorlova, O.L. Skorskaya, A.L. Kmglyak NPO VILS, Hoscow, USSR Determination of refractory elements (titanium, zirconium, niobium, tungsten, molybdenum, vanadium) is quite difficult because of these elements tendency to form the thermal resistant compositions in the atomization zone.

Distribution of the elements and their compositions in gaseous and condensed flame phases are evaluated qualitatively and quantitatively by the modelling of the atomization process thermodynamics using the computer.

It was found that the formation of carbides in the condensed phase me the stage which defined the atomisatlon efficiency. To minimize the formation of condensed phase the influence of arrange of metals (aluminium, iron, oopper, nickel) on the atomization of the indicated elements ma studied.

It was found that addition of aluminium reduoed the definition limit of these elements. In case of titanium the level of atomization is increased and «hen defining zirconium and niobium the kinetic pro­ cesses of the atom entrance into the flame working zone are improved. The patterns determined are verified by the line absorption method based on the direct measurements.

Study of influence of the medium, from which the elements have been atomized (ЯС1, НТО,, HgSO,, HP) and the same medium with aluminium ad­ dition permitted choice of the sample dissolution method and atomi­ zation conditions ensuring the titanium definition starting from 0.5 mas. % contencs, zirconium definition - from 0.2 mas. %, nio­ bium and tungsten definition - from 0.5 mas. % and more than that in the materials produced by metallurgical processes.

И NEW XOX'DISPERSION TUNGSTEN SPIRAL ATOMIC FLUORESCENCE SPECTROMETER AAS-16 3.S. GrazhuLene, V.A. Whvoatikov, M.V. Sorokin, N'.I. Vykhrestenko, u.F. Norovyatnikov, A.S, Gonchakov Institute of Microelectronics Technology and High Purity Materials, USSR Academy of Sciences, Chernogolovka, USSR Atomic fluorescence analysis (AFA) exhibits greater sensitivity as compared with atomic absorption specially with the use of powerful excitation sources and efficient atomizers. However, the development of the method is retarded because of the lock of a sufficient number of commercially available equipmeni that is suited to AFA. The potential­ ities of AFA using the pulse spiral tungsten atomizer have been previously reported [l,2J. This work presents a new model of the nondispersion spectrometer based on a tungsten spiral atomizer (Fig}. The potentialities of the spectrometer have been studied on aqueous solutions of cadmium, copper, lead, indium, bismuth and other elements, The obtained detection limits were 10 —11-1 1 —15g . The mutual influence of the elements has been investigated. The spectrometer is compact, economical and may be used for determining traces of toxic elements in environmental objects and In wash waters in the technological microelectronics processes.

Tungsten atomizer with accessories for AFA 1-excitation source, 2—tungsten spiral, Э-optical filter, 4-photomultiplier

References 1. Arkhangelsky B.V., Gonchakov A.S., Grasshulene S.S.// J.AnalyLAtom.Spectrom. 1987, Vol.2.H.8»P#B29. 2, Gonchakov A.S., Arkhangelsky B.V., Grazhulene S.S.// High Purity Materials. 1988. N6. P. 153. (in Russian)

37 DEVELOP!.^:.'I, INVESTIGATION AHD POSSIilLIT'i OF ANALYTICAL ЛЛВ-17 USE OP ELECIHOIHBRMAL ATOMIZER " PROjiE IM FUKJACE " ll.V.tfrebennikov, V.I.Baraukov Tambov Institute of Chemical Engineering, Tambov, USSR

Modern industrial electrothermal atomizers have certain limita­ tions, to cope with some innovations are suggested-pulse furnace heat­ ing by discharge of condenser battery, furnaces with a cuasiisotherraal mode of operation, evaporation of sample analysed from a platform, ballast or probe.

We have investigated a possible use of electrothermal atomization technique in isotherm!с furnace with a metal probe heated by an independent source. Instrument parameters of an atomizer are revealed, such as affect of place and temperature of probe, furnace size, probe material and some others on the value of analytic signal when an amplitude method of registration is used. The speec' of probe heating was estimated by suggested thermotechnical model of heating.

Two ways of copper determination - evaporation of sample analysed from probe and from additional pulse heating probe ( at the same operational mode of furnace ) have shown that the additional pulse heating ( pulse energy 8,2 J ) after introduction of the probe into furnace increases the analytical signal amplitude by more than three ti­ mes. In this case characteristic mass of the copper is 1.7*10" *g.

The affect of probe matrix was tested with alkali and alkali-earth elements. It has been found that a limiting value of interferring substances, having influence on valid and reliable probe testing, tends to have a normal concentration of these elements in solution as compared to conventional atomization method.

The independent pulse heating of the probe in isothermic furnace results in a sharp decrease of time in probe vapour formation and increase analytical signal amplitude which leads to a certain limi­ tations in element detection at amplitude method of signal registration. Sample evaporation in a heated furnace of an atomiser results in a less affect of the matrix on the results of analysis.

98 SIMULATION OP THE PKOCESS OP SAMPLE AUTOHISATIOW FROIJ THE f ELECTROTHERMAL ATOMIZER SURFACE AT VARIABLE TEMPERATURES [ ЛЗ-18 V.F.Grigorj'ev, B.H.Ivanov Tambov Higher Military Aviation Engineering School Tambov Institute of Chemical Engineering, Tambov, U338 On the basis of literature data analysis on the processes going on at the stage of substance transition into the gaseous phase and these processes models it was found that the intensity of sample transition from the solid state to the gaseous state for the most known atomization mechanisms may be represented as 451 = a- m"- expietj. ot

Неге: m..„0- the sample mass) Cl, 6 , fl - some constants derived from the supposition forming the basis of the model. The investigations of the opportunities of such atomization pro­ cess presentation permit ed us to receive a number of relationships to describe the transition process of the sample from monopartic- les (1), quasimonolayers (2) and polydispersed particles ensemble /the dry residual/ (3) to the gaseous state»

(1) п «jfp = о{т!Г - H -")••£• fexptbU -fl} • елР (Ы) (2)

(3) dmt (и-До-па-|гД.е*р(ЦУ ) 1 + [ехР(61Ы]}& The Figure shows some typical changes in time of masse velocity of sample transition to the gaseous state for certain cases (1,2 and 3). dm

Ш 1 л 2 3 1 •

С 2 40 2 402 4t. The Caracter of Mass Velocity Changes of Sample Evaporation

For the case of monopartlcles evaporation the relationships we­ re found to express the constants Q, 6 , n included into the mo­ del by means of physicochemioal constants of the substance. Appli­ cability of the relationship» obtained for atomization process des­ cription was veryfied experimentally.

3f SAMPLE INTRODUCTION IN ATOMIC ABSORPTION SPSCTBOHETEH - PROBLEMS AND SOLUTIONS ААЗ-19

I.Havesov Institute of General end Inorganic Chemistry, Bulgarian Academy of Sciences, 1040 Sofia, Bulgaria

Greet investments have been made in the last twenty years to modernize the electronics of atomic absorption spectrometers (AAS), while the reet components of the spectrometers remained unchanged. That is why the sensitivity achieved with the modern flame AAS is only twice better than those achieved with the early equipment manufactured in 1962» Lately a new tendency appears - development, testing and serial production of new devices for sample introduction into the atomizer. The sample introduction is a reproducible transfer of a represen­ tative aliquot of the analysed sample to the atomizer. This process should be highly efficient and should provide minimal interference with the subsequent AAS determination» The sample introduction methods differ in flame, hydride and electrothermal atomic absorption techniques. They will be separately discussed. 1. Flame AAS i) continuous introduction, dissolution in suitable organic solvents ii) flow analysis - automated dilution, addition of reagents, separation, preconcentration iii) pulse introduction - dipping method, flow injection, flow analysis with controlled dispersion, analysis of suspentions 2. Hydride technique - increment delivery, flow and flow injection analysis. 3. Electrothermal AAS i) introduction of liquid samples - pipetting of liquids and suspentions onto plstform (under STPF conditions), into tungsten atomizer, probe atomization, as an aerosol by a conventional nebulizer, thermosprsy deposition, combination of chromatographic separation with ETAAS determination ii) introduction of solid samples - into specially designed graphite atomizer, probe atoaization, after laser ablation. UNDERSTANDING GRAPHITE FURNACE VAPORIZATION I MECHANISMS USING MONTE CARLO TECHNIQUES WITH I —. SUPERCOMPUTERS

J. A. Hokombe, O. A. Guell Department of Chemistry, University of Texas, Austin, Texas 78712 USA

It is important to develop a better understanding of the fundamental chemical and physical processes in electrothermal atotnization. Unfortunately, even if a working hypothesis has been deduced, developing an accurate model to verify the suggested mechanisms is extremely difficult. The difficulty is caused by the complexity of (a) the furnace geometry, (b) the thermal heating program and/or (c) the chemical reactions. Analytical solutions (e.g., solutions to differential equations) become, at best, flflly.reasonabl e approximations of the actual system. A more accurate model can be developed using Monte Carlo techniques, when the number of assumptions being made in the model can be kept to a minimum. The basic technique is stochastic and employs random numbers to represent the processes and probabilities of reaction in the system. It is very simple to include geometric deviations (i.e., not a simple "isothermal tube"), which mote accurately represent the real world situation during the impulse heating of the furnace. Examples will be presented with the presence of a platform within the tube and vaporization proceeding from the platform into a gaseous environment of a different temperature. The presence of the dosing hole, non-isothermal heating, analyte readsorption to the wall, gas phase chemical reactions and thermal expansion of the sheath gas arc just examples of the parameters that can be explicitly taken into account using this approach. As an example. Fig. 1 shows the distribution of particles for analyte vaporization from a platform within a tube mat is ramp heated. In general, Monte Carlo simulations involve incremental movement and decision making for several thousand individual particles over the course of the atomization process. The appropriate physical/chemical equations needed to describe diffusion, desorption, adsorption, etc. are employed over very small time increments. As a consequence, the position in the vapor or on the wall is known for each particle at every time interval. Thus, a series of "pictures" of the location of the particles in the vapor and on the surface of the graphite can be generated. Trdspennitsvisualt2auon of where the atoms are positioned as a function of time. Fig. 2 shows an example of a cross sectional view of the furnace showing the location of the analyte particles both in die vapor phase and adsorbed onto the wall of the tube, The potential impact of Monte Carlo simulations in GFAAS, as well as in other analytical techniques, appears very encouraging as a means of verifying fundamental processes as well as optimization of die technique for maximum signal and ngnal-to-nob».

41 Fiture 1

ОМ v ••'л'лЬч*:-.-.-.'..- 'J::

: • • •.••••-.'.•*•? • •• : ••• •• •

~ 1 V * WALL * и •• • •

Fif nre 2 DETERMINATION OF THE DILUTION FACTOR FOR THE FLAME ATOMIC I 1 ABSORPTION SPECTROMETRY 11*8-81 j

K. Ikrenyi Hungarian Geological Institute, Budapest, Hungary

The dilution ractor, i. e. tlic concentration ratio or thu analyus in a atom source to the solution, is one of the most important factors for thr determination of the theoretical sensitivity of a spectrochemical method. The dilution factor depends on the construction of the burner and on the flame parameters therefore it Is to be determined occasionally under our analytical conditions.By the method of Magyar (1) an ionization successor (e. g. Cs) and an indicator element (e. g. Sr) are needed and the degrees

of ionization (fa and j>s) are to be determined by the sensitivities measured an the ion line and atom line of the indicator element in the absence and presence Df the ionization supressor. The dilution factor:

20 D . 6.022xl0 tCs]

«here [Cs] is the concentration of Cs in the solution, K. is the Saha constant. The values of Dj for air-acetylene and nitrous oxide-acetylene flames are about 4x10 .

This method to determine the dilution factor can be used when: - the degree of ionization is controlled clearly by the local thermo­ dynamic equilibrium, - the degree of atomization of the indicator element does not chage significantly by the alteration of the flame parameters, - the temperature of the flame during the investigations is considered a constant value.

Reference 1. Magyar, B. Fundamental aspects of atomic absorption spectrometry. CRC Crit. Rew., 1S87, 17, 145-191.

4> ON OPTIMIZATION Oi» ROD GRAPHITE ELECTROTHERMAL AAS-22 ATOMIZERS WORKING PARAMETERS S.N.Ivanov, V.P.GrigorJev Tambov Institute of Chemical Engineering Tambov Higher Military Aviation Engineering School, Tambov, lEiSH In many oaeea the choice of geometric parameters of rod graphite electrothermal atomize» used in atomic absorption spectrometry is free enough. That is why the results of theoretical and experimental investigations on optimization of rod atomizers working elements are presented in this work. On the basis of the literature data analysis and the results of the experiments it was found that under other equal conditions such rods have the best analytical properties,the width of the working part being 1.5-2 times as big as the diameter of the translucent ray and the bottom surface being flat. Such a construction provides dissection of the shielding gas supplied from below. It promotes creating aerodynamic "dead zone" over the rod and thus avoiding coo­ ling of the analytical zone by gas. Theoretical and experimental analysis of temperature distribu - tion over the rod permitted to obtain the relationships to find the velocity of heating of atomizer working element central part of cor­ responding shape and material (1), optimal rod length (2) and mini­ mal power Bupply,providing high heating velocity but not resulting in the thermal rod distruction (3)

T = ^^-[T«PM-T )-TJ.(T-TJ| «) C(T)fS 0 :

• ,кЖНт -Т ) S м н (3)

Here: L - the perimeter of the cross-section of the radiant rod surface; 8 - cross-section near current supply contact; К - coeffi­ cient depending on the law of temperature distribution along the rod;

TM - maximum possible temperature of its heating; To ~ environment

temperature; TH - average temperature in cross-section of the rod S ; p - rod material density; c(T/ - heat capacity of rod material at corresponding temperature T ; £ - coefficient of blackness; Л(Т„)- thermal conductivity; O- Stephan-Boitzmann's ronstant. 44 QUAJI-SQUILIBRIUM THEORY OP ATOMIZATIOH IH ELECTROTHERKAL I ATOUXC-ABSORPTIOH ANALYSIS \Ш-2} D.A.Katskov State Institute of Applied Chemistry, Leningrad, USSR To develop optimal designs of atomizers in atomic absorption spectro­ scopy it is necessary to predict the nature of an analytical signal va­ riations depending on a sample characteristics and experimental condi­ tions. It requires further development of the knowledge of evaporation, atomization and particles transportation processes. The present model is based on Lengmure's theory /V postulating the formation of steam quasi - equilibrium concentration at normal pressu­ re above the surface of evaporation in a gaseous layer, the thickness of which is approaching to the distance of particles free path. The boundary layer conception enables to consider the process of a sample evaporation in atomizers for spectral analysis as diffusion from an equilibrium heterogeneous system fij. The composition of ga­ seous and condensed phases within this system is determined by thermo­ dynamic properties of investigated substances and controlled by envi­ ronment characteristics /Э-§7. The value of the concentration gradient above the surface of evaporation depends on the atomizer design and the nature of mass transfer. The initial area of the boundary layer corresponds to the effective surface of a sample, and at the heating of the atomizer It is determined by the competition of the processes of the surface reduction due to evaporation and its increase due to the particles transfer in the boundary layer. The particles transfer in the boundary layer along the atomizer surface is accompanied by their chemical interaction with a substrate and the appropriate varia­ tion of the gaseous phase composition. In a tubular graphite furnace the gradient of vapours density above a sample depends on the area of evaporation surface /6/. Some signifi­ cant increase in the sample area (e,g., at the furnace lining by an investigated substance) results in the formation of vapours equilibri­ um concentration both in the boundary layer and inside the furnace. At atomization of metal oxides the boundary layer equilibrium compo­ sition ia limited by oxygen concentration above the evaporation surfa­ ce. The distribution of oxygen in the furnacies of general configura­ tions is determined by the reaction with graphite and depends on the furnace size and the effective area of graphite surface. The increase of the furnace length or the insertion of on oxygen getter into the furnace reduces oxygen concentration up to its equilibrium value. In this case the effect of the furnaoe carbon on the atomization of oxide

48 is equivalent to the reaction of reduction. The level of vapours atomi- zation in each local volume of the furnace cavity, and correspondingly, the effective length of the atomic absorption layer, depends on the energy of dissociation of gaseous oxides and the spatial distribution of oxygen inside the furnace. The Interaction of vapours of an investigated metal with graphite In the boundary layer is determined by this element chemical properties relating to oarbon and by the presence of defects In crystal structure of graphite surface. She effect of the graphite eubstrate which results in the reduction of evaporation rate is especially pronounoed in rough graphite and at the final phase of the sample evaporation process. The process of particles transport Inside the furnace is complicated by selective atomic chemisorption on the furnace walls ft J. Using quasi - equilibrium theory it is possible to interprets va­ rious effects which can be observed In an atomic - absorption uialy- sie, including the dependence of an analytical signal value and shape on the furnace configuration and material, the composition and rate of protective gas flow, the sample composition and the volume of sampling solution, the presenoe of non - volatile organic matters In the furna­ ce, au well as on the experimental data obtained during the investiga­ tions of atomization processes, determination of the temperatures of analytic signals occurrence, parameters of Arrbenius equation, ratios of sorption of vapours by the furnace materials, etc.

References 1. Langmuir I.// ttys. Rev. 1918. Vol.12. P.368. 2. Guerrieri A., Lampugnani L., Tassari О.// Spectroehim. Acts. 1984. Vol.39B.P.123. 3. Katskov D.A., Kopeykin V.A.// J. of Appl. Spectr. 1986.Vol.48.P.26. 4. Katskov D.A., Kopeykln V.A.// Ibid. 1988. Vol.48. P.187. 5. Katskov D.A., Kopeykln V.A.// Ibid. 1989. Vol.50.PH9. 6. Katakov D.A., Savelyeva, CO., Kopeykln V.A. et al.// Ibid. 1988, Vol.49. P.7. 7. Grlnshtein I.L., Vasilyeva L.A., Katskov D.A.// J. of Appl. Spectr. *'. 1987. Vol.46. P.13. fi

H A U31V K3TH0D OF PRODUCTIOM OF VAPOURS HIGH - TB.1PEHATURE ABSOBWIOi! SPECTRA AAS-2* D.A.Katakov, A.M.Shtepan, I.L.Greenshteln State Institute of Applied Chemistry, Leningrad, USSR A method of production of vapours absorption spectra in a broad tem­ perature and spectral interval has been developed, A stationary absor­ bing layer of the vapour being investigated is produced by means of a combined atomizing unit comprising spaced and independently heated ato­ mizer and evaporator. • Controlling the evaporator temperature the rate of vapours injection into the furnace is set which provides the cone- tent concentration of sample molecules and atoms inside the furnace. It requires continuous measurement of the absorption value in maximum one of molecular bends or on the absorption line of the metal eomprielng the sample molecule, ss well as the evaporator heating to keep this value at a given constant le­ vel. Thus the absorption layer is obtained with some preset density which does not depend on the fur­ l^v nace temperature. When the irra­ AJ ЛЬ 3io Ш SJ-~ diation of some continuous spec­ Fig,1. Spectrum obtained at trum source passes through the evaporation of MgP2 layer and scanning the studied spectral range, the spectrum can be found which contains in general atomic and molecular bands (Figs.1,2). «thin the range of 244 - 380 nm and 1000 - 2600 К vapours spectra have been obtained which 1800K are formed at the evaporation of halogenides, oxides and nitrates of some metals, evaporating halogenides of In, Ga, Tl, Al, Kg and Ag, as well as nitrates of some metals at excess of halogen- hydrogen acid» the speotra of the related monoha- logenides have been obtained. At evaporation of Я § 3 In, TI and their nitrates only metal lines have been found in the spectra. At evaporation of Ga and GagO, the speotrum has been obtained contai­ ning molecular bands with maximums at 250.0 nm M and 260.0 nm. The bands are related to Oa^O mo­ 265 275. lecule. The data are used to speoify the mechanism Pig.2. Speotrum of atomizatlon. obtained at evaporation of InCl,

47 IHCBKA3B OP SELECTIVITY. ЮН ATOMIC ABJORPTIOH AlfALYSE! WITJ! I AAS-25 A GRAPHITE ОТЖНЛСЕ BY FILTRATION OP SAMPLE VAPOURCi D.A.Katskov, L.A.Vaeilieva, I.L.Greenshtein State Institute of Applied Chemistry, Leningrad, USSR The proapeets of the increase of selectivity for atomic absorption analysis are provided by the application of an atomizer with the supply of sample vapours to the analytical zone of a tubular furnace through a porous filter» A lining (2) of porous graphite is inserted Into a pyrocoated furnace of standart configuration OKPig.1).

Pig.1. Central part of Fig.2. Records of determina­ te furnace tion of 0.12 mkg/ml of Cd in aqueous solu­ tion, containing 0.01 g/nl of NaOl A liquid sample is injected through opening (3) into cavity (4), dried and atomised by the furnace heating. The sample vapours are fed into transilluminated analytical zone (5) through the lining wall. To prevent the lining wetting by the sampled solution and evaporation delay in respect of the furnace heating some ballast - collector (6), e.g., a graphite thread, should be placed in the cavity. Pig,2 shows the possibilities to reduce non - atomic absorption at the definition in the furnace with a graphite filter without distur­ bances correction: a) for a 0.6 mo thiok filter; b) for a 1.2 nm thick filter; o) for 1.2 ma thick filter with a graphite thread.

« A MODIFICATION OF THE ЛТОШС-ABSORPTIOH SPECTROUETRIC AAS-26 METHOD

E, Claos, V. Odinets Institute of Chemistry, Estonian SSR Academy of Sciences, Tallinn, USSR

Up to now, by such factors as simplicity of sample preparation for analysis, sensitivity and reproducibility, atomic absorption spectro­ metry pleased the analyts more than any other method of analytical atomic spectrometry f1]. Recently, due to the progress of some instrument-making firms ICP has started to complete with AAS in a wide range of elements to be determined. At the same time, however, despite their advantages, all these methods, being based on physical phenomena only, have drawbacks as well, for example, the restricted field of application. To extend the field of application of these methods, the use of analytical possibilities of the kinetics of chemical conversions in all possible varieties is just to the point [ 21. The present communication considers perspectives of expanding functional possibilities of modern atomic absorption spectrometers. The idea of an attachment is suggested, providing, in addition to quantitative information, data about the kinetics and mechanism of reactions proceeding in solutions. By means of a given attachment to a Pye Unicam SP-1900 instrument in the flame detection limits have been obtained which successfully compete with ICP and neutron activa­ tion analysis. The information obtained by the new method on the me­ chanism of redox reactions whose rate is influenced by As is discussed. A double influence of As, viz. accelerating and inhibiting, on the rate of molybdenum (VI) reduction to molybdenum (V) has been estab­ lished. The physico-chemical reaction model constructed on the basis of the data obtained is considered. A study of the kinetics of this reaction by AAS allowed determina­ tion of As (in the conditions in which As acts as an inhibitor) with the above detection lim.ts, 0.005 jyg/ml. References

1. Price, W.I. Analytical Atomic Absorption Spectrometry. Heyden, London, 1972. 2. Pardue, H.L. Analytics Chimica Acta. 1989. Vol.216. P.G9-107.

4.3ax.413

'* POSSIBILITIES OF THE SOME RARE EARTH ELEMENTS ATOHIZAUON IN THE ELECTROTHERMAL ATOMIZER лла-г? «ТА 82

E.Krakovske Department of Chenistry, Faculty of Metallurgy Technical University, Kosice, SSFR

With the application of tungsten atomizer WETA 82 in the electrothermal atonization of REE, the atomization process is realized by reduction and thermal dissociation of REE oxides in a medium formed by the mixture of inert and reducing gas (Ar

The optimun flow-rates of gases during the atomization were determined as well as time and temperature regime of drying, decomposition, and atomization of anelytes, and the influence of rate of the atomization temperature increase upon the absor- bance signal value. The analytical calibration lines, the charac­ teristic concentration and detection limit values tor some REE were determined on the basis of the conditions found.

It was observed that the electrothermal atonization in the

tungsten atomizer ensures In some cases values of cchar and c, which are one or two orders of magnitude better than those obtained with the STPF system an pyralitic graphite. It may beassuned that the method would be suitable for de­ termination of low concentrations of REE in the presence of high concentrations of other REE owing to rare line coincidences.

И

9~ MICROWAVES IN SAMPLE PREPARATION TOR ATOMIC ABSORPTION AAS-28 ANALYSIS

I.V.Kubrakova, A.V.Dement'ev, T.?.Kudinova, N.H.Kuz'min Y.I.Vernadsky Institute ol Geochemistry and Analytioal Chemistry of the USSR Academy of Sciences. Moscow, 1ГЗЗП The influenos of miorowave radiation on the chemical prooessas is studied unsufficiently today. Therefore we investigated the effect of microwaves on some model test-systems for which the meohanisms of ehemioal reactions In the physioal fields have been determined. It was shown In our experiments that the formation of free radloals (which were fixed by seoondary produotu - ions and substances with low molecular mass) ooours under microwave irradiation In the solutions containing monomer or polymer subBtanoee (the hydrated electrons were formed as well). The existence of these active particlee oould change the type of process occurring during sample decomposition, particularly redox reaotlona and reactions with free-radical mechanisms (e.g., oxidizing of organio matrix). The acceleration of the reactions also takes plaoe under the influence of these particles. The microwave radiation causes also the dehydration of molecules and ions in solution (this property was used by us for the intensification of the substitution in the inner coordination sphere of the complexes) and in solid phase of the sample (drying procedure). The acceleration of the dissolution of inorganic samples in the miorowave field is possibly connected with the reducing of exchange interaction energy of fragments of crystal structure with the solvent and with the aotivation of mass exchange. Data obtained were used for the determination of Au, Ft and Fd in sediments and sulphide ores with the application of miorowave radiation for drying, aoid decomposition and sorption preconoentration. The time and reagents consumption has been reduced drastically. In closed systems It is possible to exclude the ashing step for the sulfur and organio substances renewing and to avoid the losses of highly volatile compounds. The netals were determined using the automatio sampling of the suspensions of sorbent powder into the atomizer of AA speotrometer (3030Z, HQA-600, AS-60).

SI аК£аЛОаО--31л02АОИшШД ATOlilC яМЧ&М iS'J jSiiiitti~-i.iIu.T.iOU [ дд~ 9Q'

01' dO.'.Ji IXl'ALB

G.il.r.uchuk, A.K.Chorykov .:Po Lenneftekhim, Leningrad, U3GR Pcrspectivity of some цгоир extraction systems with following di­ rect analysis of organic extracts by graphite furnace utociic absorp­ tion spectrometry (Gi'AuS) is demonstrated. Liquid cation exchange ex- trogents - fatty iiionocarbonic acids Cg-Cg and their solutions in

CCi. are used for determination of i*n, Л1, Snt Cd, Be, Or and oth­ er metals* To extract acidocoiaplexes such as FoClT, PtCljj", PdOlJ" , the solution of dientipyrilrnethane in ohlorophorm are investigated.

To optimize conditions of the quantitative separation, the otoi- chiometry and extraction constants of cationic and anionic complexes are determined. In most cases, they provide quantitative transporta­ tion to organic phase most of tho considered elements at volume ra­ tio of aqueous and nonaqueous phases r - 10-100. These values of concentration factors ensure a considerable decrease in dctectionli- mit and expand possibilities of G?AAS application.

Transition from aqueous matrix to liquid carbonic ucids or dion- tipyrilmethane solutions do not practically raise characteristic amounts, detection limits and do not reduce reproducibility of ana­ lytical GFAAS methods, liatrix effects (non-specific absorption) do not play essential part in such or conic systems. Extract ion-GFAAS methods of determination of heavy metals in the natural waters of different types, traces of some metals in the te­ chnological products and methods cf some medical and biological ob­ jects control based on the proposed extraction systems are developed. Relative standard deviation of these methods do not exceed 0.1, con­ centration detection limit is in the range from 0.1 to 1 ppb.

62 INTENSIFICATION OP SAMPLE PREPARATION FOR THE ANALYSIS I 1 AAS-30 BY ATOMIC SPECTROSCOPY METHODS L ±._

N.H.Kuz'min Vernadsky Institute of Geochemistry and Analytical Chemistry of the U33R Academy of Sciences, Moscow, US3H A great variety of sample preparation procedures and their combinations limit the analytical cycle duration, the labour consumption and the quality of metrologioal parameters. The stage of sample preparation in this respeot isn't normally adequate to the determination stage, especially if fully automated atomic emission, atomio absorption or atomic fluoresoense speotrometers with high quality software are applied. Hence it's necessary to intensify sample preparation procedures. The following factors and techniques for intensification of sample preparation procedures should be mentioned: l) the use of highly agressive reagente and media for sample digestion; 2) the work at high temperature and pressure (analytical bombs); 3) the use of catalysts; 4) the application of external physioal fields (effect of ultrasonics, photons, magnetic, electric or electromagnetic fields, including microwaves and lazers); 5) the combinations of sample preparation procedures. The analytical autoclaves for various purposes are now widely used. This isn't only time consuming but makes possible to determine the high volatile forms of elements as well. The vacuum extraction combining several preparation procedures is developed successfully. A catalytic digestion is used now only for the analysis of organic and organometallio compounds. Photolysis is useful for the quick destruction of metal oomplexes with fulvic acids of natural waters. The influence of the microwave energy acoelerates such sample preparation procedures as drying, decomposition with rigorous reagents, fusion and sorption preconoentration. From our point of view it should be interesting to affeot the samples by charged partioles, 7-quanta and hard X-rays. The analysts haven't paid attention yet to the new method of the transformation of eleotrioal energy into the mechanical one.oalled the eleotrohydravlio effect. It's also useful to develop the continuous analytical oyoles and new technical solutions for the design of traditional sample preparation methods.

S3 THE ROLE DF NEBULIZATION AND EVAPORATION IN THE fTI^Lx* SAMPLE INTRODUCTION

J.LAKATOS, I. LAKATOS Research Laboratory for Mining Chemistry of HAS, Miskolc-Egyetemvn'ros, Hungary

The influence of the physical parameters of the nebulized so­ lutions on sample introduction can be traced back to the following factors 1) the viscosity, density and surface tension of the sample which determine the particle size distribution of the aerosol, and 2) on account of the solvent evaporation during the aerosol transport the particle size is decreasing which results in an enhanced sample introduction. The primary aim of the present study has been the investiga­ tion of the nebulization and vaporation processes. Using a con­ centric pneumatic nebulizer and a temperature controlled nebulizer chamber different pure solvents (carbon-tetrachloride, benzene, methyl-isobutyl-ketone, water) and alcohol/water mixtures were analyzed. The parameters of the sample introduction were determined by both direct (impactot and filter combination) and indirect ways (measuring the amount and composition of the waste solution). On the basis of the experimental findings it has been concluded that the role of nebulizatian and evaporation in the sample introduc­ tion jointly depends on the actual uptake rate and the volatility of the solvent. E.g. using volatile pure solvents or high alcohol content in alcohol/water mixtures at low uptake rate the sample in­ troduction becomes primary an evaporation coltrolled process. How­ ever, if the uptake rate is high C>5 en min ) or the concentra­ tion of the volatile component in the solvent mixture is low, the sample introduction is mainly determined by the particle size dis­ tribution of the nebulized solution.

M

fP^ TK STATE АИР STATUS OF ШСТЮТКМШ ATOHISATION I I AAS-J2 D. LITTLEJOHN Department of Pure and Applied Chemistry, University of Stratbclyde. Glasgow, 61 1XL. UK

Electrothermal atomisation has been used in atomic absorption spectrometry for approximately 30 year*. Although «any mistakes vere made in early applications, the technique ia uov well-established (or the determination of щ/ч and ug/1 concentrations of elements in a variety of sample types. Ingenious studies of the chemical and physical phenomena that occur in an electrothermal atomiser have provided a better understanding of atomisation and chemical interference mechanisms. Automatic background correction procedures have been developed and most modern instruments exhibit a high degree of automation vith sophisticated data processing facilities. As a result, it is possible to perform analyses, previously considered to be difficult, vith a minimum of sample preparation and without the need for complex calibration procedures.

Xn parallel vith these advances in electrothermal atonic absorption spectrometry (ET-AAS), the graphite furnace has become an important vaporization and atomisation system in other techniques. Sensitive thermal atomic Mission measurements can be made lor many elements using a conventional graphite furnace. Ketal and non-metal analytes can bs determined by nom-tnermil atomic emission spectrometry «its a FAKES atomiser which involves vaporization of the sample into a hollos cathode discharge formed in the graphite tube. Electrothermal vaporization of small specimens into inductively coupled plasma (ICF) sources has extended the application of Icr-AES and 1СМИ in s variety of applications. More recently, extremely low detection limits have been reported for s number of elements «hem graphite lnrnace atomiaatioa Is used in laser excited atomic fluorescence spectrometry.

In reviewing the state and status of electrothermal atomisation, attention vill km focused on our current knowledge of furnace processes and the impact fundamental studies hive hid on the development of simplified ET-AAS methods. Topics covered «ill include the use of chemical modification and high temperature vaporization In the determination of trice metals In environmental and biological samples. Alternative uses of electrothermal alomisation «ill be considered vith emphasis on developments in FADES, LEAFS and novel electrothermal atomiser systems. To conclude, comments vill be given on the future development of electrothermal atomisation.

U SAMPLE ISOTONIC COMPOSITION BWIBHICE ON THE AAS-33 i RESULTS OF АТОЫ10 ABSOBFTIOH MEASUHBIHITE V.G.Kuradov Ul'ynnovak Jtate Pedagogical Inatituie, Ul'yanovsk, J3SR There was investigated the influence of the sample ieotopic com­ position on the value of linear (A,) and total (A) absorption of the resonance linee of absorbing homogenous vapour layer of a chemical element in a wide temperature range CD. It was supposed that the

determination of the AL value is performed by using the linear spect­ re source containing elements of natural ieotopic composition.

Fundamental calculations of AL * f(2) and Л • f(T) ratio were per­ formed for the absorbing cell model: saturated vapour - condensed phase when the investigated sample is enriched with this or that iso­ tope to the concentration ;»9W=. It is demonstrated that the ratio A, * f ;.T) of the A. value is es­ sentially different for different isotopes of the investigated chemi­ cal element in the region of small and medium absorption. It allows to determine the isotope the sample is enriched with. It is proved that the cross-section of atom resonance collision in the absorbing cell essentially influences the ratio A - f!.T) and the cross-section of radiating atom collision with foreign gas atoms in the light source influences the ratio A^ » f(T). She method is illustrated by the resonance lines of Jto(I) Д,«285.5, Zn.DU-»307.6, Cd(I)J.-326.I om and samples enriched with the follow­ ing isotopes: ^hbte.ZL), aoeFb(9?.S and 97.8%), ыгя(<».7*'), 67Zn(9i.9K), ^гпСЭв.Э*), IH0d(9*.e»).

The calculated values AL and A for this or that sample isotopic composition used with thermodynamic data on an element's saturated vapour pressure are in good agreement with the experimental results of the linear and total absorption of the resonance line.

И VETAL АТ0К12ЕЯЗ IT АТОЫК-АВЗОНРМОИ МП) ATOCIC-PLUOR3SCSHCH SPECTROMETRY |„AS-34

V.I..Muzgin, Yu.B.Atnashtv, A.A.Pupyshev Urals Poly technical Institute, Sverdlovsk, USSR In recent years serious successes were achieved in improving elec­ trothermal graphite-tube atomizers,in particular, platform (ballast), temperature stabilization, pyrolltic carbon coating application, fur­ nace surface modification with carbides and oxides, furnace coating with refractory metal foil, matrix modiflcators utilization. Charac­ teristic mass (n° ) factors found experimentally correspond to cal­ culated values whioh testifies both theoretical approach correctness and theoretical values detection limits (DL) reaching [1]. From the point of view of the theory [1] open atomizers must con­ siderably be Inferior to GTA in m° _ values, however experimental results achieved for different metal open atomizers (filaments, loops, ribbons, boats and especially tungsten-coil atomizer - TCA [2]) do not confirm that. Atomic vapour localization lack in this kind of atomizers is replenished by the "flash" atom density increasing at the expense of high heating rate, which may achieve 3.10' К/sec. Atomic- absorption epectrophotometres fitted with TCA are characterised by small dimensions and low weight, atomizer contact points water cooling lack, high determination rate CIS - 60 sec), the application of the atomizer itself as a precise autosampler (both for solution and metal); low DL (0.01 - 10 pg), good repeatibility of results (Sr - 0.02-0.OB). Metal atomizer utilization eliminates graphite furnace harmful in­ fluence on some carbide forming elements DL. At the same time recovery atmosphere application (Ar + H2) and atomizer surface modification with carbon make it possible to reduce DL for a large elements group as compared with atomization in pure argon. The possibility of appli­ cation of this method with atomizer automatic control temperature is of special interest. In this method calibration curve slope is equal for all elements and it la close to 45°, and calibration linearity comprises 5-6 orders of magnitude on a log-log plot. Open metal ato­ mizers can readily be used in atomic-fluorescence analysis method. In this method analytical curves linearity range is increased, M, is considerably lowered.

References

1. L'vov B.V., Nlkolajev V.G., Norman E.A. et al.//Zh. Analit. Kbim. 1969.Vol.44.?.802. 2. Muzgin V.N.,Atnashev Xu.B.,Korepanov V.E.,Pupyshev A.A.//Talnnta. 1967.Vol.34.P.197.

•7 DIFFERENTIAL-THERMAL ANALYSIS APPLIOATIWJ FOR THE STUDXl ,,_ „ AAS—35 OF THE KACROCOMi'CNiCNTS EFFECT 0»! THE ATOHIC ABSORPTION I --_l DETERMINATION OF THE ELEMENTS WITH ELECTROTHERMAL ATCMIZAIION V.K.Bagdaev Tambov Chemical Engineering Institute, Tambov, USSR The differential-thermal analysis for determination of the main thermochemical processes on the atomizer graphite surface in seg­ ment section rod form under the sample macrocomponenta effect is used, The transformations on the graphite surface at the temperatures up to I600°K have been simulated on the Dupont thermoanalyzer 990. The mixtures to be investigated have been heated up to assigned temperature and then the products composition has been determined. Products before and after thermal interaction effect have been de­ fined. The fact that the processes occurring at the temperatures above I300CK have been studied with the help of the segment section gra- p .ite atomizer placed in general-purpose vacuum sprayer allowed to dose the sample and to heat the atomizer according to the tempera­ ture program normally applied during electrothermal atomization in assigned atmosphere and vacuum. The identification of the compounds formed as a thermochemical reactions result has been carried out on the basis of X-ray struc­ tural analysis technique excluding the atmosphere reaction products interaction. It has been found that if the atoms of the defined elements and macrocomponents are formed according to the carbonic reduction scheme it is solid solutions and spinel compounds that ere formed on the graphite surface» The latter are also formed on the graphite surface in ease of the macrocomponenta atomization according to the oxide scheme. Oxides formed as a result of the carbonates decompo­ sition are effective in the gasous phase due to the oxide and car­ bon dioxide deposition. The ooncluslon ie proved by the thermody­ namic calculations. Based on the above mentioned investigations special diagrams of the elements atomization under macrocomponenta effect are coaider- •d. Methods of decreasing of the macrocomponente effeet on the re­ sults of the atonic absorption analysis with atomization on the graphite surface are also developed.

If ПШЮтмШ OF VOLATILE CHELATES OF METALS 0» I ... ,,j ELECIROIHEFMAL GRAPHITE TUBE ATOMISER IN ETA - AAS 1A 3b|

N.A.PanlcbeT, J.A.Gorev Leningrad State University, Research Institute, Sosnovy Bor, USSR The possibility to decrease the concentration Halt of detection in ETA - AAS is based on the «ay to utilise the two function of the electrothemal grapfite tube atomiser. The first one is to use atoaiser for preconcentration of an eleaent and the second one ев atomiser itself. This double function of the atoaiser may be the real one, if the determinated eleaent will font the volatile eoapound and in this Гош вау be separated from natrix and delivered in atoaiser. By that moment in atoaiser should be created conditions for decomposition of volatile compounds and hence for accumulation of element inside of atomiser. В - diketones is one of possible class of compounds forming the volatile chelates with many eleaents of the Periodic Table. The teaperature of volatalisation of different |J- diketone chelates vary froa 80 to 300 С and all of thea at higher temperatures are decomposing with educing of free metals or there oxides. The realisation of this method of preconcentration was carried out with the help of siaple device to coaaertional atomic absorption spectrometer. The possibility of suggested method of preconcentration have been tested on the examples of Cu and Al determinations in deionesed water and Be in natural waters. The limit of detection ( 26) for Cu and Be was O.OZfg/l and for Al - O.OS/Hg/1 after extratlon of an element from 100 ml of water by 2 ml 0.001 M solution of в - diketone in chlorophorm. For determination was used 20 Ml of organic solution. '

n .rtiOBLa:.! Cl< «AltS ISA.-i'l'lIS ithT.;Kb:iitU!IOM 1И jrtAPHITi; JU.tJiiJii I 1 1 AAS-37 I _.A.i-elievu, V.G.Bukhantsova scientific and Production Association "Khimavtonatika", •utperimental Design Bureau of Automation, Severodonetsk, 0333 ahen determining rare-earth elements in a graphite tube furnace one encounters many problems: formation of stable compounds of the rare earths with carbon both in solid and gas phases, formation of stable compounds of the rare earths with oxygen of the furnace atmo­ sphere, formation of stable compounds with macrocomponents of the sample Deing analyzed such as the other rare earths, Ti, ir, Si, etc.

The rare earths evaporation from various types of furnace surfaces has been investigated. She maximum sensitivity of the rare earths de­ termination was exhibited by the tantalum-lined furnaces (with or wi­ thout a tantalum boat). However, lining the tube with tantalum foil as well as punching the tantalum boats is a laborious process. The sensitivity exhibited by the pyrolytically coated furnace was an or­ der of magnitude worse and made 0.08-2 ng, with memory effect being absent. The furnace lifetime is 100-150 heating cycles at a tempera­ ture of 2900°C. On the basis of the experimental determination of the energy of activation of the rare earths evaporation process in the graphite fur­ nace there has been found a mechanism of atomizations dissociation of the oxides.

The effect of Al, a'i, Si, Fe, ir, и, Са, Зе, and the rare earths on the determination of Sm, 5c, Hd, Gd, Eu, Br has been studied. Both a decrease of the absorption of the element being defined and its in­ crease were observed. A mechanism of the influence has been proposed. She results of the analysis of geologic samples by using an atomic absorption spectrophotometer 3ATUHK-5 equipped with an electrothermal atomizer GRAJHIT-1 are discussed. i

и HE» KXFK3S3 OP CHEHICAL SAMPLE PRETREATblSHT OP SOLID SUBSTABCES ..JiS-38 L.I.Plesokach Kasakh State University, Alma-Ata, USSR At present chemical solution (decomposition) of powdered samples is carried out by means of classical analytic chemistry methods which are notable for their low productivity, labour- and energy-consuming and do not allow to carry ont sample pretreatment automatically* Very often decomposition takes over 90 per cent of time while an analysis from a solution by means of physical methods is fulfilled in a free - tion of a minute. Various methods of sample decomposition usually pre­ supposes either solution in the aoidic mixture or melting with fluxes and further solution of a melt. The autoclovic method is considered to be the guickest one but its automation is rather difficult. Ihe critical observation of acidic me­ thods shows that the methods used are mainly taken from the procedures of gravimetric, photocolorimetric and electrochemical methods of ana­ lysis without adjusraent to the specifity of atomic-omission, atomic- absorption methods of analysis Involved, The high selectivity of the latter allows to simplify and unify essentially many actual procedures of decomposition. The methods of solution process intensification wor­ ked out In chemical technology can be for the acceleration of sample decomposition. For example, in many cases intensive stirring allows to carry out decomposition in 1 to 5 min even without heating. The hea­ ting up to 70 and UV-treatment considerably widen the number of objects of analysis, the latter being guantitavely decomposed in only 1 min. These methods offer an opportunity to automatize acidic decom­ position and to carry out sample pretreatment right from the solid substances with a productivity of 60 tests perhou. The usage of ultrasound in the alkaline melting of silicate tests air- lows to reduce resolutely the labour expenditures and duration of the operation. It takes only i.5 min to melt quartz together when ultraso­ und Is used simultaneously, while in case of alkalification the process is over in 1 min. Sue to the dispersing action of ultrasound the qua­ lity of a melt corresponds to the requirements of X-ray spectral ana­ lysis. Oonsidersble reducing of time for analysis and labour expenditures is achieved by the ultrasound usage in chemical phase analysis. The solution dutatlon of lead and copper minerals in selective solvents reduces by 3 to 60 times with the selectivity being improved. When analysing the fertilizers the ultrasound allows to extract vaious forms of useful components in 2 to 5 min.

•I

^ INVESTIGATION OF MAGNESIUM-ALUMINIUM INTERACTION WITH AiS-59 FLAME ATOMIC ABSORPTION AND COMBINED QUARTZ FURNACE-FLAME AAS TECHNIQUES

J.Pasta, Z.Kovecs, L.SzQcs Institute of Inorganic ana Analytical Chemistry, Kossuth University, H-4010 Debrecen 10., Hungary The interfering effect of aluminium on the determination of mag­ nesium using an acetylene/air flame is a well known phenomenon of flame spectroscopy. It is also published, that the absorbance of magnesium in the presence of chloride changes with increasing alu­ minium concentration according to a maximum-minimum curve [l-3]. To explains this phenomenon, не systematically investigated the effect of flame composition, that of the place of flame obser­ vation and that of the aluminium/magnesium ratio on this inter­ action. For these studies we.used continuous AAS scanning [4] and titration methods [ S]. For modelling the thermal composition of the solid aerosol, formed from solutions of either magnesium chloride or aluminium chloride or both compounds, we used combined quartz furnace - flame techniques. Ue found, that in the megnesium chloride and aluminium chloride containing system - beside the mixed oxydes - a volatile magne- sium-aluminium-chloro complex is also found, the atomlsation of which is more favourable, than that of the mixed oxydes, and is practically independent of the chemical composition of the flame.

References

1. Menzies A.C.,/Anal.Chem. 32. 1940.P.898. 2. Rubeska I., Moldan 0.// Acta Chim. Hung., 1965.4».P,367. >. L'vov B.V.// Atomic Absorption Spectrochemical Analysis, Adam Hilger, London, 1970. 4. Posta 3., Oavydova, S.L.//7*" Czechoslovak Spectroscopic Conference and VIII. CANAS. Ceske Budejuvice, 1984. Abstract of papers P.151. 5. Posta 3., Lekatos 3.11 Spectrochlm. Acta, 1980. 3SB.P.601.

« COMPARISON OP ALGORITHMS FOR BOH-blTBAR AMAIITICAL Г~~ 1 FOTCTIOHS IH РЬАИВ АТОШС ABSORPTION SPECTROMETRY I I H.Alvarez Prieto, C.A. de la Fi ffapoles, J.S.Mlnoeo Oomez, O.Duque Diaz, M.R.Catasus Portuondo Institute of Materials and Reagents for Electronics, University of Havana, San Lazaro 7 L, Havana City, СиЪа

Historically the non-linearity problems of calibration curves in AAS have been studied in two directions. In the first one, the causes that originate the curvature have been considered from a phenomenolo- gical point of view /1, 2_7. On the factors that determine the shape of calibration curves, several authors and firms have reported algo­ rithms based on statistical considerations Ci, 47. la this work, 15 different algorithms are compared. In relation to goodness of fit and recoveries, nine of them were developed by diffe­ rent authors and the other six are employed in commercial available Instuments /57. Their advantages and limitations are discussed for several currently determined elements in flame. The measurements were carried out on a SP9-B00 Pye Unlearn atomic absorption spectrometer. Programs were written in ft-83 BASIC language, using double precision In the necessary oases. Conclusions in relation with the practical applications of diffe- rents algorithms are established.

References 1. Rubeslca I., Svoboda V. // Anal. Chim. Acta. 1965. Vol. 32. P.353. 2. Wagenaar H.O., Movotny I., de Galan b. // Speetxochim. Acta. 1974. Vol. 29Б. P. 301. 3. Bamett W.B. // Ibid. 1964. Vol. 39B. P. 829. 4. Andrews J.A.S., Jowett A. // Anal. Chin. Aeta. 1982. Vol. 134. P. 383. 5. Bysouth S.R., Tyson J.P. // J,Anal. Atom. Speotrom. 1986. Vol. 1. P. 85.

•3 STAHDARD ADDITION TECHHIQTJE TOR HOT-LIlfBAR AJfAbYTICAT. AAS-

The non-linearities problems of calibration curves in AAS impose limitations into the applications of the standard addition technique (SAT). They determine its use in short concentration ranges (with low precision), or the use of essential different instrumental con­ ditions with low sensitivities and poor detection limits. Twelve different algorithms for the use of the ?AT in the pre. senca of curvature are presented. These new algorithms were derivat- ed in two way» modifying the models that belong to available com­ mercial instruments ZT—27, and by means of mathematical transformat­ ions of reported ones by several authors Л, 57. Their advantages and limitations are discussed. The measuremente were carried out on a SF9-800 Pye Unlearn atomic absorption spectrometer. Programs were written in №88 BASIC language, using double precision in the neces­ sary cases. This study shows the possibilities of the SAT Mien non-linear analytical functions are presented in practical work.

References 1. Whiteside P.J., Stockdale T.J., Price W.J. // Speetrochip:. Acta. 1982. Vol. Э5В. P. 795. 2. Barnett W.B. // Ibid. 1984. Vol. 39B. P. 829. 3. Byousouth S.R., Tyson J.P. // J. Anal. Atom. Spectr. 1986. Vol.1. P. 85. 4. Wagenaar H.C,, Hovotny I., de Galan Т.. // Spectrochim. Acta. 1974. Vol. 29B. P. 301. 5. Andrews J.A.S., Jowett A. // Anal. Chlm. Acta. 1982. Vol. 134. P. 383.

И INTERPRETATION OF SIGNALS MEASURED IN THE PRESENCE OF ; UNKNOWN INTERFERENTS IN THE AAS-ANALYSIS AAS-4g

L.Pszomcki

Institute of Nuclear Chemistry end Technology. Dorodna 16. 03-195 Warsaw, Poland

A set of empiric equations describing the general character of non-additive interference effects on the run of calibration curve in the AAS analysis was formulated (1). The equations enable a theoretical discussion of the properties of all procedures used presently for the direct evaluation of analytical signals obtained for the unknown samples containing interferents. These procedures are: 1. standard addition method (SAM! 2. successive dilution method (SDH) 3. application of spectroscopic buffers 4. standard addition and successive dilution method (SASD-method) The equations enable to estimate the conditions that should be fulfiled for the correct work of the first three procedures mentioned above and indicate clearly their limitations. They also show that in many cases no one of these procedures is effective and for the correct transformation of the measured signal into the actual concentration value the recently proposed SASD-method [1] must be applied. All results of these theoretical considerations are confirmed very well by the experimental data. SASD-method may be considered as a combination of SAM, SDM. and buffer application. It cumulates the advantages of these three procedures and eliminates almost completly their shortcomings and limitations. The performance of SASD-method is very simple and no preliminary information on the nature and composition of the sample to be analized are required. Although the above sosiderations were carried out for the AAS analysis the conclusions have a general character and concern also other analytical methods for that the preliminary elimination of the additive interference effects is possible.

Reference 1. Pszomcki L,,Skwara w., "Standard Addition and Succesive Dilution Method. Evaluation and Verification of Results in AAS Analysis"// ТаIanta. in press.

5.3flK.4i3 65 THERMOCHEHICAI PROCESS IB RADIATION ADC ABSORPTION AAS-43 AHA1YTICAL SPECTRUM SOURCES EXPERIMENTAL STUDY, THERMODYNAMIC SIMULATION AND CONTROL

A.A. Fupyshev Urals Polytechnical Institute, Sverdlovsk, USSR Investigation of vaporization, atomizetlon and ionization proces­ ses taking plaoe at high temperatures in all radiation and absorption spectrum sources allows to get acceptable analytical characteristics with less material and labour expenses and to forecast, in the long run, methodical analysis conditions. Thermodynamical approach appli­ cation based on experimental data is of great assistance in these problems solution. Different thermodynamic approach levels systemati- zation and spectrochemical problems range determination indicate that the most apropriate method for multi-component geterogenic systems is thermodynamic simulation (IS) method based on equilibrium system po­ wer potential minimization» Possible equilibrium components registra­ tion, reliable thermodynamic data availability, system closeness, lo­ cal thermodynamic equilibrium (LTB) reaching are theoretical model adequacy premises to experimental results. Genuine radiation and absorption spectrum sources are open опэв in most cases with clear LTB distortion signs. Nevertheless, TS applica­ tion is extremely successful especilly with renewable sample volumes sources. Thus, TS equilibrium composition of flame CJHJ-NJO and large elements group atomizatlon effectiveness depending on the carbon/oxy­ gen ratio made it possible to reliably calculate absorption signal profiles and characteristic elements concentration and to establish dominating factors in sensitivity of analysis. TS of high-frequency jet discharge argon plasma equilibrium composition showed the possi­ bility to drastically raise analytical lines pair concentration sen­ sitivity, which was proved experimentally correct in real non-equili­ brium discharge conditions. Por non-renewable sample volumes sources with non-uniform compo­ nents utilization, it is necessary to carry out kinetics process re­ gistration while conducting TS. 28 elements atomization TS conditions in three tungsten-coil atomizer operating regimes were found, Pyrolis and atomization temperature was determined; possible modificators were predicted, TS application for complex «ample vapourisation conditions and for spectra excitation in carbon arc during chemically active agents selection perspective is shown.

M THE ROLE OF MOLECULAR SPECIES IN THE ATOMIZATION MECHANICS OF SILICON IN A GRAPHITE FURNACE ATOMIZER I**8-44 C.J.Rademeyer, I.Vermaak University of Pretoria, Pretoria 0002, South Africa

There is still uncertainty about the atomization mechanism of certain elements in the electrothermal atomizer. Numerous methods have been used in an effort to gain some information that may be used to elucidate these mechanisms. Such methods include X-ray diffraction, molecular absorption and mass spectrometry.

In this study it was attempted to identify gaseous molecular species formed at high temperature during the atomization step. Spectra of these molecular species, oxides and carbides, were recorded during the atomization cycle and identification attempted. Thermodynamic CEA) and kinetic СКАЗ parameters were determined for reactions that possibly lead to the formation of oxides and carbides. Factors that influence these reactions e.g. partial pressure of 0g, COg and CO were investigated.

Results will be presented showing the experimental spectra, kinetic and thermodynamic data. Atomization mechanisms will be proposed and comment made on the role of carbides as intermediate product.

•7 IMOREASnie OP SENSITIVITY OF THE ATOMIC ABSORPTION AAS-45 AMD PLUORSSCJJHOB SPECTROMETRY BY THE OPTIMIZATION 0? I SAMPLE AT011IZATI0N CONDITIONS

A.Z.Razyapov, V.A.Merlcushev, D.A.Shapovalov OINALMAZZOLOTO, Moscow, USSR

Nowadays the increasing of the sensitivity of the atomic absor­ ption and fluorescence spectrometry analysis is mostly achieved by a preliminary concentration and separation of components to be determined. However the application of traditional methods of con­ centration complicates the analytical procedure, increases its du­ ration and in some cases reduces metrological characteristics of quantitative measurements. Therefore it seems advisable to inves­ tigate instrumental and methodical ways of realising the potential possibilities of direct spectral methods which provide the recei­ ving of the analytical information from the detection of even a single atom.

In this work, the main factors effecting the sensitivity of the atomic abeorbtion and fluorescence spectrometry are considered. The source of the sensitivity improvement is pointed out to be a development of optimum conditions for a space localisation and re­ taining of atoms in a detection rone of an atomizer. The model of the absorbing atomic layer formation is suggested and the possibility of its application for various types of ele­ ctrothermal atomizers is demonstrated. The constructions are considered of combined graphite furnace- flame atomizers and their analytical and metrological characteri­ stics are estimated. The results are given of the experimental investigations on the determination of trace impurities in pure materials and environmental objects.

M ATOMIC FLUORESCENCE ЯЕШВШНАХТОИ 07 HEJRAOTORY HETAI6 osms o? UAS-PHASB AKWIZATIOT ' ' V.IJiiein Besearoh and Design Institute for Problems of Development oftiie Kansk-Achinsk Coal Basin, Krasnoyarsk, USSR Determination of refractory metale 07 atomic spectrometry is а те­ гу difficult problem becauae of ЪоН» complications during obtaining of analytical concentrate from initial aample weiefct and utterly low extent of atominatioa of these metale in common atomizing media on account of formation of thermally stable oxides and carbides. Obese difficulties may be obviated by use of gas-phase atomiiation of gaseous analytical concentrate obtained by conversion of determi­ ned metals into volatile fluorides, she sample weieht la decomposed by heating with xenon tetrefluoride in autoclave. ХаТд, decay at hea- tiaa to Xe and free atoms of fluorine; tbese atoms convert all the components of sample to higher fluorides.Ihe volatile fluorides of metal* are distilled off from autoclave into gas-chromatographic column where they retained and then separated from eaoh others on proper ad­ sorbent. Die eluted from column gaseous concentrate feed in atomiser. An atomisation technique is used gas-fhas* redaction of fluorides by hydrogen or vapours of aloallne metals. It has been found that reduotion of Zr, Hf, Kb, la, Ho, w, Be, 0 fluorides passed fast and quantitatively. On main stage of reduotion the free atoms of these metals are generated. Lifetimes of taws* atoms ( period of time from moment of generation to moment of formation non-fluorescent multiato- mic clusters ) are not less than 5 milliseconds. Buch lifetimes are quit* enough for excitation and registration of atomio fluoresoence. The reduction must be carried out at constant conditions. Oaa-chromatographio separation of determined elements is served instead of monoohromator since at each moment of time it ie passed through the atomiser only one of determined metale.Oils factor allows to use dieperaionless non-selective monodetector registration of ana­ lytical signal for selective multielement determinations with eonti- nous source of excitation radiance. lhe apeotrometer is calibrated on pure compound* of determined metals. Bueh technique may be regarded as nearly-absolute method of atomic fluorescence analysis. The off erring method has been used for determination of treses of abovementioned metal* in coals, dust*, biologioal object*. Deteotion limit* lie in pg-region; relative standard deviations are not higher than 0.2 at contents oa. Ю"6 %. She obtained results are in good ag­ reement with data of independent method*. MUMIELRMHJT ЕШЗТВОТНЕНМАЬ ATOMIC ABSORPTION AHAI2SIS ,,„ • WITH CONTDTOUH SOURCE V.LRigin Research and Design Institute for Problems of Development of tile Kansk-Achinsk Coal Basin, Krasnoyarsk, USSR The combination of carbon furnace atomization with multielement deteotion is potentially a powerful analytical tool. The real use of this technique for multielement analysis is restricted by impossibi­ lity to ensure the alike acseptable conditions for atomisation of the all determined elements, as well non-isotaermity of tne vapour posse in which measurements are made. These factors lead to both a lowering of residenoe times and "memory effects". Besides, it is lack of reliable multielement spectral leaps they give analytical lines of all tiledetermine d elements with needed intensities Г1 J. With a view to eliminate these limitations it is proposed a method based on two-stage atomisation of sample: at first stage the analyti­ cal concentrate is preheated to atomisation by microwave heating, at second stage the obtained plasma is feed into graphite furnace for final atomisation and measuring of atomic absorption. The final tem­ perature of microwave plasma and graphite furnace are equal to each other. These temperatures must choosed sufficiently high for atomi­ sation of the all compounds of determined elements. As preatomissr it is served the sireon capillare which is placed in cavity of reso­ nator of Binekker's type. The final atomisation is carried out of graphite furnace SP-9 ( Pye-Unieam ) fitted with modified pyrolytle graphite tabef 2 J . It may be used two versions of saapls introduction into atomiser. At first version the determined elements are isolated by liquid extraction and obtained extract is feed into capillars of preatomiser by using of positive flow-injection. At another version the determined elements are isolated into gaseous analytical concen­ trate in form of volatile compounds, and this concentrate is feed in preatomiser's capillars. As source of excitation radiance served xenon are lamp. Multielement registration is performed by means of polyohromator system from spectrometer JX-48 ( JoMn-Ivon ) with measuring channels for 16 elements. By using of gaseous analytical concentrate is it possible dispersionless monodetector registration, the selectivity is achieved owing to gas-cltt ometographlo separation of volatile compounds of determined elements. References 1. Koshy V.J., earg V.H. // Joan. 8oi. Ind. Bee. 1986.Vol.45. P.29f. 2. Klein T.I. // Srarn. anelitioh. Btin. 1989.Vol.44. P. 257.

П ШАВЕГ-АВЗОДОЕ HBTHOD OF ATOMIC SEKMBAL AMAH6IS liAS-W V.IJMgin Research and Design Institute for Problems of Development of the Ksnslc-'Aohinek Coal Basin, Krasnoyarsk, USSR One of the sain hamparines in use of any method of atonic spect­ ral analysis for environmental control consists in necessity of gra­ duation of spectrometer on standard reference material ( SDH ) of analyzed object. Conplicability and expansivity of making, sertify- ing and storage of enormous number of SRM for continuously increased vast amount of to be analysed environmental objeots wars at the bot­ tom of Idea of absolute method of analysis, in which the result a are cal­ culated oi! measured analytical signal by theoretical equation that related thin signal with content of determined element in sample. Walsh ['i J иаа the first to suggest this idea for flame absorption spectrometry; later this concept was elaborated for electrothermal atomization by L'vov f2j. In the «hole extent absolute method of spectral analysis is hardly realized. Measured value of analytical signal is depended on many unaccounted factors changing for each in­ strument: geometry and hydroaerodynamic of measuring cell, quality of maldns; of device, characteristics of light source, quality of de­ vice's accessories, extent of dust loading on optical surfaces[ 3 J As an alternative to absolute method of atomio spectral analysis we have proposed an approximation that consists in isolation of de­ termined elements in form of gaseous oompounds of the same type with obtaining of gaseous analytical oonoentrate which is feed into atomizer. In such е*я» eliminate interferences arising from matrix elements, light scattering and so on. Absence of stages of solvent vaporization, drying, melting and vaporization of solid residue allow to use atomizers of low-power, e.g., hot inert gas. In such oase analytical signal have minimal distortions. Spectrometer may be graduated on pure oompounds of determined elements; the results may be calculated by unified concentration coefficients. All inter­ ferences are transferred into stage of sample preparation from sta­ ges of speotrsl determination itself. Tor realisation of this tech­ nique is it needed to transfer the determined elements into gaseous phase quantitatively or strictly substoiohiometrie. References

1. Halsh A. // Speotrochim. acta. 1955. Vol.7. P. 108. 2. b'vov B.V. // Insb.-phys. zhurn. 1959.Vol. 2. p. 56. ?. Mandslshtsn в.£. // Bpeoteoehi*. aota. 1978.Vol.33B. P. 557.

71 METALLIC ELECTROTHERMAL ATOMIZER WITH Л PLATFORM j лАБ-49 Ju.M.Sadagov, S.V.Petnkhov, I.A.ZemBkova

Seientific and technical complex "boyuztsvetmetavtomatika"f Noscow, UJ&3 The most importaat requirement for performing AA analysis with non-adequate calibration solutions is evaporation of a liquid sanple from a platform inside a furnace heated up to a constant temperature. Platform heating delay depends on mecha - aical contact of the platform with the furnace. A metallic fur­ nace with a metallic platform is described. It's important to stress that the furnace design excludes any mechanical contact of the platform with the heated surface of the furnace. The furnace consietes of two similar sections under over lapping farming tube cavity. The aide parts of over lapped sec­ tions are taken into conductive cooling contacts. The platform looks like a cup with a holder which is fixed between the fur - паев parte. Such a position of the cup-platform is particularly good for manual samples. The cup is located in the central zone of the furnace and doesn't touch its heated parts. Power is applied to the side surface of the furnace all along it's length; by this way space homogeneity temperature is provided. Rapid heating of the furnace (epprox.4000c C/S) and stabilization of equilibrium temperature is provided by feedback temperature control.

Measurements were carried out at in AA spectrometer with background correction by broadening of spectral line. Integra­ ted values of adeorbance signals were used. Characteristic ras- ses of silver (328-1 nm) and gold (242.8 nm) are 8,5 and 78 pg в, respectively. HSD of AA measurements is equal 0.05-0.05, if solution volume is 20 1. The applicability of non-adequate solutions for determine - tion of lead in a chloride matrix was shown.

71 SOLVIHT ECTKACTIOH-ATOMIC-ABSOHPJIOir AHAEfSIS OF NATURAL SAMPLES AAS-50 A.I.Saachuk Institute of Geochemistry and Physios of Minerals, Ukrainian S3H Academy of Sciences, Kiev, USSR Atomic-absorption spectroscopy (A/) is one of most effective method» to solve analytical problems in modern geochemistry. How ever, direct At determination of low elements' concentration la natural waters, soils and rooks is still not usually possible due to interference of accessory microcomponents into the AA-signal. Combination of AA method with extraction is a way to increase its sensitivity and selectivity. Here the results are discussed of Mo-, 7-, Cu-, Pb-, Hi-, Ca­ che lates behaviour study with N-benzoylphenylhydroxylamine, H-cyn- namoylphenylhydrorylamine, ammonium diethylthiocarbaminate, acetyl- acetone, carbonic acids in graphite furnace and flame. It has been found that AA-signal value is greatly influenced by properties of both extraction agent and the used organic solvent, including their volatility and thermal stability. Comparison of atomic ab­ sorption dependence on temperature at ashing stage and that of A on 3/T enables the author to conclude that atomization mechanism and AA-signal value depend on composition and nature of a metal- ligand bond in a complex. Surface of the furnace and atomization products have undergone electron-microscopic investigation. A possible chelates' atomiza­ tion mechanism in the graphite furnace is diecussed as well as chelate extracts' aerosol formation and transport into the flame of a furnace. Sensitivity values have been compared, obtained from the analy­ sis of extracts and aqueous solutions. Procedures of extracts' mo­ difiers use have been considered to eliminate matrix influence and to increase the analytical signal. •Che obtained data have been used to work out extraction-atoaie- absorption analysis to determine Be, Cu, Pb, Cd, Hi, Mo and V in natural water, sewage, soils and rocks.

Я FIAS-200: OUTSET INTO A NEW ERA OF ATOMIC SPECTROMETRY

AAS-51

G. Schlemmer, 2. Grobenski, E Bulska and M. Hasel Bodenseewark PerWn-Втег GmbH. P.O. Box 10 11 64 FRG-7770 Oberlingen

Flow injection analysis (FIA) is one of the more recent developments successful appfed to various analytical techniques. In this work FIA has been used tor flams- and hydride generation cold vapour AAS for various matrices and analyte elements. The technique combines the advantages of defined sample volumes and analyte masses of batch systems along with the simplicity and easy automation of continuous flow systems.

A continuous stream of solvent interupted by smal portions of the sample Is introduced into the nebulizer burner system of the spectrometer. The whole system is constantly flushed with carrier solution between the samples. High flame stabilities and a tolerance towards solutions having extremely high concentrations of dissolved salts, result from this method of operation. By adding mixing devices to the system, on fine dilution and on ttie addition of reagents, such as buffer solutions, becomes possible. With the help of small co­ lumns, on Nne preconcentration/extraction can be performed at a speed of 2 complete analysis cycles per minute and a praconcentration fader of belter than 20.

For hydride and cold vapour generation a defined sample volume transported by the carrier stream is mixed with a flow of reducing agent, NaBH. or SnCfe respectively. Very good absolute and relative detection limits, a high sampling frequency of up to 3 per/mki and a significant reduced consumption of reagents are the main advantage of FIA over conventional methods for this field of applications. Flame hydride generation/cold vapour AAS can easily be My automated using the principle of flow injection.

74 HEW KBTHOD OP 0ОНТПГОШ1 SOURCE ATOMIC — 1 ABSOHPTIOH SPECTROHEffiX |""»-;« K.P.Schmidt, H.Becker-Rojt, S.Florek Central Institute of Optica and Spectroscopy of the Aoademy of Scienoe of the GDR, Berlin, GDR First results of atomic absorption measurements are presented In the wave length range lorn to 214 nm with a set-up consisting cf a continuum flash lamp source as a primary light source, a newly de­ veloped high resolution eohelle spectrometer end а CCD array as a detector in the focal plane of this apeetroEeter. An optical multi­ channel analyzer is used for the Interpretation of the optical sig­ nals. In this method of measurement every transmitted single flash of the primary light souroe contains all the information resulting from atomic absoption measurement: the I0-slgnal, the X-algnal and the nonspecific absorption. Because of the simultaneous measurement of the two values of intensity I0 and I with and without nonspecific absorption both intensity signals are processed with a coefficient of correlation of r«1. This means that flioker noise of the primary light source does not Influence the reproducibility of the calculat­ ed ebsorbance values.

Using a graphite furaaoe atomizer, we determined characteristic masses for Zn, Pb, Cd, Ifl, Pe for the critical wavelengths In conti­ nuum AAS from 213.9 nm to 283.3 nm. In relation to the spectral line AAS with the same atomizer and the same working condition» we found only a very small increase of the characteristic masses by a factor of 1.1 to 2, depending on wavelength. Atomic ahaorptlon with the element Hg was measured with Rg vapor In quart cuvettes at room temperature. With the peak height mode used, the relative standard deviations of absorbanes values greater then 0.1 are distinctly better then 5)8. Owing to the high intensity of the continuum source In the whole wavelength range, the measured intensities have to be stray light corrected. The stray light has a relatively small amount of about 5* in the wave length range below 300 ran.

78 PULSE METHODS OF HEBULIZaMOH Hf ATOMIC SPECTBOKETRY AAS-53 Yu.S.Shapkina, E.D.Prudnlkov Leningrad State University.Leningrad,USSR

The modern possibilities of pulse methods of mlcrovolumes пеЪц- lization In atomic emission,absorption and fluorescence spectromet­ ry nave been examined.Pulse nebulization of miorovolumes is carried out by the variation of nebulization time or after the preliminary selection of microsample and their nebulization.The optimum conditi­ ons of measurements for these methods may be realized «hen the samp­ le nebulization time is coordinated with sample ргевепсе time in ne­ bulizer chamber and operation time of registrating equipment.The mi­ nimum detection limits are reached in case of nebulization of ult- rasmall sample volumes about 1 mlctollter and leas.Here the volume of nebulizing capillar must not exceed the volume of nebulizing sample,the volume of nebulizer chamber 50-100 ml and the operation time of the registration 0.5-1 s.The absolute detection llmitB are reduced proportional to decreasing volume of sample.The absolute de­ tection limits may be decreased on two order of value and more in comparison with the method of nebulization up to oonstant signal. They reach 10 -10 g in atomic emission,absorption and fluores­ cence spectrometry of many elements.The relative standard deviation of one measurement is equal 0.01 for pulse nebulization methods. The application of pulse methods of microvolume nebulization In atomic spectrometry permits to increase the ассигвсу,speed up the deteotlos limits for mlcroamounts,reduce the interferences,widen the possibilities of concentrated samples analysis,carry out the direct analysis of the suspensions of powder samples and microanalysis from nlorosaaples.The advantages of microvolumes pulse nebulizeti- on methods permit to recommend them, as main way of measurements la atomic spectrometry with flame and plasms.The methods of pulse nebulization of mlerovolumes are easy in realization,they say be widely used on any commercial flame and plasma spectrometer.

» NEW ATOMIC ABSORPTION TECHNIQUE FOR DETERMINATION OF i—*— ISOTOPE CONCENTRATION VARIATION [AAS-54J

S.E.Sholupoy, A.A.Ganeyev, A.D.Maydurov, G.B.Sveshnikov Leningrad State University, Leningrad, USSR

Determination of isotope distribution for different elements attracts attention by geochemists. Recently they hare payed regard to the problem of mercury isotope concentration variation with 0.1% precision. Mass-spectroeetrie method isn't suitable for rutine analysis as it's necessary much time for analysis of one sample. One can determine the isotope distribution by means of atomic absorption technique and several monoisotopical sources of light. But in this case for every spectral lamp it's necessary to keep up the same optical density of absorbing atoms with high precision «hat is difficult to realise in practice.

Me suggest new atomic absorption technique for determination of isotope concentration variation using direct or reversal Zeeman ef­ fect. The analytical possibilities of this technique are shown on example of variation determination Hgi86/Hg202. It has been investiga­ ted the lnfluenoe of the optical density of mercury vapour in the so­ urce of light, the value of magnetic field,the pressure of buffer gas in the analyte ouvette and the optical density of absorbing atoms on precision of variation determination. The conditions when the optical density of absorbing atoms hasn't an effect on the result of analysis are found. Experimental realisation of one of the possible Zeeman schemes has been allowed to reglstrate the isotope concentration va­ riation with G.2£ precision for 5 minutes.

77 DEPHTOBJCB OF IBB RESULTS OP TUB SRAPHITB PURHACE I ATOMIC ABSOREPIOI ЗРВСТНОИВТНТ 01 THB USTHOD 0? UEASURDTG С^21 IHB BACKGROUID V.I.31moaova,v.G.Zlmballst, I.V.Androaova, G.H.Anoahln Institute of Geology and Geophysics, Siberian Branoh of the USSR Academy of Scionoes, Novosibirsk, USSR In this atudy th* determination of low concentration of the. preci­ ous, rare and toxic element» in natural eamples ( rocks, orea, mine- rale and fresh-, rain-, sea-, mineral water» ) by the graphite fur­ nace atonic absorption ia propoaed. Bard aaaplea were diaaolTed and when neeessory the aieroeleaenta were concentrated in organic fa*», fha A1S measurements ware вале with Perkin-Blaer inatrument aodal Zeeaan / 3030 system, graphite furnace HGA-600 and HGA-500. Corr»c tion of background were aade with the help a deuterium arc ( D ) and os the basis of Zeeaan effect ( Z ). The graphite tub»» were the standard or pyrolyticelly coated type. It ia found that the form of peak of abaorption on a display, ana- lyt value and characteristic amount depend on the eoapoaition of the eolutlona analysed. The highest amount of aalte in aolutin which do- ea not Influence on the analysis reaulta, ia 0,4 ag ml for oorrector ( D ) and 0*6 ag ml- for eorractor ( Z ). Subaequent increase of the •alts amount in the solution reaulta in the decrease of the peak ab­ aorption and in the increase of the characteristic amount. Thus cor­ rector ( Z ) proTldea the lowering of the limit of detection for a number elementa fromsolutions were theconcentration of the salts is •are than 0.4 ag ml-1. Possibilities of AAS with corrector background ( Z ) are ezpaaded by use of the analyt line In a complicated «mission spectrum of the hollow cathode laapa ( for examplej Ir 206.9 nm , Eu 333.4 nm ) and due to exception of apaotral overlaps from a near line of the ma­ trix elements ( for example> spectral interferences from iron - Cr 35719 ш sad Pe 358.1 nm, Ли 242.79 nm and re 242.82 na.Zn 213.9 am and la 213. 7 am ). In addition, the corrector ( Z ) determines the background more accurately in near and far ultra-violet, where a radiation of deuterium are la insufficient ( for examplei да 193.7nm 8e 196.0 ma, Те 214i3 nm, Sb 217'» am, Ru 349.9 nm, Yb 398.7 nm, Bu 459*4 mm, Ba 553*6 aa ). Due to It the characteriatic amount aeereaaea, particularly for the elementa with normal Zeeaan effect.

78 RJRHACE ATOMIZATION PLASMA EMISSION SPECTROMETRY IAAS-56 ».B.Sturgeon. S.M.Willi*, V.T.Luong and S.S.Barmen Division of chemistry National Research Council of Canada Ottawa, Ontario, X1A 0R9 Canada Research in analytical atonic spectroscopy is currently characterized by the introduction of noval sources or the assessment of tandem (coupled) sources. The latter, in particular, is a promising means of permitting efficient optimization of sample introduction/atomlzation and analyte excitation by decoupling these processes within a combined source . The analytical advantages of the graphite fur' ,ce (См.), when used as en etomlzatlon device, are well recognized - furnaces offer the possibility of subjecting the sample to controlled thermal pretraatnent (for matrix management), economy of sample, relatively long residence times of analyte in the vapor phase and high absolute efficiencies. Interest in the furnace as an emission source stems from the desire to achieve multielement capability. The limitations of a purely thermal mechanism of excitation are well recognized [1]; hence, the coupling of nonthermal excitation processes, with GF atomization have been pursued C2-5J. The FANES technique, with either the low pressure hollow anode or cathode, has demonstrated the power of this approach. Unfortunately, these low pressure discharges are incapable of taking full advantage of the GF technique - analyte residence times are short and the added complexity of working at low pressures is inconvenient. Optimal use of the advantageous features of Furnace Atomization can be made by establishing an atmospheric pressure rf Plasma inside the tube for use in Emission Spectrometry (FAPES). This novel source permits the tandem coupling of the furnace and a plasma In a single convenient unit. The advantages and analytical potential of FAPES will be discussed and figures of merit characterizing this source will be presented. References

1. Llttlejonn D. Anal. Proc. 1988. V.25. P.217. 2. Falk В., Hoffmann E., Ludke Ch. prog. Anal. Spectrosc. 1988. V.ll. P.417. 3. Ballou jr., Styrls D., Harnly J. J. Anal. At. Spectrom. 1988. V.3. P.1141. 4. Liang D., Blades M. Spectrochim. Acta. 1989. V.44B. P.1059. 5. sturgeon R., Willie S., Luang v.. Barman S., Dunn J. J. Anal. At. Spectrom. 1989. V.4. P.669.

7» SAMPLINB OP SUSPENSIONS OP SELECTIVE SORBENTS AAS-57 FOR GRAPHITE FORNACE ATOMIC ABSORPTION SPECTROMETRY L_

Z.Slovak Research Institute of Fore Chemicals, LACHEMA, Brno, 5SPR

The sampling of slurries of selective sorbents [l] is advantageous for real analysis. The concentration and selective separation of the analyte Ъу sorption on an appropriate sorbent can be made with the fresh sample and is followed in the laboratory Ъу the direct GF AAS determination with no or minimum chemical treatment. The problems with blanks are herewith dramatleally diminished. It Is easy possible to prepare standards for calibration Ъу sorption of known amounts of the analyte on the same sorbent. These standards are fully Identical with the samples» The advantages of the proposed method are demonstrated on the use of selective sorbents SPHEROlr-oxine and SPHEROJT-thiol (LACHEMA Brno, Czechoslovakia) [2-4]for determinations of As, Se and other elements.

References 1. Slovak Z. // Anal. ohlm. acta. 1979. Vol. 110. P. 301. 2. Slovak Z., Slovakova S., Smrz M. // Ibid. 1975. Vol. 75. P. 127. 3. Slovak Z., Sarz M., Dooekal В., Slovakova S. // Ibid. 1979. Vol. 111. P. 243. 4. Slovak Z., Dooekal B. // Ibid. 1980. Vol. 117. P. 293.

M KSCHANTSM OF ACTIOS OF PALLADIUM AHD HIOKBL AAS-58 MODIFIERS IH ВТ АА8

S.Tikhomirov, A.Blagin, A.Volynsky All-Union Research Institute of Organic Synthesis, Moscow, USSR V.I.Vernadeky Institute of Geochemistry and Analytical Chemistry of the VBSB Academy of Sciences, Moscow, USSR The reduction of Pb and Ga oxides with graphite has Ъееп studied within the temperature range I0O-I0OO°0. Bruker FT-IB spectroaeter IFS-IIJv with GO interface was used for the de­ termination of gaseous products of the reaction. It has been found that Pd chloride decreases significantly the tempera­ ture of PbO and GaoOi reduction with graphite, while nickel chloride accelerates the reduction of GagO. only. The con­ clusion is made, that Hi and W salts promote the reduction of analytes compounds (in atomic absorption measurements) at relatively low ashing temperatures. The resulting free ele­ ments form intennetallic compounds or solid solutions with metallic И and Hi thus reducing or almost eliminating losses of analytes due to sublimation of halides, oxides, diners and other compounds. High efficiency and universality of K. modifiers are caused by the fact that Fd metal can be easily formed from its compounds and also oy unique cataly­ tic properties of metallic Fd.

6.3ax.4I3 INFLUENCE OF ORGANIC SOLVENT - WATER MIXTURES /.,„ гл ON TRACE ELEMENTS DETERMINATION IN ATOMIC ABSORPTION l**S-59 SPECTROPHOTOMETRY AND INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION SPECTROMETRY S.Vidovld1, M.Todorovid2, Z.I1I<55 A Chemical Industry "Saponia", M.Gupca 2, 54000 Osijek, Yugoslavia о Department of Analytical Chemistry, Faculty of Science, Studentski trg 16, 11000 Beograd, Yugoslavia 'institute "B.KidriS", Vinja, 11001 Beograd, Yugoslavia

The influence of organic matter on trace elements determina­ tion is of importance when sample solution contains an organic matter that can not be eliminated. That is the case with samples soluble only in organic solvents (also in mixtures which contain organic solvents) or when organic matter is a consitituent of the molecule which contains the particular element. This paper describes the investigation of the effects of organic solvent - water mixtures on the signal emission intensity and the apsorption intensity for the trace of Ca, Cd, Cu and Fe using ICP and AAS. The following organic solvents were used: etha- nol, ethylene glycol, glycerol, dioxan and acetone. The mixtures contained from 1 * (v/v) up to 40 % (v/v) of the organic solvents. The correlation between the signal size and the physical properties of the mixtures (density, surface tension and viscosity) is also discussed in it. The instrument operating conditions were the same as those for water. It is characteristic for the ICP that the small contents of the organic solvent, 1 % (v/v), in the mixtures influence the emi­ ssion intensity in the plasma and that such influence is different from element to element, "tger contents of the organic solvents in the mixtures, with the exception of ethylen glycol and glycerol, extinguish the plasma. As regardsthe AAS, the small contents of the organic solvent, К (v/v), In the mixture do not Influence the absorption signal,with the exception of acetone, but the influence can be seen for the concentration of 5 % (v/v) and more. Bafмодою

1. Kumuaaru T. at al.// Freaenius Z. Anal. Chem.(1967) 327.P.777-781. 2. Ebdon L, Evans H., Barnett N.V. // J.Anal. At. Spectrom. August 1969. Vol.4. P. 505-508. 3. Lakatos I. // Acta Chi». (Budapest) 76. 1973. 4. Lakatoa I. //Acta Chin. (Budapest) 82. 1974.

M ИРШИГСВ OP ТНВ ORGAHIC SUBSTAUCBS OH THE PROCESSES I* THB GRAPRTTB ATOMIZERS FOR ВТ AAS IAAS-60 A.B.Volynsky, B.H.Sedykh Vernadaky Institute of Geochemistry end Analytical Chemistry of the USSR Academy ol Sciences, Moscow, DSSR

ЕГ IAS la used for the analysis of different objeots containing organio substances, such as biologioal fluids, organic extraote and eorbents. Asaorbio aoid and other organio BUbetanoes are used as matrix modifiers. Therefore the detailed study of the organio substanoe Influenoe on the processes in the graphite atomizers has been undertaken.

1. It has been proved, that the heteroatoms from the organio substances influenoe mainly on. the analytical signals for the organic eztraots analysis. Chlorine from 001. and CHOI, suppresses Ho and Sn signals. Sulfur from sodium diethyldithlooarbamate and from thenoyltrifluoroaoetone suppresses Sn signals. Hiokel from niokel diethyldithiophosphate increases sensitivity for Sb, As and Те.

2. Active oarbon and other C-oontalnlng produots of the thermal destruction of the organio sorbents "POLIORQS" type Increase the reduotion properties of both graphite furnace gas phase and the surface, la a result the concentration of oxides In the STA gas phase is decreased, for Cu, Co, Hi, Au and platinum group metals the signals shift to the high-temperature region. The maxlma ashing temperature increases for As, Cd and Pb In the presence of sorbents.

3. Ascorbic aoid aotion in the graphite atomisers is also multifunctional. Aacorbio acid eliminates the Influenoe of boron and chlorine compounds for tin determination. In the first case active oarbon bounds boron Into thermostable B.O(e). Asoorbio aoid decreases free oxygen concentration in the ИА gas phase. As a result sensitivity for the elements with strong volatile monoxides suoh as boron Increases.

M USER ATOMIC ABSORPTION ANALYSIS OF NATURAL AHD TECHNOLOGY OBJECTS AAS-61 B.K.Yulfson Vernadsky Institute of Geochemistry sad Analytical Chemistry, Academy of Soiences of the USSR, Moscow, USSR The method of direct atomic absorption analysis of powder samples with atomization of the substance in the laser torch from the graphlte- -containing target is developed. The method enables detection the raode- rately-volatlng elements within the detection limit n.10"' - n.10" %. The analysis of different substances (rocks, minerals, plants, soils, biological samples, etc.) Is performed with the standard samples pre­ pared on the base of pure graphite powder. Up to 200 determinations may he carried out from 100 ag of the sample. The powder sample is mixed with the graphite powder and is pressed under a pressure of 600 MPa-om into the tablet (target). The laser radiation (free generations conditions, pulse duration —1ms, energy 2-4 J) is focused on the surface of target. The pulsed hollow cathode lamp (pulse duration 40-60 mice) is used as primary light sources. The torch length is 55-60 mm. The measurement of the analytical signal is carried out on the torch axis at a distance of 15-17 mm from the tar­ get. An experimental investigation of the number of optical and power characteristics of the laser torch from a graphite-containing target is developed. Based on the analysis of literature and experimental data a hypothesis of thermodynamic equilibrium in the analytical zone of such laser torch has been justified. The equilibrium thermodynamics methods hare been used to calculate the gaseous phase composition in this zone and the atomlzation degree of the number elements. The model of the process of substance atomization is proposed. It allows to ex­ plain the specific feature of such torch as an efficient atomizer of the solid samples. It is shown that the reduction of detection limits of elements may be attained by using intracavity recording of atomic absorption.

M ON-LINE COUPLING OF FLOW-INJECTION PRECONCENTRATION WITH AAS-62 GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY B. Welz, M. Sperling, Z. Fang Department of Applied Research, Bodenseewerk Perkin-Elmer GmbH D-7770 Uberlingen, FRG

On-line preconcentration of trace elements with ion exchange [l] or sorbent extrac­ tion [2] columns using flow injection

FI techniques were used to develop an efficient on-line sorbent extraction precon­ centration system for GF AAS. Bonded silica with octadecyl functional groups (C,.) was used as a sorbent in a 15 uL conicaily shaped micro column. The diethyl dlthiocarba- mate chelate of the analyte element was farmed on-line, loaded on the column for £0 s, washed with deionized water and eluted into a collector tubing. The fraction of the eluate bolus containing high analyte element concentrations was pumped intu the graph­ ite tube. A 25fold enhancement in peak area sensitivity compared to the direct intro­ duction of 50 uL was typically obtained with £0 s preconcentration. The complete cycle of operation took 150 s which conveniently fitted into the time interval between suc­ cessive graphite furnace firings. Determination of Pb in sea water samples showed that the interfering matrix was almost completely removed during preconcentration, and de­ terminations were made without using chemical modifiers. Results obtained for sea water standard reference materials using matrix-matched standards are given in the following table. A detection limit of 0.003 ug/L (3 a) was achieved for lead with 60 s preconcentration.

85 Sea water standard ~ sample loading Concentration (yg/L Pb) reference material period (rain) certified found

NASS-2 39 ± 6 37 ± 2 NASS-1 251 * 27 2o7 • 6 CASS-2 19 + « 22*1

The results show that the principles and techniques of Fi could be exploited to im­ prove the performance and extend the capabilities of GF AAS. It is quite exciting to anticipate the vast number of possibilities for further improvment of the GF AAS tech­ nique when the wealth of chemical literature on ion-exchange, chelate formation, and solvent extraction is reexplored in the context of a new solution handling concept. The combination of GF AAS with FI automated on-line sample manipulation and with the appropriate chemistry could create new analytical systems with unrivaled sensitivity and selectivity.

References 1. Fang Z., Welz В./У J. Anal. At. Spectra». 1989. V.4. P.543 2. Ruzicka, J., Amdahl A.// Anal. Chlm. Acta 198?. V.216 P.243 3. Backstrom K., Danielsson L.G., Nord L./V Analyst 1984. V.109 p.323 4. Nakashina S., Sturgeon R.E., Millie S.N., Berman S.S./7 Fresenius Z. Anal. Chem. . 198B. V.330 P.592

M TaSHOCHMICAL RSAGBTS АЛ) THBIR USB II THB ATOM I tig- I ABSORPIIOI DBTBRHIHATIOB op вьшаитз op «ив IV-VA jAA8*63| MBIODIC GROUPS A.B".Zeknarya, A.B.Obebotaryev Odeaaa Stat* Unlverlsty, Odoaas, USSR Xhermoebemical (buffer) additives find wide application in the practice of emission and stout-absorption spectral analysis. Inc­ luding that for the determination of elements of the IV-VA perio­ dic groups In industrially-manufactured objects end in objects of the environment. In each specific ease, the scientific substantiation of their selection determines the expected analytical effect. Thus, when determining the above-mentioned elements, the knowledge of the chemistry of high-temperature processes which take place in elec­ trothermal sprayers ЖГ8 in the presence of chemically active reagents is an important and vital problem. Ihla work has been devoted to the study of peculiarities in the behaviour of Ge, Sn, Fb, Sb end Bi when they are determined by the flameless atom absorption method in solutions as well as la some other hard, powder-like materials (industrial and natural) in the presrnce of various sulphidizing and other thermochemical reagents. In the determination of the above elements solutions, en elec­ trothermal graphite tube served as a sprayer, and in ease of stu­ dying the powder-like hard samples, a device of "flame-furnace" type was used.

The effaot of HCI0A. HH+C1, ЙН4ВГ4, HB?4 and its darivativea, fluoroplaatio-4, CdBr2, AgBr, Cdl2, Agl. AgOI, salts of Hi, Kg Mo, W, Zr, thiourea sulphur, (SH.IjS, №.10,, HH.HgJO., H.P0., ascorbic acid, EDTA on the nature of evaporation and atomlsation of microquantities (1И0-9 - 4'10"7g) of the above listed ele- aanta has bean studied. She data obtained have been scientifically interpreted and __ used In the development of sufficiently simple methods for en atom- absorption analysis of various material».

«7 ELECTHOTHEEMAL ATOMIC ABSORPTION ANALYSIS OF HIGH | AAS™fift ТИ1РЕЙАТ0НВ SUPIBCOHDUCTING MATERIALS I N.K.Beleky, L.J.Ochertianova, I.B.Chaplygin, B.A.Tishenko, V.B.Lasarev N.S.Kurnakov Institute of General and Inorganic Chemistry of the Academy of Sciences of the USEE, Moscow,USSB Lantanum and rare earth elements are metals with a тегу law sensi­ tivity of detection in flameng atomic absorption analysis. This sen­ sitivity is two steps lower than that of ordinary metals. Metals be­ longing to superconducting ceramics, with a few exeptions, are high temperature carbide forming elements and as a result of this their sensibility of detection is reduced. The lining of the inner surface of the graphite furnace with tan­ talum foil allows to increase the sensitivity of detecting elements a short term of work of the aetal lining is its short-coming. In PL] 100 heating cycles were performed under the temperature of 2550°C, after that the edges of the lining began to break and it had to be changed. It has been proved /2/ that to meet the main lining demands: to eliminate the contact of a substance with the graphite of the fur­ nace wall and to decrease the interaction of gasiform carbon with the substance under high temperature in the volume of the furnace, it is not necessary to use the lining for the whole or the greater part of the furnace (as in Я/), it is enough to take a narrow ring in high temperature part. The resource of electrothermal atomiser (the num­ ber of heating cycles) increases 4-5 times, the sensitivity changes slightly in this case. The lining of graphite furnace by means of a ring with the length equal to I/16 part of the furnace length gives highly sensible,well- working atomizer with a hightened accurateness of detecting elements. Optimum conditions have been chosen to detect elements belonging to high temperature superconductors, in the electrothermal atomizer with the ring, mentioned above, on the atomic absorption spectrophotometer Ferkin-Elmer 403 with the atomizer HGA - 72 in mycrocrystals, film, powder. Beferencea 1. L'vov B.V., Hikolaev T.G., Norman E.A. // Journal of Analytical Chemistry. 1988. Vol. 4J, II I. P. 46. 2. Belsky H.JC., Ochertyanova L.T., Shaplygin Т.Б. et al. // Journal of Analytical Chemistry. 1989. Vol. 44, К 4. P. 646.

88 HIGH-FREQUENCY EbBCTRODLESS LAMPS WITH COHBDJED |"S-65 UERCURY-CADHIIK PILLIKO D.X.Bersinye, S.Ya.Futninya, G.V.Bevaiae.A.Ya.Skudra

Department of Optics and Spectroscopy, Latvian State Ibiveraity, Riga, USSR High - frequency electrodleee discbarge lamps (SSL) are used as the most intensive atomic spectral sources in analytical spectros­ copy. The idea to produce multielement EDLs «nice emit spectra of all the components at the same time attracts the attention. She conditions of high frequency discharge strongly depend on pressure and components of the filling. Therefore It's important to limit the volatile mercury component in the lamp to provide the stable cadmium discharge* He have performed new stable and longlived SDLs with intensive, narrow mercury and cadmium spectral lines over the wide spectral range. Figure shows the absolute intensity chance of the stron­ gest spectral lines of the combined lamps depending on current of the exciting generator ППЫ1 - 3M.

The paper discusses the problems of th6 Cd11* - Hg202 £DL spec­ tral line profile stu­ dies in the visible and ultraviolet spectral region. The experi­ ments prove that the production of multi­ element b'DLs is pers­ pective.

Intensity of spectral lines as a function of generator current i. »A HIGH-FREQUENCY, ELECTRMlLffiS LAMPS Of MERCURY ISOTOPES AAS-бб! POR AHALYTICAL SPECTROSCOPY; D.K.Berzinya, S.Ta.Futninya, G.V.Rlvalde, A.Xe.Skudra Department of Optics end Spectroscopy, Latvian State University, Riga, USSR High - frequency electrodless lamps (EDL) are widely used as the source of Intensive atomic spectral lines for respective elements. In our laboratory the research work on the optimization of BDL production and determination of their parameters is carried out |1]. Jhe spectroscopic characteristics of EDL samples on the basis of mercury isotopes are described in this work. We have done a detailed analysis of spectral characteristics for 253.7 nm resonance line. The profiles of spectral line are investi­ gated by means of a pressure - scanned Fabry - Perrot interferome­ ter. For mathematical processing of the experimental data curve - fitting method is employed. In the mathematical model resonance trapping on complex profile spectral line is taken into account according to real Voigt'a profile. The definite temperature is 500 - 600 К for emitting meroury atoms in 3DL. Sffect of resonance quanta trapping distributes intensity of components on hyperfine and isotoplo profile structure. There­ fore cardinal emission profile changes for 253.7 nm line take place in case the lamps are filled with asperate isotopes, taking into account impurity of other mercury isotopes, experiments prove that in case of stronger excitation regimes even for 99.3 % purification the structure of emitting spectral line has a little distinction on comparison with lamps filled with natural mercury. She analysis of the obtained results enables to optimize fillment and SDL excitation regimes for their qualitative application in accomplishing different spectral tasks. Reference l.Putninya S.Ya., Silinah Yu.A., Skudra A.Ya. at al. // Prac. IX CANAC Heubrandenburg (DDR), 1986. P.232. ВЕТЕЮПНА'ПОИ OP АЫСАЫИЕ METAL IMPURITIES IN | .,_ ,_ AAS-67 HIGH-PURITY MATERIALS BY ETA, I LI ATOMIC ABSORPTION TECHNIQUE E. S.Blinova, I.D.Ouzeyev, V.N.Antonov, V.G.Miakaryants State Scientific Research and Design Institute of Bare Metal Industry, Moscow, USSR The presence of mlcroquantlties of alkaline metal impurities af­ fects the quality of materials used in electronics and laser produc­ tion. The task of sodium and potassium determination under the concent­ ration level of 1 ppm is rather sophisticated because of the large correction value of the reference experiment. There are two ways of avoiding contamination: О to use the minimum volumes of reagents during the sample pre­ paration to the analysis and to conduct the sample treatment in ana­ lytical autoclaves; 25 to analyse samples without previous chemical treatment. The possibilities of direct electrothermal atomizatlon (ETA1, atomic absorption technique in application to the determination of sodium, potassium and lithium in high purity niobium and tantalum pentoxldea, titanium nitride, niobium, vanadium and lead ruthenates, monosilane, aqua ammonia and ammonium fluoride have been studied. Thermodynamic calculations performed by the "Astra" routine allow­ ed to choose the optimum thermal regimes of the analysis and to de­ termine the composition of the gaseous and condenced phases during atomization of the investigated and referenoe samples. Water soluti­ ons of the alkaline metal Baits were used as the reference samples. The kinetics of sodium, potassium and lithium atomizatloD from dry solution residue and solid sample was studied in the graphite furnace "HGA - 72». The possibility to use solutions as reference samples in solid sample analysis is established. Reference 1. Sinyarev O.B., Vatolin H.A., Trussov B.G., Molsseev G.K. // Pri- menenie BVM dlia termodinamicheskih raschetov metallurgieheakih prozessov. M. > Nauka, 1982. S. 263.

tl DBTERMIKAraOH OP ARSHJIC AIID SELEHIUM 1Я 1 T~—AAS-68 HTGHbr MUfHlAUZEO) WATERS BY FbOW-IHJECTIOB I HTDRTDE GENERATION AAS G.Bozsal, M.Sohubert-Jacob», B.Welz Department of Applied Research, Bodenseewerk Perkin-Blmer & Co GmbH, Uberllngen, FRG on leave from National Institute of Hygiene, Budapest, Hungary A simple and automated method is desirable for the routine analy­ sis of water for trace elements Including highly mineralized water samples. The method should be free from interferences over the con­ centration range of the ooncomltants. For public health protection the analytical method should be able to measure 10S of the maximum allowable contaminant level in drinking water. The graphite furnace and/or hydride generation AAS are the analytical techniques which шву fulfill these requirements. Two special Hungarian mineral waters used for medicinal purposes were selected for this study. These waters contain 20-40 gl of salts, mainly as sodium and magnesium chlorides, bicarbonate» and sulphates. A Perkin-Elmer Model 2100 atomic absorption sptotrometer equipped with s PIAS-200 flow-injeotion hydrite generation system was used. Arsenic was determined after KI-ascorbic acid pre-reduction. Se(VI) was reduced with HC1 by the heating of the solution at 80° 0. Sample volumes were 40 piL and 500 pL for As and So, respectively. Recoveries of the spiked additions ware found 100* for both of elements. The limits of determination (4.65 в ) were 2.0 MgL for As and 0.2 MgL for Se. Comparing these data with the performance of the graphite furnace AAS [\J It can be concluded, that in the presence of high sodium sulphate matrices the flow-injection hydride generation method Is more favourable. There are no interferences, which may ooour In the graphite furnace. The sensitivity for Se is one magnitude higher than In case of G7AAS. Reference 1. Bossal 6., Schlemmer G., Grobenski Z.Determination of As, Cd, and Se la highly mineralized waters by GFAAS // Talenta, accepted for publication

M DETERMINATION OP As, Bi, Sb, 3n, Те BY ATOMIC ABSORPTION SPECTROSCOPY AAS-69 I.A.Brovlco, A.Davirov, Sh.Ishnijazova, M.A.Rish, A.Tursunov, D.Shakirova Samarkand State University, aaoaritand, UAS.4 An AA3-technique has been developed for qualification of hyd­ ride- forming elements, involving generation of hydrides, their thermal decomposition, concentration inside as electrothermal ato­ mizer and subsequent atomization. The determinations were carried out with a "Saturn" spectrophotometer equipped with an electrother­ mal atomizer, furnace length-90, inner diameter - 6 and wall thick­ ness - 1mm. Spectral sources were high-frequence electrodeless lamps ВСБ-2. Analytical wave lines: As-1^7-2i Bi-223.0i cib-217.6; 3e-204.0i 3n-224.bj Te-214.2 nm. Potassium hydride solutions were used for evolving hydrides, the concentration for Те being - 1.5* for the other elements - 1 J, and a sample to reactant ratio 5J1 (v/vj. HG1 concentrations in test solutions for SD were 0.1; Те - 5.0 and for the other elements - 2,0 ii. for As and Se - determinations preliminary coating of the internal surface of the furnace with a Sb-iilm (mass 15+5 ugj was employed by introducing SbHj into the furnace preheated to 570+15 ii in its central part. Impurities of As and Se were removed by further raising the temperature to BOO К after which followed she deposition of As or Se in the furnace. For an lining of the furnace with a J,1 шш Та foil was employed. The flow rate of the gases from tne generator, set by the feed­ ing rate of the reactant solution was for Te-00+5, and for the other eleaents - 15+5 ml-s'^.The temperature of the central section of the furnace was: for deposition» ofi As-575+25 K, Bi-400+15 K; 3e- S25+ 15 K, S-n-500+^5 Ki Te-570+15 K. Atomization of Bi, Те, Se was car­ ried out at 2000 К, of 3b and As - at 2500 X and of on - at 2900 K. The recovery of the eleaents was 92+4J6. The method was verified with roci reference materials ГС0 3032- -d*(copper-molybdenua stern ore;,E00 7#*-?<= rus 4 (copper-zinc sul­ fide skarn ore.). The lower detection limit equalled for As-Ji hi 16; Sb-0,45; 3e-90i 3n-0,60i Te-0.50 ug. At element contents exceed­ ing 5 С , the relative standard deviation (ns5; did not exceed 0.12.

И STUDY OF CONDITIONS FOR COBALT DETERMINATION IN BLOOD A4S-70 SERUM BY ELECTROTHERMAL ATOMIC ABSORPTION SPECTROMETRY

E.BulBka. K.WrObel *. B.Godlewska ** * Chemistry Department. Warsaw University. POLAND ** Chemistry Department, Warsaw University. Branch in Biaiystok, POLAND

Cobalt, as a component of vitamin Bl2. belongs to the essential elements in human body. It acts also as nonspecific activator of many enzymes. Daily intake of cobalt for healthy person is 0.2 to 0.4 ug/kg.

It is absorbed through digestive tract as vitamin B12, but also by respiration in inorganic forms. Large doses of Co may accumulate in liver and kidney. Normal cobalt content in blood is 0.1 to 0.6 ng/ml. Sensitivity of ETA AAS determinations ranges from 0.04 to 2.0 ng/ml of cobalt. It is impossible to use simple dilution of serum to eliminate matrix effects. Many pretreatment procedures are reported in the literature. Among them there are digestion with mineral acids, cobalt separation from matrix by extraction into organic phase or by ion- exchange chromatography. All these procedures are time' and labour- consuming, and this can increase the risk of sample contamination or losses of analyte during procedure. On the other hand, application of sample dilution procedure combined with matrix modification technique in many cases leads to excessive results. This may be connected with spectral interferences occurring when large amounts of protein are present in the sample. It may be concluded, that contamination control and optimisation of analytical procedure is an important problem in the case of Co determination in serum. In this work the conditions of atomization for Co were studied. The influence of inorganic acids, their salts and serum albumin on analytical signal of Co were investigated. The selection of interfering agents was based on possible composition of final solution obtained from serum sample. The choice of matrix modifier was also takes into account. The problem of sample contamination in every step of analytical procedure was also studied. For this purpose blood sampling, serum preparation, sample storage, pretreatment procedure and determination were treated separately. Each of these steps was performed independently for standard solutions of Co (aqueous and serum standards ). The changes in Co content in these solutions were investigated. The obtained results facilitated the qualification and elimination of the systematic errors in analytical cycle.

M GRAPHITE FURNACE ATOMIC ABSOBFTION ANALYSIS Г~~— OF BIOLOGICAL AHD VEGETABLE SAMPLES WITH Л |AAS-?1 DIRECT AXOIIISATIOH OF PARTIALLY CARBOHAZE» MATERIAL U.Burilin, G.Grinkina Horth-Caucasian Research Institute of Oattlebreeding, Krasnodar, USSR B.L'vov Polytechnical Institute, Leningrad, USSR Among different methods of sampling of materials into graphite furnace for atomic absorption analysis, the injection of water sus­ pension is the nost simple one Л/. As it was demonstrated, the samples of plant and animal tiBsuee as well as samples of food pro­ ducts is desirable to introduce into the atomizer in partially car­ bonated state (250-500°C). The state of materiel after this temperature treatment was inves­ tigated using the methods of differential thermal analysis, electron spin resonance and scanning electron microscopy. The dipth of struc­ tural conversion and degree of coke formation were determined. These data permit to select the temperature and time of the pyrolisis stage. The results of atomic absorption analysis are in satisfactory ag­ reement (the relative error 10-15$) with certified values for Co, Cd, Cr in etbcAard reference materials of wheat grain and potato tubers. At the concentration level of 10"*#, RSD was 6-8*. The values of characteristic masses ft/ were used for a quantitation of the analy- tes. Background correction with a continuum source was ueed. References 1. Miller-Ihli H.J. // 3. of Research of Hational Bureau of Stan­ dard. 1988. Vol. 95- P. 352. 2. Instruction Manual. Techniques in Graphite Furnace Atomic Absorp­ tion Spectrophotometry. Ferkin-Elmer Corp. 1985. Fart Number 0993-8190. F. 106. GRAPHITE PURNACE ATOMIC ABSORPTION SPECTROMETRY FOR I 1 AAS-72 SPECIATIOH 0? СШИШШ IK HATDHAL WATERS I 1_! J.R.Castillo, J.H.lIlr, P.Haborda Department of Analytical Chemistry. University of Zaragoza. Spain Experimental approaches for chemical speciation of trace elements in natural waters are based ins 1) analytical techniques which res­ pond to one particular chemical form of an element, 2) preliminary separation steps and determination of the concentration in the ob­ tained fractions. A type 2) methodology have to be used in a epeclation scheme for chromium, due to selective instrumental techniques as anodic stripp­ ing voltammetry cannot be used directly for this element. In this paper we describe the use of Qraphlte Furnace Atomic Absorption Spect­ rometry (SPAAS) in speclation studies. Although GPAAS is a very sen­ sitive technique, it le non seleotive and we made up for this lack by a previous extraction step. River water samples were •analyzed. Solid content was 2 g.L~ (Fe 3.5*, an 0.2», Ca 10.9%, Hg 2.256, Al 9.11%, Ti 0.3%, Cr 0.01%), hard­ ness was around 130 mg.L . Soluble chromium was in the range of 0.1- 0.2 fig.L and total ohromiuo 0.1-0.2 mg.L . The scheme is based oni 1) determination of total chromium in the Whole sample and in the filtrate (0,45 pm). 2) differentiation of Cr(iri) and Cr(VI) both soluble phase and preolpited one. Differentiation Cr(III)-Cr(VI) la based on the seleotive extrac­ tion of chromium-pyrrolidine dlthlocarbamate to 1ПВК (pH 4.5) both the whole sample and the filtrate. Cr(VI) is extracted at room tem­ perature and CrClII) plus Cr(VI) heating at 1O0°C. Extraoted chromium form the solid belongs to absorbed chromium or labile precipitates. Stabilised temperature platform furnaoe was used to determine total chromium in the whole sample with mg(!t0,)2 as matrix modifier and deuterium leap as background correotor. The suspension was homo­ genized by magnetic stirring and 20 fiL were injected directly onto the platform (drying 120*0, ashing 1600°C, cooling-down 20°C, atom- ization 250000, cleaning-up S650°C). Relative standard deviation was In the range of 2-3%. Results obtained by acid digestion of the samp­ le (НР-НИ0,, olosed reactor) were In agreement with those obtained by the direct method (average reoovery 99+7%). Organic extracts, after separation by oentrifugatlon, were inject­ ed directly Into the graphite furnaoe (drying 120°C, ashing 500»C, atomlaatlon 2300*0, cleanlng-up 2650°C). Relative standard deviation was in the range of 1-2%. Determination was free from Interferences.

И DETERMINATIOH OF SOME ORGAMOHETALLIC COMPOUNDS OF IV AND AAS-73 VI GROUP ELEMENTS BX CmOMATOCRAPHY-AIOMIC-ABSORFTION SPECTROMETRY

V.T. Demarin, Ye.V. Portnoya, U.K. RudneYsky Research Institute of Chemistry, Gorky State University, Gorky,USSR The combination of chromatographic and atomic-absorption methods of analysis was used in the determination of organoailicon and tellu­

rium compounds: (CK^Si, (CH^SiCl, CHjSiHClg, (CH3>2Ie, (C2Hg)2Ie. An experimental deriee consisted of TsYet-152, 500 gas chromatograph and Saturn atomic-absorption spectrometer with a graphite or quarts atomizer. Organosilicon compounds were separated on a glass column (5m x 4mm) packed with Chromaton with 15% of 'Squalen1 and organotel- lurium compounds on a column (3m z 4mm) packed with Chromaton with 15% of SE30. After chromatographic separation the тарогв of components analysed were successively passed in a helium flow through a thermo- atatted connecting pipe Into the atomizer. Atomic absorption bands for SI and Те were recorded at 251-1 nm and 214*3 nm, respectirely. With integral absorption measurement a graphite furnace was heated to the temperature of atomization during the period of passing of all the anylitee through the atomization zone, while measuring the atomic ab­ sorption from a peak height the preliminary thermal decomposition of organosilicon compounds was carried out at 750 К with the decomposi­ tion product accumulation on inner walls of the graphite furnace, and the atomization was performed at 2720 K. Ibis permitted to decrease the detection limits by a factor of 5-6 in comparison with the values of integral absorption. The dependence of tellurium absorption on the quartz furnace tempe­ rature and the rate of hydrogen feed Into the atomization zone has been studied. The calculations of temperature dependence of Globe function iC°) for the decomposition process of dimethyl- and dlethyltellurlum in the presence of hydrogen and without it were made. The decomposi­ tion of alkyl compounds of tellurium In the presence of hydrogen was shown to occur easier. An appreciable reaction of dimethyltellurlum decomposition is possible even at 500 K. The detection limits of organoailicon and -tellurium compounds were calculated to be 2.10 -10 g. The determination technique of organo­ silicon compounds In silicon tetrachloride and diethyltellurium and dimethyltellurium In diethyltellurium was developed. The relative deteotion limits are equal to 2.10""-5.10"*wt.Jt and the relatiTe stan­ dard deviation Is within 0.05-0.10.

7.3ак.413 И ATONIC AM01PTIOM вПСТЯОаСОРК ВжТШММАТЮМ OF SOHB ААБ-74 И1ТА1Л IN ШИМОРВОВЮ P., Dobrowolskl, J. Mierzwa Central Laboratory UNCS, 30-031 Lublin, Poland

The halopboaphato luninophoree for fluorescent leaps have bean studied. Tfaa salected metallic components ware determined by atoalc absorption spectrometry (AAS) in eome samples of luninophoree. The influence of halophosphate Matrix on antimony, manganese and cadmium abaorbances at C^Hj - air flame has been investigated. The determinations of heavy metals traces -included

in lumlnophoree (by using; of C^Bj - air and CjH2 - N^O flames) are compared. Instrumental parometera important in reducing matrix effects were discussed. Some traces of heavy metals were determined by graphite furnace AAS. The influence of ecids and interfering elements on their ebsorption signala haa been diecussed. The dieeolution method of eamples wee proposed. The precision and the accuracy of the results are evaluated.

И SEPARATION AMD ENRICHMENT OP TRACE METAL IONS Г~ ~" AAS-71 PROM THE SAMPLES CONTAINING HIGH SALT CONCENTRATION! ~ ВТ ADSORPTION RESINS

M.Dogan, M.Soylak, L.Elci Erclyes University, Department of Chemistry, Kayseri-Turkey

Most conventional instrumental analysis methods are not sensitive enough to be used for direct determination of most elements at concentrations lower than 10 %. In addition, even if a given element an adverse effect on die accuracy and precision of the result. In this case , the best approach is preconcentration, and separatist of the trace elements from the matrix. The use of adsorption resins for the separation and preconcen­ tration of metal ions at trace levels has substantially increased in recent years. In particular,Amberlite-XAD resins have found widespread application in this field. Because they have good physical and chemical properties such as porosity, high surface area, durability, nonpolar structure and purity.

Our working involves retention of trace metal ions t-ith tlie use of chelating agent in the column packed with Amberlite XAD-4 or 8.Chelating agents used in this work are APDC and N, N-Hexamethylenedithiocarbaraic acid, hexamethylene-amnonium salt. For this process, the aqueous solution containing of metal ions was adjusted previously to the optimum pH. and then the chelating agent was added to the buffered solution. After five minutes, the solution was passed throught the column. Finally the trace metal chelates retained on the column were recovered by elution with a small volume of a powerful eloent. The metals in the eluent were determined by FAAS. The optimum working conditions were determined with respect to the pH, the adsorption capasities of the resins, and the effect of salt concentrations in the sample solution and the number of elution from the same column.

Analyte recoveries were found at least at the 95 %. The optimum pH values depend on the chelating agent and the elements. For the elution, the same column can be used at least a hundred times. Reproducibility was 3 - X for 20 g/L Cu in pure water.Adsorption capasities for the resins were 2.1x10 rnnol Cu/1 g.resin at pK 10. ANALYSIS OF ASHES USING AAS AAS-76 M. Fara, R. Spirkovd EGU-Power Research Institute, 190 11 Prague B. Krdtke "Vodni zdtoje", 166 00 Prague, Sspfi Samples, of ashes are analyzed for Al, As, Ca, Cd, Co, Cr, Cu> Fe, Mn, Ni, Pb, V and Zn after their decomposition with hydro­ fluoric, perchloric and nitric acids using both flame and ETA AAS; As is determined using hydride technique.

Samples ate decomposed in cylindrical PTFE test-tubes of 25 mm bore, 80 mm length and 2 mm wall thickness heated in a home-made aluminium heating block electrically supplied via thyristor controller. Approx. 0,2 g of the sample in the test- tube is digested with particular acids which are fumed off in following steps:

step acid volume of fuming added acid temp. 1 hydrofluoric, 39% 2 ml SO °C 2 hydrofluoric, 39% 2 ml 90 °C 3 perchloric, 704; 4 ml 180 °C 4 nitric, 65% 2 ml 1»0 °C 5 nitric, 65% 2 ml 140 °C

Resulting total solids are dissolved in 4 ml of 65* nitric acid under heating to 50-60 °C, the solution is cooled down and diluted to 250 ml with de-ionised water.

For the determination of Cd, Cu, Pb, and Zn by AAS-ETA the platform technique is applied.

The samples analyzed are mostly ashes originating from the combustion of brown coal. The method of determination was verified using different reference materials.

In particular cases the results were compared with neutron activation analysis. DETERMINATION OF SODIOM IK SODIDM SAMS OP ЛПОГЬ AND I ; AAS-99 ! ARYL SUXPHONIC ACID BY. ATOMIC ABSORPTION SPECTROMETRY I '' I Gan Zengyuan, Gu Tianyan Research Institute of Shanghai Petrochemical Company, Shanghai, China

A large number of determination of high concentration of sodium by flame photometry and gravimetric method «as reported in the lite­ ratures. But these methods are trouble, time-consuming and low pre­ cision. Determination of high concentration of sodium by flame atomic absorption spectrometry is convenient, quick and considerable precis­ ion, if the experiment condition could be selected carefully. The ab- sorbanee of sodium was measured at 330.2/330.3 nm and optimum operat­ ion parameters of the Instrument were established by the orthogonal design and other testa. The sample was dry-ashed at 700°C in a nickel crucible for about four hours. The influenoe of temperature, time and vessel material of ashing upon the Na recovery was examined.

There are serious interferences from coexistent alkali metal in the determination of sodium by atomlo absorption apectrometry.Becauee there are only 89 ppra of potassium and trace other coexistent ele­ ments in the samples, so the Interference from coexistent elements may be ignored. Our experiment a.so showed that the interference from nickel (come from the nickel crucible) may be also Ignored. The Na recovery of this method for two samples Is between 98& and 101$. The average RSD of eight determination» for four typical samp­ les containing 6-11# Na la +0.57%.

References 1. Orba v. // Analysis. 1975. Vol. 3. P. 363. 2. Manning D.C. // Atomic absorption Newsletter. 1967. Vol. 6. P. 75. 3. Deng Bo // The Application of Mathematical Statistics in Chemical Analysis. 1981. P. 103. 4. Narasakl Hisatake // Chen. Anal.(Japan). 1972. Vol. 21. F. 284.

101 DETEfflUKATIOK OP CESIMI IN EHVIROroiEHTAL SAMPLES |ддз_„8|

ABSORPTION SPEOT80UBTSY H.Gegusch, B.Samuel Staatllohse Amt fur Atomsiehsrheit und Strahlenschuts, Berlin, om

la radio-ecological investigations for the purpose of environmen­ tal muttering the determination of stable Cs is of special interest. the aethod of flameless AAS analysis enables the direct determinat­ ion of Ce in sediment sample and ashed biological materials. The Св eonoentrationa of the environmental samples are in the range of 0,004-10 JAg/g. Investigations «ere conducted by the AAS-з and БА-3 equipment of TBB Carl Zeiss Jena. The variant of STPP - concept was used. The optimum temperatures for charring and itemization in case of glassy oarbon platform use were found to be 450 °0 and 2400 °0, res­ pectively. The platform technique brings a clear decrease of the in­ fluence of the matrix interferences for sample material.

53» influence of the matrix modifiers (ШЛО,, Hg(NO,)2,?a(ITOy2) on the volatilization of the sample material was studied and opti­ mized. The use of certified sample material from the International Atomic Bnergy Agency (i.e. sediment Sl-3, soll-7, animal muscle H-4) permit­ ted the control of the decomposition method as well as of the automa­ tic-introducing of suspended materials. О» suspension ni prepared in an ultrasonic bath und stabilized with magnetic stirring. The standard deviation for measurements by slurry atomization amounted to 30%. The detection limit for Cs in 10 fil sample volume was 0,005 ppa.

IM ATOMIC-ABSORPTION ШЕШЦНАИОН ОТ MBTALS USING THE AAS-79 IMPROVED BUHNER ADD PULSE NEBULIUATION OF SOLUTIONS !!.>:.GoncharovB,E.D.Prudnikov,H.V.Gor'becheV3k83e Irkutsk State University,Irkutsk,USSR

The accuracy and rate of metals determination nave been Increased for the atomic absorption spectrometer "Saturn" by using the Impro­ ved flame burner.This burner is characterised by executing the exit openings for the fuel gas mixture in the projection of a small mass/V*The advantages of this burner are as follows «the decreasing of blank influence and the increasing of the accuracy of the analy­ sis along with the increasing of the experiment safety.The burner Is made of titanium. Its projection being 10mm high and A mm «lde has 30 openings 1 mm in a diameter.This burner «as used for different

flames s air-acetylene tni tried) oxide-acetylene,nltrie(1) oxide-pro­ pane. The method of pulse nebulization of the seniles solutions has been used/g7.Uethod made It possible to increase the rate of analy­ sis and to decrease the Influence of nebullzatlve chamber contsmina- tlon.These results in the more effective procedures of determining metals have been developed. This technique has been used for the determination of molibdenun in the technological solutions by using an air-acetylene flame.The catalytic properties of Ho-eonteinlng catalysts of oil and coal pro­ cessing sere studied by mesne of this procedure.The relative standard deviations are equal 0.O3-0.O1 for 10-200 mg/1 nolibdenum.The sensi­ tivity of element detection can be Increased by using a nitried) oxide-acetylene flame. The techniques for the determination of manganese and iron with organlo addition by using air-acetylene flame neve been suggested. Also these techniques for the determination of calcium and magnesium for the silicate analysis have been carried out by using nitric(l) oxide-propane flame.The latter Is very perspective because of the decreasing the Influence of the sample composition on the absorption and emission of alkaline-earth elements/3/. References LPrudnikov B.D..Bychkov Yu.A.//Zh.Prikl.Spectrosc.1982.Vol.37.P.339. 2.Prudnlkov E.D. .Shepkina Tu.S.//Zh.Anal.Khim.198«.Vol.39.P.588. 3.Goncharova H.H.,Banchak L.A. .Ivanovo B.I.//Zh.Anal.Khlm.1982. Vol.37.P.2174.

IM ATMCC-ABSORPTION APPARATUS POR EXPRESS I DBTECTIOH OP SHAIi AHOUHTS OP MERCTOY |AAS-8Q

M.V.Hashchlna, I.G.Bogdan The All-Union Scientific Research Institute of Water- Protections, Kharkov, USSR V.A.Bocharov Kharkov State University, Kharkov, USSR

The most widely used apparatus for routine determination of small amounts of mercury at the ecological researches Is the apparatus for unflamed atomic-absorption control such as serlaly produced portative apparatus JtJLIA-2. In this paper we describe the new unflamed atonlc-absorptlon appa­ ratus for express determination of eubnlerogramme amounts of mercury In the sample. Apparatus Is developed for automatic analysis and per­ mits to fulfil serial measurements with 30 samples during I hour. Apparatus Includes eonjunoted In one block consequently disposed two parts: sealspherical chamber for mixing and reduotlon of sample (it Is In the same time the focusing ultrasonic piezoelectric radiator) and cyllndrlc absorption chamber. The ultrasonic field, 20-40 kHz, created by radiator, accelerates reduction of the mercury In the chamber for mixing and reduction and Improves the reproducibility of analytical results. Apparatus permit to determine the mercury con­ tent In the environment at the level of admissible concentration limit. The scheme of apparatus Is presented at the figure.

input of J* rfduc tent 25 3,7nm( )1 absorptioabsoruti n -+-• ohB'rabfr radiator input of air ") Q vacuum П output of sample

Scheme of apparatus for detection of small mercury amounts by atomic absorption method.

1M TRACE METALS IN BIOLOGICAL FLUIDS - PROBLEMS AND AAS-81 POSSIBILITIES IN ANALYSIS BY ATOMIC ABSORPTION SPECTROMETRY

Adam HULANICKI, Ewe BUL5KA end Katorzyna WRuBEI.

Deportment of Chemistry, University of Warsaw, War-saw, Poland

Determination of trace elements In biological material Is becoming increasingly important. The knowledge of reference values for trace metals Is the starting point for establishing tho correlations between observed levels and their physiological effects. The study of the Influence of the environmental and pharmaceutical treatment has elso various ecological and biomedical aspects. Among numerous analytical techniques used for these purposes atomic spectrometry ami especially atomic absorption spectrometry Is widely used, lit most cases the detection limits for electrothermal stomlsatlon are sufficient for direct determination of trace metals In biological samples, however the presence of organic and inorganic matrix components moy Interfere with the analysis. Many procedures of sample pretreatmeni have been proposed and tested for determination of cadmium, Load, mangai^s*. cobalt, olumlnlum and chromium. In some cases the use of matrix modifiers Is also advantageous. The determination of drastically low levels of elements sufiers from a number of errors, principally from contamination at various stages of the analytical procedure. The possibility of their elimination will be discussed.

1M MATRIX SEPARATION BY SOLVENT EXTRACTION PRIOR TO THACE l ANALYSIS IN rURE GOLD USING AAS АА8-в2

E.Ivajaova, N.Jordanov, I,havezav Institute of General A Inorganic Chemistry, Bulgarian Academy of Science в, Sofia lOiiO, Bulgaria the им of nigh-purlty gold In microelectronics has prompted to* Interest towards traca element determination la this metal during the last daeadaa. Several approacneo have been developed for elimina­ ting or reducing the effeot of tne gold matrix - standard addition Tl], buffering^] or matrix separation[3j. Tbe present paper deals with tlie application of the extraction system metbyletnylfcetone/ehloroform to matrix separation prior to the AAS (beta flame and electrothermal) determination of the trace element content In high-purity gold. Gold(lII) is extracted from hydrochloric acid solutions vita aliphatic saturated Icetonaa in the prasance or absence of an Inert solvent as toe species:

It was found tost tetraohloroaurate Is extracted from nitric acid medium as wall, which is more suitable for toe electrothermal AAS determination of some trace eleuenta (e.g. As, Sb, Sn, a.o.). After optimizing tne extraction conditions, tbe concentration of the mmtvlx component was decreased by mora tban k orders of magnitude, toe majority of trace elements remaining quantitatively in the aqueous solution. Tne content of Cu, Fa, Pb, Ni, Co, Mn, Cd, Cr, fd, KB awi Zn (10"'-W j») was determined by flame AAS, tne content of As, Sb, Sn, Bi, Al, Se, Те, V and P* (Ю -10"%) was determined by electro­ thermal AAS. The procedure of matrix separation was optimized in order to minimize the number of contamination souress.

References t. Moffett J.//Varian Instruments at work. 1987. No 11-75. 2. Balundina E.A., Khrapmi V.P., Judelevich I.G.// Zh. Anal. Kbia. i076.V0l.3i. P.265. 3. «erpo» Ju.A., Judelevich I.G., Gilbert E.N., startseva K.A., Kormilitsin D.V., Shuvaova O.V.// Ibid. lOSS.Tol.'tO. Р.Э7Э.

IN APPLICATION OF АТОМГС ABSORPTION KETHOD BOH ANALYSIS AAS-83 OF FERROUS METALXOHGI MATERIALS L.V.Kamaeva, L.I.Barmina, N.D.Fyodorova, N.N.Bakina ICRHs, CBIfermet, Sverdlovsk, USSB Possibilities of application of atonic absorption method for de­ termination of K, №| Zn, Pb, Co, N1, Cu, V over the range 0.001 - 1 % , Or, Ug, Ba, Ti over the range 0.003 - 7 56, Ca, Al over the range 0,01 - 20 % and Fe, Mn over the range 0.01 - 70 % in iron, man­ ganese and titaniferous ores, Kg over the range 0.001 - 3 S5, Un over the range 0.003 - 0.1 % and Ca over the range 0.003 - 3 % **• irons, steels, nickel alloys and ferroalloys are studied [.1,2] . Conditions of determination of foregoing elements by means of ato­ mic absorption spectrophotometer "Saturn" in flame atomization regime are optimized. She influence of acids and fusion mixtures used for decomposition of the sample and the influence of associated components as «ell as methods of elimination or correction of interferences are studied. The ways of matrix separation for the determination of Ca, kg, Cr, Ni and Co for their contents less than 0.003 % are proposed. Precision characteristics for a number of elements are considered. Equal precision for atomic absorption method and corresponding chemi­ cal and physioo-chemical method of determination of elements for studied ranges of contents is determined with the exception of iron, manganese and titanium.She method is recommended for iron and mangane­ se contents up to 10 % and titanium contents up to 1 % only. Procedures for determination of Ca, Kg and Al or Al,Zn,Pb and Cu or Cr and Mn with the use of one test portion in ores, and of 11, Ca, Kg, Cr and Mn with the use of one test portion in ferroalloys are elaboraited. She techniques of atomic absorption determination of foregoing elements were used for standardization of methods of analysis of iron, manganese and titaniferous ores and for certification of CBHs of fer­ rous metallurgy materials.

References 1. Slarin V.//Atomic absorption spectroscopy. L.:Khlmlya, 1971. P.296. 2. Bsrlaaov I.P., Bryomina G.V.//Atomic absorption analysis in ferrous metallurgy. M.: Hetallurgla, 19Э2. P.166.

I#7 TRACE ANALYSIS OF ALUMINIUM - DETERMINATION IN SERUM

Jifina Koreckova Institute for Glass Chemistry and Ceramic Materials of t^e Czechoslovak Academy of Sciences* Prague,

I have studied the electrothermal atomic absorption measurement of aluminium in serum samples using platform technique, A proposed analytical method covers concentration range from a limit of detection (* 2 ug.l"1) up to 1000 mg.l-1 of Al. In this range the analytical results were obtained from normal healthy people and chronic uremic patients on periodical haemodialytic treatment before and after desferrioxamine (DFO) administration. Before measurement serum samples were diluted 1+2 by Triton X-100 (0.1% solution In O.OOIM-HNO3). The use of less sensitive resonance lines instead of great dilution of samples is recommended for high concentrations. To prevent contamination all analyses were performed in the dust-free laboratory with filtrated air providing a class-100 working environment. The possibility to use a pyrolytic graphite L'vov platform

treated by soaking in a 10X-Th(NO3)4 solution was investigated. Using Th-treated platform signals of Al from diluted serum samples increase and exhibit less tailing but the results show lower values compared to atomization from an untreated platform,probably due to losses of some volatile compounds of Al. The determination of Al from Th-treated platform can be done only after digestion of serum samples involving nitric acid. The evaluation is possible directly from water calibration curve with the addition of 1000 mg.l"1 of NgCNQah. A digestion method requires great care to prevent contamination and it is somewhat time consuming. For a number of routine analyses the method of dilution of samples can be recommended with a standard pyrolytic graphite platform used for measurements.

References 1. Freeh W,, Cedergren A., Cederberg Ch., Vessman J.: Clin. Chem. 1982, 28, 2259 2. Slavin W.i JAAS 1986, 1, 281 3. Gardiner P. E., Stoeppler M.: JAAS 1987, 2, 401 4. Fagioli F., Locatelli C, Gilli P.: Analyst 1987, 112, 1229

1И D3Ti-Hi'.:lIUTI0H OP COPPER BY FLO'.'/ ПМВОТЮН J AHALY3I3 WITH MiAMrf AAS DETECTION AFTER | AAS-8g PRBCOHCEHTRATION BY 30LV3HT BXTRACTIOH V.Kuban, J.Komarek, D.SaJkova' Department of Analytical Chemistry, J.B.Purkyne University, Brno, 6SPR

The basio parameters of a PIA - FAAS apparatus for the "in-line" solvent extraction and of the FAAS detecting system using acetylene • air flame were optimized, A procedure was worked out for the determination of trace concentrations of copper after its preconcentration by solvent extraction of its chelates with ammonium pyrrolidine dithioearboxylate (APSC) into 4-methyl-2-pentanone (MIBK) from 0.2 M acetate buffer at pH 5. The limit of determination was 1Q = 2 ng ml" for the injection of 150/ul of the organic phase into a continuous stream of air as the carrier medium. The maximum loroughput was about 40 samples per hour. The method «as applied to the determination of copper in high purity waters from the secondary cooling circuit of a nuclear power station and in samples of drinking water. The data for the cooling waters were in a very good agreement with those obtained by the PIA - PAAS method coupled with precon­ centration of the copper ions on microcolumns of the Spheron Oxln 1000 ohelating sorbents and elessioal ETA AAS method. References

1. Kuban V., Komarek J., Zdrihal Z.// Collect. Czeoh. Cheo. Commun. 1989. V.54. P.1785. 2. Kuban V., Komarek J,, 6aJkova D.// Collect. Czeoh. Chem, Commun. 1989. V.54. P.2683.

IM SIMPLE PREPARATION ПГ CLOSED TXSSSIS FOR THE JUS ИЕГЕИПКАТЮТ OF GOLD AHD SILTffi IAAS-86 I.Y.Kubrakova, Ya.L.Luss, b.A.Prostyakova, H.M.Kuz'min v.I.Vernadsky Institute of Geochemistry and Analytical Chemistry, D5SR Academy of Solenoes, Moscow

Simultaneous determination of gold and silver is the nost complicated for the oarbon-oontaining rooks analysis. It's oomwoted particularly with the variety of foins in which gold presents in rooks - free its complexes with fulvio aoids up to forms sorted on the carbonized substanse. The removal of organic substances by their oxidation in opened vessels is oonsidered aa a radioal way for the elimination of organic matrix Influence on the determination. A comparison of various sohemes of sample preparation shows that the use of opened systems leads to the losses of gold as a highly volatile organio compounds. This disadvantage oould be avoided by applying of closed vessels (e.g. autoclaves developed in OIRBDUED by T.Orlova and V.Smimov). These systems make possible to reduoe the sample preparation time and reagents consumption so аь to exclude the gold and silver adsorption on the silica aoid during the decomposition. It was shown that the organio substanoss remained In solution don't prevent the separation of gold and silver from the matrix solution, so aa the AA determination of the elements. Data obtained demonstrate the best (in comparison with the other teohniQues) reprodusiblllty. For the automation of sample preparation the installation was designed whioh provides the simultaneous heating oontrol of the bottoms of six autoolaves and the cooling of their tops. The metal determination was oarried out by flame or electrothermal atomlsation in SIP? conditions.

110 CADMIUM AND LEAD DETEHMIHATIOIT IN BIOLOGICAL I AAS-87 MATERIALS BY MEANS OF ETA-AAS I ZU

H.-L.Hartln, M.Grun Institute of Plant nutrition and Ecotoxlcology, Academy of Agricultural Sciences of the GDR, Jena, GDR The control of the heavy metal exposure of the environment re­ quires the determination of the elements Cd and Pb in different en­ vironmental media. Even in exposed areas, the concentrations can be so low (e.g. grain, fruit, muscle) that ETA-AAS has to he used as analytical procedure. Due to high nonspecific absorption during the atomizing process the aatrlx of biological samples renders the ETA- AAS determination dlffloult. If this background absorption la compen­ sated for by means of a Dg continuum lamp systematic mistakes, par­ ticularly in the case of high concentrations of phosphate Ions, can occur due to an overcompensation effect [лJ. Our Investigations aimed at avoiding these mistakes by the application of в modifier and at developing a routine procedure on this basis. The presence of the modifier H-BOj leads to the formation of Cd and Fb borates in the graphite furnace, which dissociate thermlcally more easily than the corresponding phosphates. Therefore, the element- specific atomliatlon peak occurs earlier than the nonspeoific absorp­ tion due to phosphates in the highly resolved absorptlon-tlme-diagram. Thus, the element peak oan be measured free from overcompensation ef­ fects. The routine procedure is suited for biological samples with P: Cd,

5 Pb relations oft °рЮ04 <1 • 10 ; ye^ «c 3 • 10 . The working range Is

12 8 11 -7 3 • Ю" g<»oQ<3 • Ю" g and 4 • 10" < mp,, < 4 ' 10 g

The "characteristic masses n0" are

m0(Cd) « 2.1 pg/0.0044 A.s, m0CPb) - 28 pg/0,0044 А.в The accuracy of the procedure was proved by the standard addition pro­ cedure In different blologloal materials and by the analyses of refe­ rence samples (hay, IAEA/7-10)t Cd (jig g"1) Pb certified 0.03 1.6 confidence Interval 0.02 ... 0,05 0.8 ... 1,9 found (P • 0.95( f •• 7) 0.024 + 0,002 1.06 + 0,31 Reference 1. Slavln W., Oarnrick G.R. // Atom. Speotroso. 1986. Vol. 7. P. 9- 13.

• II DETERMINATION OF LEAD, CADMIUM AND MANGANESE IN i . AAS-88 CHLORIDE MATRICES USING DISK-ENDED ATOMIZER FOR I 1

ERAPHITE FURNACE ATOMIC ABBDRPTIDN SPECTROMETRY

E.Matanova, Tsv.Jotov Sofia University, Faculty of Physics, 5,A.Ivanov Blvd.,1126 Sofia,Bulgaria

The Disk-Ended Atomizer ( DEA > is a technique for spatial isothermal atomization Nith an increased temporal isothermality of the atomization zone. The design of DEA and the tube dimensions have been already published Cl-41. Some analytical applications of DEA Hill be discussed in this paper. Results of Pb, Cd and Mn determination in chloride matrices and the potential of DEA for interference free analysis Mill be presented and compared to those obtained with Massman type graphite tubes.

References 1. Tsv.Jotov, Bulg.Patent N0.3S704 (19B3) 2. Tsv.Jotov, E.Matanova, Fizika 3, в (1988)

3. E.Matanova, Tsv.Jotov, VII Polish Spectroanal.Conf. and X CANAS, Torun, Poland, 19SB, Abstracts PA2B. 4. E.Matanova, Tsv.Jotov, XXVI CS1, Sofia, Bulgaria, 1989, Abstracts.Vol.I, p.104. 5. E.Matanova, Tsv.Jotov, Post-XXVI CSI Symposium on Electrothermal Atamization, Pamporovo, Bulgaria, 1789, Abstracts.Vol.IV, p.74. INTERFERENCES IN THE SPECTR0CHBH1CAL DETERMINATION OP RARE EARTH ELEMENTS IH MARINE ROCKS AHD SEDIMENTS Ambrogio MAZZUCOTBLLI |AAS>8< Cattedга di Chimica Analitica Istituto di Chimica Generale-Universita di Oenova V.le Benedetto XV,Э - 16132 Genoa, ITALY

Rare Earth Elements (REE) determinations interest has been increased recently particularly for what concerns their abundances in marine sediments and in oceanic basalts. The analytical techniques employed for the REE determinations are mainly electrochemical techniques such as Electrothermal Atonic Absorption Spectroscopy (ETA-AAS) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). Moreover major elements such as calcium, magnesium, aluminium, iron, sodium and potassium always present in geological samples strongly interfere in these spectrochemical determinations of trace amounts of REE. The experiments performed on solutions containing interfereing elements and lanthanoids show that interferences are particularly strong when ETA-AAS is used. Elements such as europium . ytterbium and erbium appears as the most sensitive (few pg) «hen determined by eleotrothermal atomic absorption. Other REE are more difficult to be analyzed owing to the strong affinity to form carbides with the graphite atomisers; several coating have been examined (titanium dioxide, hafnium carbide etc.) and the reproducibility and sensitivity of other REE euoh as dysprosium» holmium and thulium have been improved. However the presence of major elements interfere in the determinations showing not only spectral interactions (Iron and aluminium) but also chimico physical intereferences. ICP AES shows also spectral interactions even if the checking of appropriate wavelenghta allows to find some interference free lines but the presence of another kind of interference due to an increase or a decrease of single REE signal (calcium, sodium and potassium) and strong spectral overlapping when all REE and matrix are analysed together need a chromatographic separation when trace amounts of REE must be analysed by spectrochemical techniques. Classical chromatography (with macro glass columns and mineral acids as eluents using strongly acid cation exchange column) has been used to separate matrix and whole REE group; the most interesting application appears nevertheless the coupling of HPLC nation exchange separation to ICP detection. Data obtained on artificial solutions simulating geological matrix and on international reference samples show a good agreement with literature values.

8.3ак,413 119 110Ы1С ABSORPTION DETERMINATION OF IHOH,COBALT AND NICKEL 1H BARIUM FLUuHIKS ATOMIZED IN RiRNACES ГПТ7Г IAAS-90 V.K.Nagdaev, S.K.Ualakhov Tambov Chemical Engineering Institute, Tambov, USSR Atomio absorption determination techniques of iron, cobalt and nickelin barium fluoride are developed. The methods mentioned pre­ suppose samples doeaolving in boric-muratic acids mixture in glass- carbonic Teasels. Barium fluoride products пате been dissolved in autoolaves at 210 K.

Elements determination has been carried out by means of AA Per- kin-Elmer spectrometer 2280 model with atomization in graphite sur­ face. The effect of the main sample components on the analysis result.! has been studied and optimum conditions of its realisation have been chosen. Standard solutions hare been prepared on the basis of high purity barium fluoride crystal.

The samples macroooaponents effeot hoe been studied by means of differential-thermal analysis. The identification of the compounds formed as a thermochemical reaotions result has been carried out by X-ray structural analysis excluding the atmosphere reaction products interaction. It is found out that the greatest effeot takes plaoe in the gasous phase.

Determination likehood estimation пае been done by the "intro- dueed-found" technique. The elements detection limits are approxi­ mately the same and make up X.O-Io'Sjt of masses, relative deviation being -0.10. The devised techniques sake possible to control elements content both In ram and optical materials on the barium fluoride basis.

114 THE OPTIMIZATION OF EVAPORATION CONDITIONS IN GRAPHITE | I FURNACES AS APPLIED TO ATOMIC ABSORPTION ANALYSIS OP 1 I SPECIAL PURE АШМ11Ш1М A.V.Novichyhln, A.D.Hartslzov, V.I.Moeiohev The Central Research Institute for Structural Materiela "Prometheus", Leningrad, USSR The results of condition optimization to determine the impurity amount in special pure aluminium (the total amounts to <0.001S) in graphite furnaces are presented. For the preparation of the samples the method of spare dispersion in an ageons medium was used. The ab­ sorption for STPF conditions was measured by the spectrophotometer "Perkln-Elmer" 110OB model equlped by HGA-700 atomiser and AS-70 autosempler and the model 5000 (Zeeman) with HGA-500 atomizer and AS-40 autosaapler. When developing the method the intensity and the spark dlspereion time of the specimen, the way of dosing the suspension obtained in the atomizer and the temperature programme of the atomizer were op­ timized. It was found that at the eeleoted conditions the absorption sig­ nal is a linear function of the amount of the dosed suspension,which is the evidence of the absence of matrix effeetes in a gaseous phase and vapours output in dosing the analyzed specimen up to lOO^ug. The data of addition method confirm the absence of a matrix effect. That is why the calibration of the spectrophotometer with respect to one element aqueous solution of the determined element or the use of the characteristic mass estimates is allowed. The analysis of the stand­ ard specimen containing the element of the order 10% shows the cor­ respondence of the experimental results and the standard values. The detection limit for Pb, lln sad Cu, calculated with respect to 2&- criterlum equals (10' 1.2, 0.3, 0.7 for 11O0B model and 1.4, 0.4, 1.4 for 5000 model, respectively. The characteristic mass estimates for the first case are 10, 2, 4 pg and second - 12, 2.2, and В pg. The advantages of the method are following! the considerable de­ creasing of the blank value, the analyses excludes the application mineral acids, the low detection limit of concentration, the decrea­ se the cost and time of the analysis, the incresed reliability of the results.

US SPiSCIAlIZ2i) ATOEIiijSRS OP POIVDJSHS AKD SOLUTIONS FOH I Ais_92

DliUOT AiOlilC ABSORPTION BiililMalHATIOi; OP VOLATiLJ IbiTALS ID Illr) iSMVIROMHiSHTAL SAI.iPLiiS V.H.Oreshkin, Ifuil.Belyaev, G.L.Vnukovskaya Institute of Soil Science and Photosynthesis! Vemadslsy Institute of Geochemistry and Analytical Chemistry, USSR Academy of Sciences Uoscow, USSR For the direct atomic absorption (AA) analysis two/nulti-chanbers electrothermal atomizers of powders, solid samples and solutions hove been developed. They consist of two main parts graphite crucible and graphite cells which are heated independently» Sue to independent multistage heating of a crucible (evaporation zone) and a cell Cato- mization zone) the processes evaporation, directed diffusion (locali­ zation) and atomization of vapour's elements can be controlled and optimized. In the general case the atomizers similar design always contribute to the decrease of non-selective absorption in the atouiza- tion zone at AA determination metals in the difficult samples. Greater effect is obtained by selecting the best modification of the atomizer depending on the properties the matrix analyzed and the element to be determined, i.e. it is necessary to develop atomizers with specializ­ ed design. About 10 modifications of the two/multi-chamber atomizers with various configurations (geometry) of the working surface of a crucible and a cell have been tested. These modifications were used for AA analysis of powders according to the following schemes: with evaporation, directed diffusion and localization of vapours in the preliminary heated zone of atomization; with a delay of evaporation and vapour diffusion and subsequent forced atomization; with fractio­ nation of vapours and their accumulation inside the atomizer with subsequent atomization of condensate on the surface microholes etc. (the intensity of resonance matrix vapour absorption is the general criterion for selection). On the basis of the experiments there is an idea on the perfection of metrological parameters of AA analysis of complex objects, which suggest to combine the given matrix of the sample and the element to be determined with the optimum configuration (geometry) of the work­ ing surface of the atomizer. This approach allows to decrease the de­ tection limits of Cd, РЬ, Т1, Bi, Hg, Ag and In in rocfcs, soils,bottom sediments, water dry residues, plants and other samples by 3-10 times as compared with the values obtained (earlier (10~7-10~4$).

IK THE APPLICATION OP ATOB-ABSOKPTIVE SPECTBOUEPRY liJiS-93 IN THE ANALYSIS OP SECONDARY PRECIOUS UbTAtti ' KAVi BATJSSIALS V.H.Pavlova, T.A.Vlasova Glnalmazzoloto, Moscow, USSR The extension of precious metals use in different branches of national economy increases the assortment of raw materials involved in processing with the purpose of precious metals extraction. The secondary materials variety of physical conditions and chemical composition and technological processing distinction leads to the numerous different objects of analysis.

The main difficulty in the analysis of secondary precious me­ tals raw materials and its processing products consists in the op­ tion of decomposition and solution transfer methods. The research of more than 20 types of secondary precious metals raw materials unsealing methods is made by authors.

The research allowed to apply the different unsealing methods combinations (add and alkaline decomposition, oxidizing-alkaline melting) for gcld-containing and silver-containing secondary raw materials, some platinum alloys and products of ruthenium waste chlorination.

Mutual influence of platinum metals and accompaning components determined by atom-absorptive method is studied. It was established, that introduction of copper and nickel salts as apectral buffers is optimum for the elimination of hindrances from the being presented elements, which distort the values of analytic signals.

The research and elaboration of secondary precious metals raw materials analysis methods were implemented with the use of Pye- Unicam" atom-absorptive spectrometer SP-9. Some methods of gold, silver, platinum, palladium, ruthenium, copper, nickel, iron, lead and zinc in the wide diapason of con­ centrations are offered.

117 ATOMIC ABSORPTION DETERMINATION OF YTTRIUM AND GADOLINIUM 1И SEMICONDUCTOR SOLID SOLUTIONS BigTe^BigSey^Tej (udgTe^) AAS-94J H.V. Pollkarpova, K.N. Poplavskay, I.E. Svechnikova A.A. Belkov Institute of Metallurgy, Academy of Sciences of the USSR, Moscow, USSR The use of rare earth elements as alloying admixtures in semicon­ ductive materials and development of high-temperature superconductive ceramics Save generated increasing interest in "express" physico- chemical methods of determining yttrium and rare earth elements. In recent years atomic absorption spectrometry with the use of acetylene- nitrogen oxide flame, electro-thermal atomizers and atomic-emission spectrometry with inductively coupled plasma have been successively employed for this purpose. The goal of the present work was to develop atomic-absorption methods for determining yittrium in BigTi-j-BigSe-j-YgTe^ system and

gadolinium in BiTe,-Bi2Se3-Gd2Tej system. A 'Perkin-Elmer'atomio absorption spectrophotometer (model 403, flame version) and hollow-cathode lamps of different companies were used in the study. Yttrium and gadolinium atomic absorption were measured at 41Q£ nm and 407.9 nm, respectively. fo determine the optimum conditions for determining yttrium and gadolinium, the absorbance of yttrium and gadolinium was investigated as a function of various factors (the height of light beam over the torch, slit width of the monochromator, proportion of gases in the combustible gas mixture). The effect of hydrochloric and nitric acids, bismuth, tellurium, selenium on the atomic absorption signals was investigated. It is found that the presence of tellurium in proportion Y(Sd)i Те - 1 t 100 and selenium in proportion Y(fld) : Se - 1 : 10 causes no noticeable effect on the atomic absorption of some elements. The increase of the bismuth concentration causes a significant increase in absorbance. The effects of buffering admixtures of salts of potassium, lanthai» num and strontium were investigated as a means of eliminating undeei- red influences. On the basis of the obtained data, a method of determining n-10"1 - nj6 of yttrium and gadolinium semiconductor solid solutions Bi^e-j-BijSej-Y^e^SdgTej) was developed for acetylene-nitrogen flame with a relative standard deviation of 0.05-0.03. DETERMINATION OF HEAVY METALS (Cd, Hi, Cu, Mil and Fe) IN "OOD PRODUCTS OP VEGETABLE ORIGIN BY ATOMIO ABSORPTION SPECTROMETRY R. Popko W-95~l Technical University of Lublin, Poland

la the Technical University of Lublin, determination of heavy metals content in bean and pea (dry seed) coning from 5 different sites of Lublin region has been carried out by atomic absorption spectrometry, with the use of an atomic absorption spectrometer AAS-3 (Carl Zeiss - Jena). The samples were preliminarily dried in temperature 103 °c, слеп burnt in oven at 550 °C. In order to hasten mineralization the oarap- les were treated with 2 cm^ HN0,(10!6). the ash was dissolved in 5cm' HHOj (10%) and then filled up with re-destillated water to 50 cm3. Cadmium content determination was performed on the spectrometer by means of flsaeless absorption technique, while for other elements determination the technique of flame absorption was used. Heavy metals content in the examined products was: for pea: Cd(0.019-0.038) mg/kg, 111(0.42-0.94) mg/kg, 0u(3.64-5.78) mg/kg, Un(7.30-10.30) mg/kg, Fed 1.5-34. Ю) mg/kg) for bean: Cd(0.014-0.032) mg/kg, №1(0.84-1.16) mg/kg, Cu(4.70-6,78) mg/kg, Ия(7.61-11.54) mg/kg, Pe(32.20-46.90) mg/kg. The research results analysis shows that the acceptable limit of nickel content (0.6 mg/kg) was significantly exceeded in almost all products, while other elements content remained within acceptable limits.

I» DETERMINATION QF SOME MICROELEMENTS IN THE ENAMEL I OF TEETH BY AAS METHOD 1

E.ReitznerovS, M.Kop&dkova' Research Laboratory of Metal Materials, Technical University, KoSice, CSFR Department of Stomatology, Faculty of Medicine, University of Pavol Jozef Saf^cik, KoSice, CSFR Enamel can be considered a suitable indicator of how the chemistry of the environment influences the organism of an individual from the point of view of geographical conditions of life in various historical periods- In relation to the ecology of the sorroundings of Kosice and to the influence of some microelements on the decay of teeth, sets Df samples from the whale enamel according to age cate­ gories under 20 years of age and over 20 years of age and from teeth from Bronze Age were analysed. In addition, the contents of micro­ elements in the whole enamel surface were compared.

In all the sets of samples the elements Cu, Fe, Mn, Pb, Sr and Zn were determined. The way of obtaining pure enamel, its dissolution as well as the way of etching the enamel surface were worked out. With regard to their relatively higher contents and to the sufficient detectability of the method, Fe and Zn were analysed by flame AAS method with atomic absorption spectrophotometer Perkin- Elmer 2330. The elements Cu, Mn, Pb and Sr were determined by AAS method with electrothermal atomisation with HGA-500 graphite furnace and Perkin-Elmer 2380 instrument.

Analytical calibration curves were constructed with regard to the various concentrations of the matrix in solutions / 0,002 - 0,020 g.rnl / by the standard addition method. The values of detection limit C, of the individual elements in the given matrix were counted. As the weight of samples was limited, only the values of the relative precission of measurements - s /4/ were counted from 20 measurements of the same sample.

IM ATOMIC ABSORPl-ONAL AHA1Y5IS OP CSLBSHTE COHCHHBAMS l yf •• N.H.Roeva, L.H.Ssparova, f.V.Cnernova, H.H.Yevjanov Chemical Institute of the ISSB Academy of Sciences, Ashkhabad, USSR this paper is devoted to Mac development of the method* of atomic absorptional defining the strontium eulphate, the oslcluB sulphate and the ferric oxide (II) In eeleatlte concent­ rates in Oaurdak Productloo Enterprise "Turkmenainaral". We tried to appreciate the posaiMlltiea of using thia method In order to create the express methods ef eeleetlte conoentratee analysis. the optimal conditions of chemioal preparing the eelestlne oencantratsa, baaed on their canveralon to the Instant fora by aaana of alloying with the natrium carbonate under 900"C. measuring the atomic absorbing the strontium, calcium and ferrum «as dosa at the nave lsngthes: 460.a, 422.? and 248.3 a In accordance with each of the indicated elements. Die straight forwardness of the graduated graphics for strontium, calcium and ferrum was observed Is the Intervals of the concentrationsi 1-20, 2-10, 1-20 ag/1 correspondingly. The content of the strontium sulphate, the calcium sulphate and the ferrio oxide (II) In eeleetlte concentrates has constituted 95-96.5*, 2.12- -2.3**, 0.016-0.022*. the method is noted for its sufficient sensitiveness and exactnees. The corresponding standard deviation Is Sr.0.0117, the exactness of the direct definition in accordance with trusting probability L-0.95 la 7.95, the corresponding rated error of direct definition ia 0.83*. It was stated that magnesium, barium, aluminium, aillciua which are the moat of all accompanying strontium in natural and industrial plants, do not affect the results of its atomic absorptions! definition.

Ill BTAAS дашатшпон op AKSBMIO(V) AND ASSBNIC(IXI) r ; Л WITBSS AFTER THMR SBPARATIOH ВТ. EHRACTIOH JAAS-96 | СИЮЖАТООНАт

B.Ruaaeva, I.Havezov Institute of Oeneral and Inorganic Chemistry, Bulgarian Academy of Sciences, 1040 Sofia, Bulgaria The known approaches for the separation of As(v) and As(lII> can be grouped as follows: i) extraction of As(V) as heteropolyaolybdate complexes, or extraction of Aa(lll) as AaX,; ii) sorption of As(III) or of As(v) on various sorbents; iii) photometric methods; iv) gene­ ration of AsH.. All mentioned procedures involve the determination of only One lipeeies, while the other is estinated by the difference.

The present work suggests a combination of ETAAS analysis and speoifie extraction chromatographic separation which provides subsequent determination of both As(lll) and As(V) in a single aliquot. Areenie(V) is quantitatively «orbed on en inert support modified with an organotin extractant. The effect of pH, the type of acid, the aeidity and the interference of foreign anions and cations usually present in water samples are studied. Op to 10 g/1 of CM>^-, 1 g/1 of SO,8", 0,1 g/1 of ?" and СЯ3ООО", 5 g/1 of Ou, Ifci and Ca, 1*6 g/1 2n and 0.1 g/1 Cd do not interfere. Fe(lll) interferes seriously, but up to 0.5 g/1 of 7е(Ш) can be successfully masked with fluoride. The aorbed Ae is eluted with 2 ml of Я HC1. The eluate is analysed to determine the As(V> content.

1И ANALYSIS OF HIGH PURE CESIUM SALTS AND THEIR APPLICATION FOR ALKALINE ELEMENT DETERMINATION AAS-99

T.Schikora, R.Hom Institut fuer mineralische Rohstoff- und Lagerstaettenwirtschaft Dresden DDR-8036, ODfi The manufacture of high purity cesium salts for optical, bio- technical and analytical applications has been started at our insti­ tute this year. Quality control, i.e. determining netal ion contents in these salts is carried out by f lane excitation AAS using an AAS3 (Carl Zeiss Jena). The measurements were done fron aqueous solutions containing 1 Ж or 3 % of Cs2C03. In the table below the concentrations of the elements to be determined are related to solid salt, whereas in solution these con­ centrations are only 1/100 or 3/100 of those of the solid salt. elenent cone.range excitation measure salt cone, in ppn (in salt) solution in % Li < 1 C2H2-air emission 1 №, ft, Na, 5. .100 C3H8/C2H2-air absorption 1 Ca 5. ..SO C2H2-H20 absorption 1 наZn,. Cu 1. .. 5 C2H2-air absorption 1 Pb 5. .10 C2H2-air absorption 3 Ba, Al 20. ..SO C2H2-N20 absorption 3 In the case of Li < 1 ppn the determination by emission was more sensitive and «ore reproduceable fjhan by absorption. The measurement in a 3-Х salt solution was not free of problems, because the burner often had to be cleaned. Generally it was possible to determine the above mentioned elements in their low concentration ranges with flame AAS, which la much more economical than with GF-AAS. The calibation procedure was based on a standard addition method. Becau­ se the major component Cs increases the sensitivity of elements having a low excitation potential, the calibration solution must have the same Cs-levels as sample solutions have. Cs salts, especially CsCl, are important for the determination of Na, К and Li by flame spectrometry. H.Schuhknecht and H.Scninkel \X\ showed the role of CsCl in combination with A1(N03)3 as ionisation buffer and matrix buffer. In some countries this effect stayed in the background, because Cs salts were not available or were very expensive. Using geological reference samples we could show, that better results were obtained for alkali element determination in geological materials in the case of buffering with pure Cs salts or in combination with Al salts. ^Reference 1. Schuhknecht 4., Schinkel H.// Fresenius Z.anal.Chen. 1963. V.133. P. 161

I» COMMON CONDITIONS FOR THE DETERMINATION OF TRACE ELEMENTS IN MEDICAL SAMPLES USING GRAPHITE FURNACE

hAS-100

G. Schlemmer, Z. Qrobenski, E. Bulska and M. Hasel Bodenseewerk Perkln- Elmer GmbH, P.O. Box 10 11 64 FRG-7770 Oberlingen

Graphite furnace AAS Is an excellent tool for the determination of trace elements In samples from biological origin. There are some peculiarities which distinguishes the graphite furnace among other techniques for this type of samples: Very email sample consumption, typically in the range of 10 uL or below; detection limits in the 1 мд/L range; no need tor a complex sample preferment Important trace elements, such as №, Cd. As, Bi, Se, Al, Mn, Cr. № have been determined in body fluids such as serum, whole blood, orik and urin. All samples have been introduced into the graphite furnace without prior decomposition or extensive sample pretreatment but only after a 1:3 dilution with a 0.1 % Triton X-100 solution. The drying and pyrolysis procedure can be essentially the same for an analyte elements Investigated with only minor modifications in the maximum pyrolysis temperature. An oxygen ashing step has been found advantageous for this type of samples. The atomizatkxi temperature had to be adjusted for each element Individually. For the determination of these elements in biological tissue a nitric acid pressure decomposition proved to be most suited. Another promising approach for this type of samples is the determination in the sold material without any decomposition. The determination could be carried out by measuring directly against acidified standards or against reference materials. For some of the elements investigated a thermal prereduction of the modffier is necessary in order to obtain an interference free analysis.

IM INFLUENCE OF THE SAMPLE COMPOSITION ON ATOMIC ABSORPTION i, ,,„ | AAS-101 DETERMINATION OF NICKEL,СОВАЫ,CHROMIUM AND MANGANESE IN ' ' THE ORES OF CDBA K.A.SemenenRo.K.Dlas Lopes,YU.Ya.Kuzyakov Moscow state University,Moscow,USSR, Habana University.Habana,Cuba The method of chemical phase analysis combined with successive atomic absorption determination of nickel,cobalt,chromium and manganese In Beveral resulting phases Is suggested In application to analytical study of Cuban ores. Complex Investigation of media and solution composition (hydrochloric acid,ammonium citrate,ammonia-chloride mixture)effecting on absorption of analyts and also the exploration of matrix interferences (iron,aluminium,magnesium and silicon) have been carried out.

The mechanism of thermal atomization in flame evaluated In our study became a clue to practical application of the data obtained by means of equilibrium composition thermodynamical calculations.The partial preassures of bulk flame constituents, nickel,cobalt,chromium and manganese gas phase as well as condensed phase species were involved into account. The understanding of the atomization mechanism enabled us to affect free atom fraction In air-acetylene flame, displacing the equilibrium by means of proper medium maintenance.

Complicated phenomena occurred In air-acetylene flame during chromium atomization were elucidated in terms of this mechanism depending on flame stolchlometry.lt was the first such a calculation In which the contribution of chromium dioxide In atom-molecular equilibrium was evaluated. The computer calculations have been confirmed by experiments. Practical recommendations for the analysis of Cuban ores have been made.

I» ATOMIC АВ80ВИЮН DEHEHIHAIIOH of DIFORMIES |А48-10е'| Of Ctt, Zn, Fb, Cd, Co and Hi in CARBONATE ROCKS C__—! N.A.Sbatkowskaya, D.N.Faehadznanov, L.K.Goncharova Institute of Chemistry, Academy of Science of Tadjik SSE, Dushanbe, USSR The atomic absorption spectrometry method allow» to deereaae the limit of detection of Cu, Zn, Fb, Cd, Co, Hi contents In natu­ ral objects comparing with chemical analyses. How it Is necessary to determine the low concentrations of these elements in carbonate rocks for the geoebemical purposes when investigating the oarbo- nate formation conditions. She direct determination of these elements at 10~J-10~5* is difficult procedure in consequence of the negative influence of matrix, In particular calcium content, whioh can be reached up to 50». Therefore it is necessary the preliminary concentration of impurities and their simultaneous separation from matrix. It was investigated the co-precipitation of impurities of these elements with metals hydroxides depending on pH, concentration and salt background and content of hydroxide-collector [1]. It wae es­ tablished, that the maximal concentration and separation of Cu,

Zn, Fb, Cd? Co and Si took place in case of using of zirconium hydroxide (IV) as a collector In alkaline evironment. This proce­ dure increases the impurities oontents sediment by the two orders of magnitude. The sediment was dissolved in 1 в НС1 acid and absorption mea­ surement was conducted with using of spectrophotoaetr AA8 5 (Carl Zeiss Jena, 01») In acetllen» - air name. She lampes with hollow cathode were used as a souroe of constant radiation. Che calibrated curves were constructed with using of mixed solutions, containing all determinated elements. Ibis method allow to determine the Impurities with detection limits between 10"* and 10~5*.

Reference 1. Co-precipitation with the hydroxides. Dushanbe: Tadjik State university, 1977.V0I.2. 109 P.

1» ATOUC ЛВвСВИЮН ВЕТЕЮШШРХОН OF MIGHBSimi AMD CALCIUU EI HIGH PURITY АШИЖОИ B.A.Shatkovskaya, D.B.FachadBhanov, B.U.Vachobova Institute of Chemistry, Academy of Science of the Tadjik S3R, Dushanbe, USSR The constant expending of using of high purity aluminium requi­ re* Improving of hie obtaining technology and nothode of analyti­ cal control. The atonic absorption spectrometry method (IAS) is widely used in practice for determination of impurities of alkali­ ne and alkaline-earth elements» Nevertheless the presence of alu­ minium decreases the absorption of magnesium and calcium. This in­ fluence can be eliminated by addition of releasing reagent• in par­ ticular lanthanium salts and others [i]. Our investigations aliased to decrease this influence and wor­ ked out the method of direct flame atomic absorption analysis of these elements with sensitivity about 10 -10-5*. measurements were conducted In flames of mixtures of propan - butane and aoetylene-alr with using of spectrophotometer AAS 3 (Carl Zeiss Tena, 6SB). Lamps with hollow cathode were used ав а source of constant radiation» It was established, that addition of 5000 ppm lanthanium salt was sufficient at content of impurities in aluminium about 10"'s», In ease of increasing of ratios MeUl m 1*10000 sad 1i100000 the influence of matrix can't be excluded completely only by additi­ ons of lanthaniun salts even in high temperature flame» for that the other reagents were Investigated. It was determinated the optimal contents of lanthaniun and po­ tassium salts additions. The addition of 1ОООО-150ОО ppm lantha­ nium and J500 ppm potassium completely eliminates the negative ef­ fect of aluminium and increases the absorption of determinated ele­ ments In acetylene - air flame» that is effective for plants labo­ ratories» She calibrated ourves were constructed with using of standard solutions of calcium and magnesium, containing aluminium, lantha­ nium and potassium, and blank solutions. Ins aluminium samples we­ re dissolved by electrochemical method. Reference 1. Kanaev H.A., Trofimov IT.V.//Atomic absorption and flame-photo­ metric analysis of alloys. If.'t Hetallurgia, 1983. Г.65.

117 EVALUATION OF ANALYTICAL RESULTS IN THE PRESENCE DF | _ _ AAS-10л 4 INTERFERENTS IN GRAPHITE FURNACE AAS L —J

Hltold Skwara and Jakub Qudek Institute of Nuclear Chemistry and Technology Dorodna 16, 03-195 Warsaw, POLAND

The standard addition and successive dilution method (SASD method) (ZO far elimination of non-spectral interferences and verification of the analytical results in graphite furnace atomic absorption spec­ trometry (GF AAS) was practicaly tested. Some examples of the calibration curves in the presence of various types of interferents, in graphite tube, are shown. For testing of the SASD method several test samples of different interferent-analyte systems were used. The obtained results are shown that the SASD method can be sur- cesfuly use for elimination of non-spectral interferences in GF AAS. The performance of the procedure is very simple and it enables not only to obtain the correct results in the presence of any inter- ferent or interferents mixture but also to verify their correctness. Reference

1. Pszonicki L., Skwara Ы., "Standard Addition and Succesive Dilution Method. Evaluation and Verification of Results in AAS Analysis", Talanta, (1989) in press.

Ш FAST SLURRY ANALYSES WITH FURNACE AAS J\AS-105

ТЯ. Slavin and G.R. Carnrick, Perkin-Elmer Corporation, 761 Main Avenue, Norwalk, CT 08859-0237, USA

Graphite furnace AAS has gradually become better understood and instrumentation has become generally available that was widely expanded the applicability o£ Furnace AAS to trace metal analysis. The gradual acceptance o£ modern Stabilized Temperature Platform Furnace (STPF) procedures have provided reliable results using simple aqueous solutions as standards. Nevertheless, STPF methods are still slow, taking typically 2 to 3 minutes per determination. We will show that, in some situations, the practical analytical time can be reduced to less than 1 minute per determination by avoiding the use of a matrix modifier and also avoiding the pyrolysis step. These fast methods were applied to a wide range of well-characterized SRMs with results that were accurate and precise to 1 or 2% RSD.

We have also applied these fast methods to the analysis of solid materials introduced into the furnace as a slurry. A small ultrasonic agitator is mounted above the autosamplec table and an automatic program is used to introduce the agitator into the cup containing the slurry just before the autosampler probe picks up the aliquot to be delivered into the furnace. In this situation, also, the determinations require about 1 minute and the precision is typically about 21 RSD. We will report data for As, Tl, Pb and Se in coal and coal fly ash samples and №i in a variety of biological and botanical materials.

The generality of these results will be discussed in relationship to the state of the art of furnace AAS. We will make some effort to predict how furnace AAS will compare with other trace metal analysis techniques.

II* 9.3ак.413 3PECTR0CHBMICAL DBTBHHUfATIOH 07 HBRCURY IN DIFPEREHT BMVISOSHBHTAL SAUPLBS Сиамки Xu.I.Stakheev, Yu.G.Tatey Veraadsky Institute of Geochemistry and Analytical Chemistry, Moscow, USSR Hamzs B.Hamza Analytical Laboratory, Radiochemical Department, Tajuru Huelear Research Centre (ТИМ), Tripoli, libya

Determination of mercury contenta in boilogical and environmental samples lb an important factor for environmental protection and for defining the sources of contamination, because mercury is strong ecotoxicant.

Contents of mercury in uncontaminated environment samples are very low, less ррЪ and sensitivity of commercial analytical devices is insufficient for direct determinations of mercury. The present work was uimed to determine mercury concentrations directly in gaseous, liquid and solid environmental samples with the aid of some simple eelf-made instrumentation» connected with AAS FIT 9000.

The liquid samples were analysed by oold vapour method, the solid samples were analysed by electrothermal vaporisation. The gold wire collector of mercury vapours was used in both methods to enhance the sensitivity, for determination of Kg in air the ability of collector to absorb mercury vapours from Gases пае been used.

The absolute detection limit of the method is 30 pg. The BSD for contenta above 0.5 ng is O.05. This combination of accessories was used for determination of Hg in atmospheric air, air of working rooms of TMBC, fresh water, sea water, algaes, fish, molluscs, soils from territory aurrounding TlfflC, urine and hairs.

IM DIRECT DETERMINATION OP SILVER AMD CADMIUM IN WATERS AND A45_1(W WINES BY ATOM TRAPPING - ATOMIC ABSORPTION SPECTROMETRY • Sun Han wen, Shao Jlan hui, Zhang De qiang, Zhang Jin jie and Zhang Tie ling Department of Chemistry, Hebei University, Baoding, China

Normal flame atomic absorption spectrometry has lower sensitivity. It ie difficult for direct determination of trace elements at ppm-ppb in water and wine samples. In 1976, a quartz tube atom trapping-flame atomic absorption spectrometry was described (1). The design of atom trap apparatus, selection of trapping and releasing conditions, app­ lication and progress of the atom trapping technique have been review­ ed in our prevenient paper (2). The atom trapping technique has higher sensitivity than normal flame atomic absorption spectrometry. A stainless steel atom trap apparatus prepared In an our laboratory has been used to determination of lead In water and wine samples (3).

The stainless steel atom trap apparatus has been found to increase sensitivity of lead, silver and oadmium. la present paper,the effects of various conditions such as reaponce time of the instrument, posit­ ion of the atom trap, water flow rate, passing-air time, nature of flame and trapping time on sensitivity of silver and cadmium were in­ vestigated in detail, respectively. The measured atomization appear­ ance time was 11 s for silver and 4.6 s for cadmium. Under the selec­ ted conditions, silver in water samples and cadmium in water and wine samples were directly determined with recoveries of 85-115Й for sil­ ver and 88-100$ for cadmium. The relative standard deviation was 3.3$ for silver and 3. 0-5.0* for cadmium. The Improvement of 10-100 fold for silver and 100-375 fold for cadmium was obtained as compared with the normal flame atomlo absorption spectrometry.

References 1. Lau CM. et al. // Can. J. Spectrosc. 1976. Vol. 21. P. 100. 2. Peng Hui, Sun Han wan 7 XXVI csi (Bulgaria). 1989. 3. Sun Han wen et al. // VII Polish Speotroanalytioal Conference (Poland), 1988. P. 0-06.

131 DETERMIHATIOH OF HEAVY METALS (Cd,Fb,Cr,Ki and Zn) IN LIBYAN SOILS BY ETA-AAS Yu.G.Tatay, Yu.I.Stakheev Vernadskii Institute of Geochemistry and Analytical Chemistry, Moscow, USSR Hamsa B. Hamza Analytical Laboratory, Badiochemical Department, Tajura Nuclear Research Centre (DIRC), Tripoli-Libya The method of atomic absorption with electrothermal atomisation was used to determine heavy metals in soils of Libyan Mediterranean area and to estimate possible technogenous pollutions. Ihe sample dissolution was carried out in pressure bombs, using acid mixture vapour decomposition technique. The concentration profiles about 500 m long for Cd, Cr, Hi, Pb and Zn traced from the Mediterranean sea cost across the beach, highway and greenhouses. Ihe soils from the most polluted regions were analysed. Ihe concentrations of heavy metals in the region under consideration are compatible with background levels and show the possibility of simple registration of technogenous pollutions.

I» INFLUENCE 0Г THE TYEE OP ATOMIZER AHD OP I THE HATHIX MODIFIER OH THE DETEBMINATIOH OP |AAS-1Q9 TRACES ID ORGAHIC SOLVENTS E.Tserovski, S.ArpadJan, I.Earadjova University of Sofia, Faculty of Chemistry, Sofia,Bulgaria The influence of the type of complexes speci'B of Al, Ав, Bi, Cd, Co, Cu, Pe, Un, Hi, Fb and Se present in the organic solvents used on the electrothermal atonization has been evaluated, Uncoated gra­ phite tube, tungsten-impregnated graphite tubes and uncoated gra­ phite tubes nith L'vov platform were applied for the investigations. Acetone, methanol, ethanol, outylacetate, methylisobutylketone, o- xylene and toluene were studied as organic solvents. The problems of calibration and chemical modification for analysis of organic solvents are discussed. The analytical characteristics of the ITA-AAS for analysis of high purity organic solvents are presen­ ted.

ISS FURTHER ANALYTICAL APPLICATIONS OP ATOMIC ABSORPTION METHOD IN ON-LINE CONTROL OP VACUUM METALLURGICAL PROCESSES ' ' V.B.Ustlmenko, V.I.Severlu, A.S.Kovalenko OkrHIIspetsstal, Zaporozhye, USSR Atonic absorption method is being Introduced in on-line analytical control of vacuum metallurgical processes, such as melting and refining Q 1 J , coating and producing of composite materials from vapour phases QjJ. One of the problem is met in the analysis of the vapour flows of base components in metallurgical units» It is high optical density, which approaches to D«ln(Io/I)<-~103- 10* for resonance lines» In such conditions the use of nonresonance lines, as well as lines with the low oscillator strength is limited by the absence of non­ zero energy levels for some elements and low intensity of such lines in the light sources. Traditionally, the optical density decreases to the acceptable values of D~1 by analytical zone reducing. In vacuum it causes a sharp narrowing of the Doppler absorbtion line width due to oriented atom movement along the normal to the light beam,that results to high lose of sensitivity. However, if you take into account, that geometrical variations of both vapour flow and probing light produce an equivalent effect upon light absorbslon, then the investigator will be able to form the desirable contour of the absorption line and to increase the control sensitivity by varying angular parameters of the light flux at a narrow analytical zone. The experiments showed, that for the copper resonance line 324.8 nm with the decrease of the angle between the light beam and vapour flow fromS"/2 to 574 the analytical sensitivity will be increased twice at the pulse current of 65 mA through the spectral lamp with the hollow cathode (pulse length of 180*10 s) and approximately by an order at the pulse current of 700 nA. References 1. Mejorov I.A., Timpfeev B.P., Eliutin A.T. at al.// Speetrochim. acta. 1981.Tol.36B. P. 1223. 2. Lu C.// Thin solid films. 1977.vol.45.P.481.

IM SA-IOMP ATOMIC-ABSORPTIOH SPECTROPHOTOMETER US-111 G.V.Valeev, A.H.Gil'mutdinov, M.M.Mavlyutov, S.S.Murzieva, Xu.S.Nagulin, A.I.Uskova, R.A.Safina, S.A.Shaidullin Kazan State University, COO "Photon", Kazan, USSR An automatic atomic-absorption spectrophotometer baaed on advanced home-produoed optica and electronics is developed* An optical circuit of the device includes off-axis ellipsoidal and paraboloidal mirrors providing its optimal energy and optical charac­ teristics. A narrow cylindrical beam is formed in an atomizer zone providing a good separation of working radiation from radiation of graphite tu­ bular atomizer walls.

4 o^o—^ Optical circuit of a spectrophotometer

Flame, tungsten spiral and graphite tubular atomizers are used in the device. EC-1340 miorooomputer and a built-in microprocessor cont­ rol a spectrophotometer, measurement data recording and processing. It is possible to oonneot another computer which input corresponds to the international standard. Software allows to work with the devioe in a dialog regime. For processing an analytical signal and plotting calibration graphs an application package with non-olassical problem solution is obtained. Experimental results are given and discussed.

I» EITEACMON ATOMIC ABSORPTION ANALYSE 07 AAS-112 1ЙА0Е ELEMENTS HI HIGH НШ1И GOITER SALTS I — E.Vaseileva, S.Arpaddan, S.Momchilova University of Sofia, Faculty of ChemiBtry, Sofia, Bulgaria

The possibilities of some Ions chain quaternary ammonium salts for extraction preconcentration and flane atomic ab­ sorption determination of traces of Ag, Cd, Be, Ho, Fb, Sb, Sn and Zn in nigh purity copper salts are evaluated. The influence of the surfactants presented in the organic sol­ vent (MTBK, butylacetate, o-xylene) on the atonization of the ionic associate complexes of the microelements in an air/acetylene flame is investigated. The mechanism of ato- misation of complexes dissolved in organic phase in pre­ sence of long chain quaternary ammonium salts is discussed. The analytical characteristics of the proposed extrac­ tion flame atomic absorption procedure for trace analyses of high purity copper salts are presented.

IM АРРШСАИОН OP GBAPHME FUBHACE FOH GSOIOGXCAL AM j EBVIROMllHtTAI. SAMPLES AHAIXSIS |AAS-113 M.A.Vorontova, V.S.Voskresenskaja, B.G.GorlevekaJa All-Union Eeeearch Institute of Mineral Resources, Uoscow, UBSB Last investigations proved importance of electrothermal atomizat- ion in graphite furnace for determination of microquantity elements for solving geological and ecological problems. As a result of research work the methods of determination of fol­ lowing elements: selenium, silver, bismuth, tin, arsenic, antimony, lead, cadmium, thallium etc. in microsamples of minerals (malachite, stannite, cassiterite, molybdenite, asurite, ehalcocite etc.), in natural water, porous solutions, soils, plants, rocks and ores were developed. Authore mark influence of some factors upon the sensitivity of analytical signal and accuracy of measurements i.e.: construction peculiarities of graphite furnaces; tubes material; the type of atom- iaation(,from wall or from the platform); the type of solvent;the type of measurements fpeak-heigbt or intergration). Taking tin ав an example the authors showed that the behaviour of this element during the atomisation cycle differs greatly due to dif­ ferent types of furnaces(HGA - 500 and EA - % which explains distinc­ tion of published data. Application of integration method of an analytical signal measur­ ing minimised interference effects from matrix components which is very important for analysis of complicated samples and for determi­ nation of elements after fusion procedure with the flux. These high-sensitive methods could he suecesfully used for sol­ ving great variety of geological, ecological and monitoring problems. A number of methods for elements determination could surve as stan­ dards of Ministry of Geology of the USSR and could be used for attes­ tation of standard samples composition.

I» CItEUICAL AWAMSIS OP AIJiOYS APPUEI) IU MEDICIHR BY AAS-114 ATOMIC ABSMimON SHSCTKOWlSTKi

A. Yiycislik Sllesian Technical University, Institute of Materials Science and Engineering, Katowice, Poland

Among the implantating materials for the needs of surgery the co­ balt-base alloys plaoe a speoial role. In the present work the AAS method for determination of Cr, Ni, Ре, Но, А1, ИП and Cu in these alloys has been described. A Perkin-Elmer Model 503 atomic absorption spectrophotometer with Intensitron hollow cathode lamps wa3 used. Ace­ tylene was used as the fuel for all elements. Air was used as the oxi­ dant for Ni, Pe, Mn, Cu and nitrous oxide was employed for Cr, Mo and Al. Less sensitive analytical lines - Ni 341.5 nm. Pe 372.0 nm, Mo 317,0 nm, Mn 403.1 nm - were used when Ni, Fe, Mo and № elements were determined^]. Detailed measuring parameters have been assigned and compiled. Por the dissolution of samples mixture of HC1 and НПО, was used[2,3] . Three synthetic standards for each deter- iJl-|| взЯВ"""""""""'^! mlned element were prepared. An a- 4lil | xt « » » » » • » »| nalyticel diagram has been presen- 4—III И.1Ч11И1Ш I ted in Pie* 1- The precision and

ifri ^wi"""']'""""""l ?t.i accuracy of proposed method Hvere determined by replicate analysis of standard materials or values ob- Analytical diagram for tained by wet chemical analysis. analysis of alloys applied in medicine by AAS method Reftrenot» 1. V/ycislik A.// Proo. 8th Czechoslovak Spectroscopic Conference, Севке Budejovice (CSSR), 1988. P. 43. 2. Belcher CO., Kriege O.H//At. Absorption Nov:8lett.l970.Vol.9. P.61 3. V/yclslik A., Jurczyk J. // Proo.xIII. Hilttenmahnischeii Material- prUfertagung, Balatonaliga (Hungary) , 1988. P.468

II» SOKE IHVJSSTIGAMOTS Of OHHIICAL DITBRPBRENCBS ВГ THE Г' _ " _Г DETBRKDUTION О» СШВХПВ-ТОИШО BLBKOriS ПГ MBTAL I**3-1"15 llMyS BY AAS UEIHOD

A...yci&lik '*, J.Jurezyk 2' 'sileslan Technical University, Institute of Materials Scie-.st and Engineering, Katowice, Poland 'Institute of Ferrous Metallurgy, Gllwice, Poland

Carbide-forming elements such as Or, Mo, V, Tl, Та, '.V and Zr are purposely added to metal alloys, to improve their mechanical proper­ ties. Some alloys such as cobalt-base ones are strengthened with car­ bide phases. Thus the content of the carbide-forming elements should be analysed properly. Their determination is a complicated analytical task regardless of the applied nethods and research techniques. This paper presents the results of some revealed chemical interferences existing during determination of the above mentioned group of ele­ ments in different metal alloys by FAAS method. During the examina­ tion the attention was paid to the important role of acid influences in the atomic absorption signal of such elements as Cr, Ho, Ti, Та, в end Zr. The results of the interelement reactions of these elements in caee of their simultaneous appearance in steels ana nickel-base alloys were also presented. The paper describes some methods of cor­ recting these interferences both by introducing proper buffered so­ lution and the change of burner height or the ratio of gases flow, and even by the application of other flame as in case of chromium and molybdenum determination. To compensate the influences of ma­ trix at the carbide-forming element determinations it is possible the analytical curve preparation using a single specific standard. It is based on the use a few different weighed amount of the stan­ dard, to which after the dissolution the given amount of main ele­ ments (matrix) are introduced to equalize their content in standards and Bamples analysed to the same level, compensating at the same time their influence on the determined element [1,2]. Some results of the carbide-forming elements determination in various metal alloys were also presented.

References

1. Gregorozyk S., Wyclslik A.// Hutnik (Poland) 1979.Tol.46. P.514 2. Wycisllk A.// Proo. IX. CAMAS, Neubrandenburg (GDR). 1986. P.120

I» ATOEIC-ABSORPTIOH METHODS POR LAY3R-BY-LAYER ANALYSIS f~ OP IMPURITIES IM SEMICONDUCTING EONOCRYSTALS AND PILUS |*ig-,H6| 07 Si AND GBAB

i.G. Yudelevich, И.Р. Beiael Institute of Inorganic Chemistry, Siberian Branch of the USSR Academy of Sciences, Novosibirsk, USSR Determination of traces of elements in thin films is essential for characterization of materials used in microelectronics. This requires both ways for separating thin films sod highly sensitive methods for analysis of small samples (0.1 meg). In recent years the atomic-absor­ ption spectrometry with electrothermal stomlzstion (ЕТЛ-AAS) has began to be employed for this purpose along with the neutron-activation and spark mass spectrometry. At the Institute of Inorganic Chemistry the ETA-AAS methods have been developed for leyer-by-lsyer analysis of impurities in Si, Ge, OaAB, InSb, InAs. The possibilities of the method are illustrated for the esse of Gs and As In Si end of Bi in GaAa. The lsyer-by-lsyer etching of Si was performed with a HF+HNO, mixture. To remove the bese, the etching eolution was evaporated and treated with НПО, with subsequent dissolution of the residue in deionized water. Por GaAa

etching, mixtures of HP, Hg02 and tartaric ecid were used. Before the analysis the etching solution was diluted with deionized water. The solutions being snslized and the reference solutions (20 mcl each) i.ere pipetted onto a glassy carbon platform placed into the graphite furnace of Hitachi Z-8000 Polarized Zeemsn AA- spectrometer. After that 10 mcl of a matrix modifioator waa pipetted onto the platform and the furnace was heated according to the program: drying 30 8 at I • 100-150«C; ashing 30 a at T • ?00°C(Bi) or 1000°0 (Ga,As); atomiz- ation 6-10 s at 2400°G (Bi) or 2900°C (Ga.As). Of several modificatora tested ( nickel nitrate, palladium and magnesium nitrates and their mixtures), a 10 ppm solution of Ni for Bi determination, a 100 ppm solution of Hi for Aa and a mixture of 1i1 solutions of Ug and Fd nitrates ( 200 and 300 ppm, respectively) for Ga were used. Evaporation from the platform and the use of modi- flcstors made it possible to increase the atomic absorption of As end

I 3AMPLI110 01» C0IIDI3NSBD PROBES IH SPARK DISCHARGE AHD ICP ' AHD THEIR RADIATIOH HOISE IA8iS "1 R.Antanavicius, R.Buteikis, P.Serapinas Institute of Physios, Vilnius, USSR

It was shoim earlier that in spark discharge and ICP some radia­ tion noise exists which is produced in the probe sampling and atomi- zation processes [1,2]. In this report results of the radiation noi­ se spectra measurements, relation between noise spectra and atomiza- tion processes and role of that noise in analytical spectroscopy will be discussed. In the spark discharge intensive radiation noise at frequencies lower than 20 HHz is observed. It is due to cathode spot microstruc- ture. Some noise peak at lower frequencies (0.9 MHz) is also observed. Poasibly it is generated by the groups of microcraters working simul­ taneously. The noise study allowed us to measure the microcrater life- tine (about 100 ns), mean crater current (10-100 A) and current den­ sity (10 A/cm2). If addition information about the cathode spot temperature (5-6-10%) is used, it follows that the cathode vapour Pi -3 density at the surface is about 10 cm . In such conditions electron current filamentation in the near-cathode plasma ought to take place, which can be the reason of the current instability at the cathode. In ICF radiation noise at frequencies below 10 kHz is observed due to aerosol structure of the sample introduced into the discharge. Ma­ thematical analysis of the noise enables from the spectra measure­ ments easy measurement of the aerosol particle density and flow velo­ city, allow to get information about the aerosol particle accelera­ tion, atomization rate and diffusion coefficient of the atomic par­ ticles. So the radiation noise measurements produce much information about the sampling of the probe in the plasma. The negative role of that noise in the reproducibility of the analysis can be lowered by the signal integration. She radiation noise relation to the probe inhomo- geneity, inhooogeneity contribution to the flicker noise, noise and spatial radiation intensity correlation measurement application in the study of probe inhomogeneity and inclusions will be discussed as well. References 1. Serapinas P.//J.de Fhys. 1988.Vol.49. P.01-315. 2. AntanaviSius R.L., Hailenas Е.Г., Serapinas P.D.//Optics and Spec­ troscopy (in Russian). 1989.Vol.67.P.280.

144 DEVELOPMENTS IN AUTOMATED INDUCTIVELY COUPLED AES-2 PLASMA SPECTROCHEMISTRY

Ramon M. Barnes, Edward H. Thome IV, and Laura J. Martines University of Massachusetts, Department ol Chemistry, GRC Towers Amherst. MA 01003-0035 USA

Inductively coupled plasma (ICP) spectrochemistry has reached a stage of mature development so that some ICP research and instrument design efforts have shitted to sample preparation and introduction and to their integration into an automated ICP laboratory system. Since sample handling for ICP spectrometry rather than the spectroscopic measurement now often limits the performance of modern ICP instruments, significant improvements in practical ICP analyses requires advance­ ment in the sample manipulation component of an overall ICP system.

Research underway to automate ICP spectrochemistry in our laboratories focuses upon the evaluation of processes necessary to develop an enhanced expert system and the practical implementation of expert-system-driven sample preparation.

The current extended expert system under development for automated ICP spectrochemistry is capable of modifying the application of rules from real-world feedback. Based upon the Texas Instrument software Personal Consultant Plus (PC*), a system is being designed to perform automated solid sample analysis using a laboratory robot and automated ICP atomic emission spectrometer (Perkin Elmer Plasma II). As part of the expert system, spectral and internal reference wavelength selection, spectral and matrix interference corrections, and optimization ol sample presentation are being considered. The extended expert system scheme will utilize input from practical chemical analysis experience to add rules into its knowledge base dynamically.

Another feature is the application of an automated, computer-controlled microwave digestion system for sample preparation. Using a commercially available microwave digestion apparatus (Prolabo) and flow injection techniques, controlled sample digestion with expert system supervision is being devised.

This presentation will examine the background, the design concepts and objectives, and the status of an automated ICP spectrochemistry system.

148 I0.3an.4I3 IMPROVEMENT IN ICP/OES AHO IN FLAME-AAS BY HYDRAULIC HIGH PRESSURE NEBOblZAXXON -SAMPLE INTRODUCTION AES-3 IHHPN-SAMPLE INTRODUCTION)

Institut fur Spektrochemie und angewandte Spektroskopie Bunesn-Kirchhoff-Str. 11, D-4600 Dortmund 1, Fed.Rep.Germany

INTRODUCTION: The nebulization of liquids with pressures from 5 Co 40 MP* ( 50 to 400 bars ) is well known in the field of Diesel engine 'manufacture. A liquid is forced through a special nozzle and a very fine aerosol is procuced onl; by the high hydraulic pressure. This principle is now used to produce an aerosol from the solution to be analyzed which is then passed into a flame or an ICP for elemental analysis.

In analytical chemistry, work with high pressures has been performed for a lenghty period of time (high pressure, high performance liquid chromatography); for this purpose, there are appropriate high pressure pumps available, as well as sample loading valves. In order to generate an aerosol for sample introduction to spsctroscopical sources < flames, plasmas ) a EPLC-pump is connected via a normal sample valve to a special high pressure nebulization nozzle.

Nozzles of 10, 20 and 30 urn were utilized in these investigations. Solvents (water. MIBX, methanol...) are continously forced through the nozzle via the high pressure pump. The sample to be investigated is introduced into the solvent stream at the high pressure side with sample loops of 5 uL (micro technique) to 2 mL with the aid of the sample loading valve. The fluid is sprayed with the nozzle into the mixing chamber (spray chamber) of an flame AAS or an ICP/OES - spectro­ meter. A lower pressure aerosol -j»E is thus formed which is converted to an. aerosol cloud on collision with an impact bead. The aerosol is then transported with the combustion gases (air, acetylene) into the flame (flame-AAS) or with an argon stream into the ICP.

Ilame^.

aeetylsne sample 'Ma valve/ sample loop high pressure pump

- solution ressrveir gas mixing chamber I water, org. solvents) drain Impact bead ' solvent tiller high pressure nebulization nozzle 120 pm I into 30 urn) with integrated protection «'Iter

Schematic diagram of an exempts of hydraulic high pressure nebulization as applied to sample introduction in fleme AAS.

14* RESULTS:

Aerosol Yield and sensitivity; In flame AAS more than 50* of aerosol yield. This leads to a higher sensitivity; due to the element 3 со в time? better {measured in peak area). For ICF/OES the HKP-nebulization leads to the 2.5 to 5 times higher sensitivity.

Saturated salt solutions: (e.g. 26% Had): The solutions are nebulized without difficulties, the higher viscosity of the solutions being auto­ matically compensated by the flow rate regulated high pressure pump.

Fluids, with very hinh viscosity (e.a. undiluted oils): The nebulization of undiluted fluids Kith a high viscosity, e.g. 20 cP , is possible without any problems. So the sensitivity with HHP-nebulization is about 10 to 30 times higher (comparison of a diluted oil sample and conven­ tional pneumatic nebulization with an undiluted oil sample and the new HHP-nebulization).

Organic solvents! Organic solvents ( MIBK, methanol, acetone...) can also be used as carrier (pressure! fluids. The determination in small aqueous sample volumes between organic solvents as carriers luads to an additional increase of the sensitivity.

Base line stability: There is "no jump" in the base line between different samples and carrier fluids due to the continuous flow of the carrier stream. Memory effects: The memory effect from sample to sample is relatively small because of the continuous flow of water or organic solvent through the sample loop and ИНР-nebulizer nozzle. "Continuous, automatical cleaning".

Independent optimization of the spectroscopics! source and of the nebulization: No nebulization gas is necessary; therefore the optimization of the source (flame, ICP, DCPI is independent from the nebulization. HHP-nebulization includes also flow injection techniques: With an additional loop, e.g. 500 uL. between the sample loop and the HHP-nebulization nozzle, there are also FIA-techniques possible, al Extension of the working range of the spsctroscopical methods by eutomatic dilution. Ы Lowering of very high viscosities by automatic dilution with the carrier solvent (e.g. oil analysis; calibration independent for different oil samples). c) Additon of buffer solutions. Interfaee-free coupling of HPLC-tachninuss with atomic sp.ctrometrv using HHP-nebulization: Kith the HHP-nebulization there exists the possibility of a new, effective on-line-connection between the chromatographic separation (HPLC1 and the subsequent atomic spectroscopic determination. The HKP- nebullzsr nozzle pss the function of an interface. Overall, the combina­ tion of the HPLC and HHP-nebulization is the simplest way for element speciation with higher power of detection (nebulizetion with a,better aerosol yield). There is an improvement in peak-height up to 7 times and in peak-area up to 10 tines compared with the conventionel nebuli­ zation (flame AAS).

Manufacturer of the HHPW-.aeple introduction avstem: Or.Herbert Knauer, Wissensehaftllche Cerate Кб, Heuchelhelmer Str. 9, D-6380 Bad Homburg. Fed.Xep.Germany, FAX: 06172 - 31768.

147 KIHKTICS OF WASHING OF HEBULIZAIION SYSTEM FOR ICF AB3 AES-4 A.V. Bobkov Kurchatov Institute of Atomic Energy, Moscow, USSR One of the most time-cosuming (and important for accuracy) stages in measurements on an inductively coupled plasma spectrometer with pneumatic nebulizer is cleaning of nebulisation systems from the pre­ vious sample solution. For understanding the factors affecting the «ashing time, the kinetics of this process has been studied. The analysis of the plot showing the time dependence of signal in the semilsgarithmic coordinates in replacement of the solution at a high concentration of the element for the cleaning solution, revealed two linear sections: section (i) -/ \ refers to the ргосевв of remo­ te/ val of aerosol from the spray chamber, section (ii) refers to the process of cleaning the liquid path. The parameters of the linear section of the curve mainly slope, are the quantita­ tive characteristic of the me­ mory effect of the nehullzation У system elements. The deep clean- out time (up to reaching the detection limit (Db)) is determined by slower washing of the liquid path (ii) and is very sensitive to the state of the inner surfaces of the tubes supplying the solution and primarily those of the working tube of the peristaltic pump. Use of the accelerated solution supply at the stage of cleaning the nebuliza- tion system with the peristaltic pump, permits the time of the liquid path cleaning to be reduced. If eamples differ a little in their composition, it is enough to reduce the signal of previous sample by 2 to 2.5 orders of magnitude; than the cleaning time is determined by the process (i). In this si­ tuation any methods accelerating removal of the aerosol from the spray chamber permits the time of the analysis to be reduced. Comparison of the kinetics of cleaning processes of various nebu- lization systems have been made. The experiment was carried out on JY38HR spectrometer equipped by a demountable Srlnfield tourch in Trassy modification, peristaltic pump Minipuls-2 and RP-generator Plasma-Therm 1300,

m LODIFICATIOII OF THE ELECTRONICS AND SOFTWARE OP THE ; JY32 AND JY38 SPECTROMETERS I ^^

A.V. Bobkov, E.G. Chudinov Kurchatov Institute of Atomic Energy, Moscow, USSR A description is given of the modified electronics and new soft­ ware of JY32 and JY38 spectrometers, enabling measurements to be car­ ried out simultaneously on two spectrometers. The work has been done for the Jobin Yvon (Comef) spectroanalyzer provided with the direct reading spectrometer JY32 with the dynamic background correction sys­ tem and provided with the sequential spectrometer JY38HR with a sine scanning mechanism. The spectrometers are controlled by the PDP/II com­ puter via three DRIIC general device interfaces. In the spectroanalyzers of the first generations each spectrometers is provided with a separate program. The apectroanalyzers of later ge­ nerations have the common control software; however the measurements are carried out subsequently by the following scheme: washing of the solution supply system - adjustment of the initial wavelength JY32 - measurement cycle JY32: adjustment of the wor­ king wavelength, signal integration, data acquizition - adjustment of the initial wavelength JY38 - measurement cycle JY38 - calcula­ tion - data output. After changing the electronics and creating a new software we could realize an improved measurement scheme (set of operation performed simultaneously are shown In brackets): (washing of the solution supply system, adjustment of the initial wavelength JY32 and JY38) - (measurement cycle JY32, measurement cycle JY38) - calculation - (data output, cleaning the solution sup­ ply system). For simultaneous control of the spectrometers the electronics of the monochromator JY38HR is added with an autonomous scanning unit. The unit is installed "in breakout" of the initial control line of the stepping motor (SM) JY38HR. The computer passes the number of steps into the unit and all other operations including runaway and retradation the SM unit performs autonomously. The simultaneous control software of both spectrometers permits 3-6 lines on JY38 within the range 190 - 300 nm to be measured ad­ ditionally during measurement of the sample on JY32. In a new soft­ ware the functions of the old software of both spectrometers are kept and some now functions facilitating development of the measurement techniques are added.

14t ICP-ABS ВЕТЕННШАТТО» OP THE BLBVBHTS И ЛЛЕКОШЯВО VOLATILE PLUORIDBS ПТО IHB PLASMA IiBS "6 A.V.Bobkov, I.P.Kuznetsov, E.C.ChudinoT Kurebatov Institute of Atomic energy, Moscow, USSR

Introduction of elements into the ICF in the gaseouse form is advantageous. In this oaae the whole anount of the analyte entera the plasma while in the traditional nebulisatlon of the solution» the part oomlne into the plaaaa doei not exceed a few per cent. Conversion into the gaseous phase enables the analyte to he separa­ ted in aoit oases from the matrix and the aoouraay of the signals to be improved by suppression of the noises produoed by nebulicler. In these type of analyses It la important to ensure the full con­ version of the analyte into the gaseous form and to acoount for the chemical and thermal stability of volatile compounds. The In­ strumentation of the method and the way of signal recording is essential. The number of volatile compounds are suitable for introduction into the plasma is very limited. For this purpose simple substan­ ces (Hg), hydrides (As,Bi,Ge,S,Sb,Se,Sn,Pb,Te), oxides (0s,3), chlorides (Al,Ge,P,S,Se,Si,Sn,Tl,V), fluorides Ue,B,Ge,Ir,Ho,P,Pt,

Re,S,SbtSe,Si,!Ee,7,w,U), elemental-organic and complex metal com­ pounds (diketonates, oarbonylea, etc) are used. Host of these elements can be converted into the gaseous phase in the form of fluorides, including some elements which are difficult to be de­ termined and noble metals (Si,B,P,Ir,Pt). •Fluorides as compared with chlorides have higher ehemioal and thermal stability and, when using a relatively high fluorising agent can be obtained from any objects. Among the reagents used for the synthesis of volatile fluorides

(HP, HH.P, F2> halogen and xenon fluorides etc.) xenon difluoride is the moat suitable for work. This strong fluorooxidlser repre­ sents a solid substance, is easily sublimated, converts into liquid state only under pressure. Its handling is quite safe. Its reac­ tions with most simple substances and compounds are thermodynamleal- ly possible; however In many oases the reaction does not proceed because of kinetic difficulties (e.g. In formation of dense fluo­ ride films). In the present paper various ways of gas production, its supply into the plasma and measurement of the analytical signals are des­

cribed on example of S,BtSi,no determination.

150 PECULIARITIES OF ANALYSIS OF ORGANIC MEDIUMS BI I AES-7 METHOD OF ATOMIC-EMI6SI0H SPECTROMETRY VISE I _ INDUCTIYELI-COIJPLED PLASMA (AIS-ICP) S.I.Buchbinder, L.N.Shabanova, B.H.Gil'bert "Hydrotsvetnet", Novosibirsk, USSR Determination of elements in organic mediums by the AES-ICP is dif­ fered from analysis of aqueous solutions by optimal conditions of ana­ lysis, spectra, the used reference samples. On decomposition of the sain organic molecular fragaents the additional power is required so the power, bringing to plasaa is increased on 0.? kW. Simultaneously the flow, cooling a torch and the auxilliary flow, deereasings depo­ sits on the auxilliary torch tube are increased. Vertical distribut­ ion of temperature in the central channel of IOP with the organic aerosol has the maximum on the larger height than ICP with the aque­ ous aerosol and so emission observation zone is moved nearer to tail part of the flame, itemization of organic solutions with the rate more I ml/min iB not effective because mass of analyte, reaching ICP, doesn't increase. Better sensitivity in ICP is provided by the mode­ rate volatile solvents (Яьпзд " I40-IB0°C): xylene, decan, diisobutyl- ketone. The easily volatile solvents (aetanol, hexan and others)cause the deterioration of sensitivity or quenching of ICP, because of con­ siderable loading ICP by organic solvent's aerosol. Spectrum of organic substances in ICF is complicated because of ap­ pearance in it of molecular bands С,, СВ, CB types. However the sensi­ tive lines, being free from the spectral errors of organic formation can be chosen for many elements, excepts lanthanides. multielemental influences in ICP with organic aerosol are expres­ sed weaker than in ICP with aqueous aerosol. However the effects of different kinds, stipulated by distinctions in samples'* viscosity, nature of the used solvents are observed. She question of reference samples CBS) preparation for the direct analysis of organic solutions, the composition of which is considerab­ ly various than one of the aqueous solutions is the actual one. For preventing of possible effects the unificating method of ES preparat­ ion is developed. The reaction between the acidified aqueous solution with certain concentration of the defined elements and acetic anhydri­ de, addition to reaction's product of organic solvent or the mixture of solvents and aliquotie part of basis of the analysed sample is the method's basis. Correctness BS is checked by analysis of the standard samples C-2I of "Conostan" company.

Ml РВ00ЫАВ1Т1ВЗ OF THB GLOW DISCHARGE USB MR THB QIMITOHBTRIO ANALYSIS 0? SIHPIB ADS COKPLKX-AtLOYBD STBBLS Yu.H.Buravlyov, V.P.Zamarayev,B.V.Cheraravskaya Donetsk State University, Central Scientific Institute of the Ferrous Metallurgy, Donetsk, USSR The glow discharge is finding lately more and more extensive ap­ plication for the atonic emission speotral analysis. However the pe­ culiarities of its use are yet unsufficiently studied, and the re­ sults of some works are controversive. ЧЬе aim of this work is to study the features of the influence of alloy oomposition of there structure, of the surface relief, and of the sparking effect on the results of the ferrous alloys spectral analysis with the use of the glow discharge. The apparature was the "ARb-ЭЮОО" and "Polyvac E-1000" quantome- ters with glow disoharge generators. The generalization of the obtained data permits to note the listed factors, in the analysis of alloys on the ferrous base. The influence of the "thirds" elements and of the structure due to dif­ ferent thermal treatment or technology of manufacture results in the shift and in the slope ohange of the corresponding calibration cur­ ves. The systematic deviations may achieve 10-30 rel.% and more. It is characteristic that both the enhancement of the alloy composition and their structure influenoe on the results of analysis due to the superposition of these factors as its slaokening in the opposite ac­ tion. Shis oiroumstanoe permits to explain the contraversity of the conclusions of some investigations In this direction. The variation of the surface roughness grade (from 0,02-0.03 till O.i-O.ljua) in the determination of carbon, silicon, chromium and other elements in the steels may cause the systematic errors achie­ ving 10-15 rel.jC. The manifestation of the sparking (burning) effect depends essentially on the type of the element to determine, on the alloy composition and on the glow disoharge parameters. The mean time of the approaoh of the kinetic ourves to the horizontal line which oharaoterises the definite equilibrium in the processes of the sput­ tering of different elements, is equal to 30-40 s . The obtained data show the neoessity to take into acoount the in­ fluenoe of the aforenamed faotors in the development and application of the technique of the spectral analysis to the particular alloys with the use of the glow disoharge.

IM H0HSPECTRA1 MATRIX E?EECIS DJ ICP-AES ПАЁЗЗГ B.e.Chudinov I.V.Kurohatov Institute of Atomic Energy, Hoscow, USSR

On* of the reasons why the ICP-AES has been Intensely Introduced into wide anslytloal practice ma the data suggesting the absenoe of strong matrix effects. However these effoots should not he negleoted. They, though comparatively small as they are, nay notioeably distort the analytical results by changing the sensitivity of both the analyt and the interferrlng components. If we neglect the nebuliser's clog­ ging and other similar effeots, we have the fallowing main nonspeo- tral interferences: 1. The effeots due to the transport and nebulieation of the high matrix content solutions: i. the signal intensity reduction as a result of decreasing the rate of solution supply because of the chan­ ge in its physical properties; 11. HSD increase of an analyt signal in high solut concentrations solutions; lii. Increase of the "memory" effects in the presenoe of sons ««trices (acids, HH,, B, etc). Chans»з la the signals, occurring at the nebulising stage, are easily corrected using the simple Internal standard method (ISU), 2. The effeots due to the change in the physical conditions of the plasma* 1. Change in the signal sensitivity wich is different for eaoh line and шау reach 10 to 50Jf. The matrix effeots inorease In a series of adds < alkaly «stale < transition astals < second group aetals, and depend on the RP generator type and it* adjustment; 11. At low concentrations (lower than 0.005 HA) some matrices (HC1, НПО,, Al, Zn, la, eto) increase the sensitivity for some lines; ill. The total effeot of the matrix ooaponants sum Is not equal to the sum of Individual oomponentsi lv. The calibration function cur­ vature at high concentrations (exceeding 100 ng/al) ocours for re­ ason» other than self-absorption or self-reversal of the spectral lines. The mechanism of matrix effects in plasma is not dear yet. In presence of matrices both plasma temperature and contribution of various exoltation channels ohangs. under these conditions the in­ ternal standart method in its simple version cannot oorrsot the ef­ fect*. They oan be partly oorreoted by ohanglng the parameters of the 1С? system or using more complicated versions of the ISM. •onspeotxml matrix effeots change the sensitivity of the signals and deoresss the signal-to-background and slgnal-to-noiae ratios, which result in the deterioration of the detection limits, precision and aeeuraoy.

in STRUCTURE AND lUTHaiATXCAl MODEL FOB THE RESULTS OF Ma AMD К DETERMINATION IN THE URINE BY FLAME PHOTOMETRY IN POPULATION STUDIES V.I. Dvorkin, I.H. Timonin, B.I. Minchenko AES-10 USSR Research Centre for Preventive Medioine, Mosoow, USSR The analytical system (AS) developed in the USSR for quality control and standardization of the results of the flame photometric deter­ mination of Na and К in the urine has been investigated. The main goal «as to study the differences between the average concentrations of Na and К in the speolmens of urine obtained from different populations (samplesJ. The investigations were performed in many laboratories. External quality assessment was performed by the Reference Center IRC). RC manufactured and certified standard materials (SH) and also processed the data. The used SH are stable and similar to the specimens under study. AS has an hierarchical structure. The result analysis was performed in both the laboratories engaged in population studies and the RC. It has been shown that the distributions of the major kinds of random error are close to the normal. The relation of the intrarun, run-to-nm, vial-to-vial etc components of variation to the oonoentratlons of the determining elements in the studied range is approximately linear. The relation of the concentrations of Na and К measured in an ordinary manner. I.e. graduated by the water solutions of the elements, to the true values is linear in each run, however, its characteristics suoh as an angular coefficient and a free member of the regression equation, are changing from run to run significantly. In view of the struoture and properties of AS, a mathematical model for the reeults is suggested. It is consist of the 3 linear models which correspond to a) the SH analysis in the RC; b) the SH analysis In the laboratories; o) the analysis of the population specimens in the laboratories. Model (a) Is used for ANOVA, models (b) and (c) for the analysis of oovarlanoe. The problem of heterosoedaetioity and the ways of its resolution are under discussion. Within the framework of the suggested model unbiased estimates for the mean values of the Na and К contents in the population samples investigated by different laboratories can be obtained, and the slgnifioanoe of the differences between them can be assessed oorreotly. When the results for population biochemical studies being analyzed, the analytical errors are usually Ignored. However in many oases it leads to incorrect «valuation of the mean values and confidence Intervals for them and, consequently, to erroneous oonolusiona for the study results as a whole. The utilization of the RH analysis results for processing of the population study data within the framework of the suggested model permits us to' decrease the systematic errors and to increase the signlflosnoe of the estimates for the small differences between the populations under study. IM STAHDARD SPECIMENS FOR АТОКГС-EMISSIOH AH» X-RAY IAES-11 FLOORBSCEHSB SPECTRAL AHALYSES OF STEELS ADD ALLOYS I — G.L.Dobrovolslcaya, Y.V.Malanuk, V.I.Moslchev, A. D. Kharciaoir The Central Research Institute for structural Materials "Prometheus", Leningrad, USSR Characteristics of available standard specimens sets are presen­ ted in this paper» The set for constructional steel analysis con­ sists of 9 specimens standardized as to Si, Mn, Cr, N1, Mo, Cu, V, Ti, Al content (additionally data on W and Ce are presented). The set for I14HD steel analysis consists of 4 specimens standardized as to Mn, Si, Cr, N1, Cu, 0, S and P. The set for X15H4MD steel analysis also consists of 4 specimens standardized as to the same elements and additionally to №. Two sets for ИКС and BM type iron analysis consists of 5 speci­ mens standardized as to Mn, Si, Cr, Hi, Cu, C, S, P, Hg. The set for Л7Н4Ж2 bronze analysis consists of б specimens stan­ dardized as to Al, Hi, Pe, Mn, Si, Ti, V, Zn, Sn, Pb (additionally data on So, S and Cu are presented). The set for A7Mu,14ЮН2 bronze analysis also consists of б speolmens standardized as to Al, Hi, Pe, Hn, Si, Zn, Sn and Pb (additionally data on С and Cu are presented). The set for А6К2Ж.1 bronze consists of в specimens standardized as to Al, Si, Pe, Pb and Zn (additionally data on Hi, Cr and Cu). The set for Cu-Hn alloys eonslats of 10 apeoimens standardized as to Mn, Al, Fe, Hi, Zn, Mo, V, Si, Pb and Sn. The first set for Tl-base alloys analysis consists of 4 speoimens standardized as to hydrogen content in 0,002-0,03£ range. The second set also consists of 4 specimens standardized as to Al, V, Fe, Si, Cr, Hi, Zn, Mo, Cu, Zr and Sn content. The third set is standardized as to the same elements but it differs from the above one by the higher Al and V content. The fourth set consists of 5 specimens stan­ dardized as to Al, Ко, Zr, Hb, Fe, Si and C. The set for ifS7H1 alloy analysis consists of 6 specimens standar­ dized as to Al, Cu, Fe, S, Hg, Ti, Fb, Sn and Cd content. The set for AU/Wg2 alloy analysis oonslsts of 5 specimens standardized as to 2a, Mg, Cr, TI, Cu, Mn, Zr, Pe, Si, Pb and Sn. The specimens are dellved to the customer at the oontract price.

IK ATOMIC-JuasSIOM SPJSCTHAL ANALYSIS OP SOLID STATO SAMPLES AES-12 I USINO A COOLED HOLLOW CATHODE DISCHARGE A.I.Drobyshev Leningrad State University,Leningrad,USSR The modern level of development of science,technology and produc­ tion has put up before the methods of analytical control the problem of both bulk composition and layer-by-layer distribution of solid state composition.Along with traditional physical methods,such as mass-spectrometry of secondary ions,electronic Auge-spectroscopy, X-ray electronic spectroscopy and so on,the method of atomic-emission spectroscopy is aquiring a more and more wide application for these purposes.Sources of light with laser probe atomization and ones with atoaization by the cathode sputtering process are being used.The la­ tter include the glow discharge in the cooled hollow cathode. A theoretical examination of surface bombardment process by positi­ ve ions of monolyth dielectric sample putting into the space of cy- lindric hollow cathode showed that with supplying the discharge tube by current impulses of microsecond duration dielectric materials sho­ uld sputtering just in the ваше way as metals,Experimentally this co­ nclusion is confirmed by analysis of stoichiometric substitution in the samples of ferrite mono- and polycrystals. The ionic sputtering probe in the cooled hollow cathode makes it also possible to use this source of light for means of layer-by-layer analysis.However for obtaining reliable data it is necessary that the effect of the changed surface layer formed due to the difference bet­ ween individual component sputtering coefficients of the probe should be in the range of apparatus error of the method.A theoretical study of the problem enables to evaluate the relative accuracy of the mea­ sured layer-by-layer distribution with a value of 0,01 ,which is qui­ te admissible for layer-by-layer analysis. An experimental investigation of macroplanarity of surface ion et­ ching of disk-form enmples enabled to determine optimal conditions of plane-parallel etchirr.A microscopic study of etching surface snowed that Ionic bombardment in a cooled hollow cathode does not inorease the surface microroughneas of solid bodies and does not display sele­ ctivity in the case of phase-inhomogeneous samples. Oiving in the paper examples of layer-by-layer element distribution analysis in metallic Bsoples,oorroeion films and artificial monocrys- talline films of ferrltes illustrate wide possibilities of the deve­ loped method and prospects for its application.

1И PHISICAL PARAMETERS AHD SFEOIRDK-iHAHTICAl AES-13 CHARACTERISTICS OF THE HIOBOWAVE DISCHARGE OF AaiosncEEio HIBSSURE Y.V.Oruxhenkov, lu.I.Korovin, V.A.Kuehumov АН-Union Research Institute of Inorganic Materials, Moscow, USSfi Riysieal and spectrum-analytical characteristics are investigated for the atmospheric pressure microwave discharge, being formed with the coaxial plasmatron. The discharge is initiated in the plasmatron coaxial line section at the tangential injection of molecular plasma- forming gas (nitrogen, 5-6 1/min) and the axial injection of the other gas flow (argon, nitrogen, air, 1-2 1/min) through the axial channel of central electrode. The discharge is fed by the 2*50 IIHz magoetron with up to 2.5 kU power. The space distribution of the va­ rious elements emission intensity (both being injected through the axial channel of central electrode and the plasmaforming gas) gives evidence to the fact that the discharge is a toroidal one and the ex­ citation of atoms and ions takes place in its narrow central channel, dia. 7-8 mm. She range of excitation temperatures, taken by relative line inensities of various elements, is 4400-6700 K. The gas tempera­ ture wae estimated by relative intensity of the CD molecular bands and made up 5100-5400 E. And the maximum values of temperatures were ob­ tained in the near-electrode region and decrease, depending on the bight of observation. The temperature measurements indicate the dis­ charge plasma space inhomogeneity and the deviation from the local thermal equilibrium of particles of different kind, particularly in the near-electrode region. The estimation of n , made by the relative intensity of magnium lines in central channel with T-5O0O K, gave the value of 4хю"-1хЮ cm"'. The additions of easily ionized elementв results in a strong redistribution of atom and ion emission intensity depending on the discharge height. Besides, depending on power, the height of observation and addition concentration, both the intensity increase and decrease take place. While using this discharge as a source of excitation of spectrum for various elements, the detection limits of 0.005-0.1 mg/1 were ob­ tained. The microwave discharge can be used to determine the content of various elements in the O.OW-IOO» concentration range.

IJ7 INDUCTIVELY COUPLED PLASMA STUDY AND OPTIMIZATION AES_«. USING HOLOGRAPHIC INTBVEROHETRY S.Yu.Dudnikov Stale Optical Institute, Leningrad, USSR Advantages of induotively coupled plasma (ICP) as a light source for atomic emission spectrometry (AGS) are well known [1]. The impor­ tant analytical problem is the optimization of 5 basic operating parameters : power, observation height and three argon flow rates. The solving of this problem is often uneasy having as an output para­ meters intensities of several analytic lines, as in this case it's necessary to study the gazodynamic and thermal processes occurring in ICP more perfectly. Holographic interferometry [2], which allows to visualize the warmed-up streams in the discharge, is the most conve­ nient method for this. In the present work the JI-38P ICP-spectrometer was investigated by holographic interferonetry. The double exposure method in the bands of finite width was used, similar to the scheme described in [3]. The resultsshow the opportunity to judge about the configu­ ration of the gas streams in the discharge by the view of interfero- metric picture, and to determine the bounds of warmed-up zones, that permits to give valid recommendations for choise of an optimal combination of the basic parameters. In the laminar flow zone the radial distributions of Ar atoms and temperature were calculated from the shift of the interferomeric bands using Abel invertion. So long as result doesn't depend on the models of plasma equilibrium, the degree of approximation of the discharge to the equilibrium can be estimated after comparison with the spectroscopic data. Such comparison was made in a wide range of basic parameters. Thus the results show thet diagnostics and optimi­ zation of ICP sourses using both spectroscopic and interferometric methods are perspective. References

1. Boumans P.W.J.M. Inductively coupled plasma emission spectromet­ ry// M.Y. 1887. Vol.1, 2. 2. Zaidel A.N.// Usp.fiz.nauk. i898.Voi..U9.N 1. P.105. 3. Dudnikov S.Yu.//Opt.mech.prom. 1988. N 1. P.l.

1И ANALYTICAL ADVANTAGES OF PULSE DIRECT POHDER INJECTION \ш-15 INTO AN INDUCTIVELY COUPLED PLASMA USING LASER BLOW S.Yu.DudnikOY, II.A.Kartasheva State Optical Institute, Leningrad, USSR Direct injection of powder samples is perspective for atomic emission spectrometry with inductively coupled plasna (ICP- AES) [1], especially for analyses of materials with low solubility. However in this case the interpretation of analytical results became complicated by the non-simultaneous entering of elements into the discharge. An original method [2] providing a simultaneous entering of all the ele­ ments and keeping the advantages of direct insertion (easy to prepare samples, free of memory effect and losses) was realized in this work. The powder in a transparent envelope placed inside the torch near the discharge is subjected to the powerful laser pulse. The envelope evaporates and its vapours chucks out the sample into discharge. Investigations were carried out on the Л-38Р ICP spectrometer. For the envelope evaporation the YAG-ND3faser (S J pulse energy in the free generation) was used. Laser light was focused on the light guider, the end of which was placed inside the torch near the dis­ cbarge under the quarz plate with the sample enclosed into a poly- styrol envelope. The device of samples replacement and the charging speed of the lazer circuit provided i analysis per minute. It was determined, that analytical pulse have equal form and length for all elements, that allow to fix the common integration time (0.3-0.5 s); spectral background doesn't change during the lazer pulse; detection limits are about I0-4- 10"5 % using internal standartization one analysis requires 1-10 mg of sample. The results of this work show that the described method is pers­ pective for quick simultaneous analysis of powders in ICP-AES. References 1. Reish U., Nickel H., Mazurkiewich II.// Spectrochim.acta.в 1889. Vol.44. P.307. 2. Dudnikov S.Yu., Kartasheva M.A.// Pat.USSR N 1498247. Bull.USSR "Otkrytja, izobretenija". 1989. N 26. P.196.

1(9 SAMPLING in EMISSIVE SPBCTHAL-SOIHTILLATIVE ANALYSIS I FOR GOLD-OOBIAIHIHG SOLIDS |*M-16 V.S.Engelsht, A.N.Salchenko, L.A.Salchenko Institute of fbysice, KlrgbizSSR,Academy of Sciences, Frunze, US3K •hen analysing gold-containing solids it i* necessary to use an imposing hinge, 1* e. to use each sample moss which represents the material analysed with the given accuracy. Tor estimation of imposing hinge mass simultaneously with gold evaluation automatised spectral- sclntillatlve assembly combined with two-jet plasmatron has been ap­ plied flj. An analytlceJ. parameter in this case is a number of scin­ tillations due to golden particles registered by a radiometer. A sig­ nal from the radiometer was read every second and was treated by mic­ ro-computer in the real range of time. According to the parameters of grading diagram preliminarily Informed to the micro-computer each single impulse was transformed into the percentage of gold containing In elementary hinge, 1. e. such mass which has passed through plasma for the time interval equal to one seoond. Beginning from the follow­ ing case of evaluation the micro-computer gives the average percenta­ ge of gold content and the relative standard deviation of arithmetic average. Sample feeding into the plasmatron will be taking place un­ til computed relative standard deviation of arithmetic average beco­ mes equal to or less than the given accuracy for the quantitive eva­ luations, i. e. equal to 0,1. Sample mass having passed through the plasma for that time Interval will be the imposing hinge for the ma­ terial analysed. In such a way masses of imposing hinges (mA have been evaluated for some gold-containing State Standard Samples and

compared with the clrtificatad ones (me). This Information la given in the Sable following below. Prom the Table it can be seen a good agreement between the data analysed that permits us to believe that *"м method of evaluation of imposing hinge masses applied is correct. liasses of Imposing hinges for gold-containing State Standard Samples (SSS)

Б SSS 1787-80 1788-60 1789-80 1738-83 1790-80 1791-80 2740-83 1121-77 Ggld, 0.0036 0.0033 O.OOC45 0.00046 0.0001 0.0002 0,00005 0.00205 v« 15 1.2 24.0 - 114.0 150.0 - 10.0 mi(g 2.2 2.0 27.0 29.0 120.0 110.0 90.0 9.0 Reference 1. 3alehenko A.X. et aW/Zavod. lab. 1987.Vol.53. K.2. P.28.

1(0 IMPROVING OP EMISSIVE SPECTRAL-SCIKTILLATIVE ISBIHOD OF GObD l^-- _~| EVALUATION IH POWDER SAMPLES I ZJ V.S.Engelsht, A.N.Saichenko, b.A.Salohenko Institute of Physics, KirghizSSR Academy of Sciences, Frunze, USJH When evaluating the content of gold and eome other native elements in powder samples detection limit of the analysis can be significant­ ly reduced with ocintlllative registration of signal. The principle of the method presented is that it reguiree counting up a number of scintillations of spectral line intensity for element analysed, the amplitude of which has been correlated with the mass of particles [1J. Minimus level of the signal registered is fixed above random fluctua­ tions of plasms emission. A good ratio of signal/noise is achieved due to the event mentioned above. Block-diagram of modified combined is shown in Tig. Powder sam-

Bloek-dlagram of mo­ dified automatized combined assembly for spectral-scin- . . tlllative analysis

pie feed into the arc two-jet plasmatron (2) is realized by a dosime­ ter (1). Emission from the ezitation source is decomposed into spect­ rum with the spectrograph 3TE-1 (3) in which the sections with the analytical gold line in the fifth order and the background in the fo­ urth order are distinguished by the unit of output slots (4). Star­ ting signal from two photomultipliers (5) is fed to a differential amplifier (6} and discriminator <7). cutting off noise, the amplitude of which is lass than the given discrimination level. Further, this signal is fed to a digital voltmeter (8), input-output element (9) and computer (10) with an electro-printer (11). Analyser of impulses (12) with a digit printer (13) draws a hyatogram of impulses from gold particles. Using a radiometer (15) the total number of impulses can be calculated. An oscillograph (14) survea for observing impulse shapesi lamp LK-2 (16) aurves for slot tuning. Detection limit of gold is (1-5MO~6* that ie oompared with the value obtained due to ICF-apparetua. The time-interval for one evalu­ ation procedure is 2-3 «in. The combined assembly presented baa the possibility as well for evaluation of granularity of gold partioles and for estimation of powder sample segregation. Reference 1. Proeoptehuk S.I. et al.//3peetroohlm.aota. 1981.VO1.36B, P.11B5.

II.Зек.413 III THE STUDV OF EVAPORATION PROCESSES OF RARE EARTH f— Г ELEMENTS IN D. С ARC I 1

K.Florien, E.TerpekDvS Svermova 9, CS-063 85 Kosice, Ss?R

The total efficiency of spectrographs analysis of nonconducting powder materials is first of all influenced by two fundamental and closely connected processes : evaporation and excitation of the sample. The evaporation of the powder sample components from the carrier electrode cavity is the dominating process the course of which influen­ ces all processes in the plasma and consequently, the performance characteristics of the method. The evaporation of REE from the model matrix of oxide mixtures was studied in addition to classical evaporation curves I = f(t) also by standardized correlation curves according to PLSKD |l|. The method of KANTDR and PUNGDR |z| based on the calculation of half-life of evaporation as well as of matrix-specific marameter "average volati­ lity constant" enabled some quantification of the evaluation. Using the above valuation techniques, the evaporation of chosen REE (ho,Tm.Tb,Dy,Y,Gd,Er,5c,Eu,Nd,La,Pr and Ce) was evaluated with application of various spectrochemical additives (LiCl,NaCl,KC1,RbCl>

CsCl,CuCl,BaCl2) Li2C03,Na2C03,BaCQ3; Na2B407,Li2B4u7) and different experimental techniques as differently prepared carrier electrodes, various exposition times, utilization of Ar atmosphere and so on. The halogenating ability of CuCl additive applied for REE oxide mixtu­ res was verified and proved by a separate experiment. The comparison of individual additive influence from the point of view of multicompo- nent spectrographic method was done by a method |4| based on complex evaluating criteria or on the information theory.

References 1. Plsko E.// Pure Appl.Ch». 1976.Vol.8. P.69. 2. Kantor Т., Pungor E,// Spectrochim.Acta. 1974.Vol.29B. P.159, 3. Floridn K.// Vestn.Slov.Kem.D.us. 1988Yol.35, p.9. 4. Fl6rien K.// Chem.prflmysl. 19B9.Vol.39. P.91.

Itt INTEGHATED APPBOACH OF ЕНГ1ВОШЕ1ПШ, ICP ANALYSIS I _ P.Fodor University of Horticulture and Food Technology Chemistry and Biochemistry Department 1114 Budapest, Villanyi 51, Hungary

Although the use of ICP-AES method in environmental analysis vide spread, the data measured in different countries mainly incomparable. She use of etalon samples permits the comparison in case of equivalent sample preparation, but like in any comparison the environmental ana­ lysis needs for fundamental reference data. To contxoll the environmen­ tal pollution or to trace the absorbed concentration or form of toxic ) and non-toxic elements we need expensive and sensitive analytical pro­ cedures.

She pollution of Hungarian power stations was controlled in the area of wine making district. For the complex analysis the airborne particulates, soil, water, plant, grapes and wine samples were collec­ ted. In sample preparation different methods were compaired. The Hun­ garian soil standard extraction method was compaired with the extrac­ tion methods used in Hungarian Environmental Survey. The comparison of different geochemical sample preparation methods was also made. The digestion of plant samples was made in furnace with matrix modifier, in home made PFTB digestion bomb and using microwave assis­ ted acid digestion procedure. The comparison of data using adequate reference materials and the critic of standard methods was made and described.

For the measurements an Jarrell-Aeh ICAP 9000 direct reader with 27 ehannels was used. The instrument conditions were optimised for different matrices using simplex optimisation. The spectral interfe­ rences were measured and taken into consideration using a computer software. The pollution maps of the power stations were described and compaired with unpolluted reference numbers. ^

>i

I» PRINCIPAL FEATURES OP THE DEVELOPMENT OF THE AES-20 HUXTICOMPOBENT METALLIC SYSTEMS ANALYSIS METHODS BY ATOMIC-EMISSION SPECTROSCOPY WITH INDUCTIVELY COUPLED PLASMA

G.I. Freedmsn, L.N. Timofeeva, V.A. Oaipova, V.V. Guearflky NPO VILS, Moscow, USSR Atomic-emission spectrometry with Inductively coupled plasma has steadily risen to the forefront as a subject of diverse metallurgical material analysis and first of all this method is applied to the de­ termination of compositions of the new and experimental alloys, slags, fuses, master alloys and so on. The necessity of simultaneous determination of diverse number of the elements in multioooponent metallic systems causes a few principal features of tbeir analysis development methods. 1). A special attention should be paid to the method of sample dissolution to ensure sufficient dissolution rate and prolonged con­ servation of all analysed elements in a condition of absolute solu­ tions. 2). It is also important to find optimum conditions for measuring of analytical signals (power, gas flow rates, height of the observed plasma zone) securing required sensibility and accuracy for simulta­ neous determination of both alloying elements and impurities. 3).As interelement influences in the inductively coupled plasma an expressed stronger than in other aouroes the revealing of these in­ fluences and the development of technique for their elimination or registration is essential stage of the study, 4). Exacting requirements for metrologieal characteristics of met­ hods cause necessity to choose the element - inner standard which substantially reduces the deviation of the relative standard results. 5). Obtaining the results, corresponding with real content of the elements in the object to be analysed, is directly connected with the choice of the speetroanalyser calibration, which also re­ quires new Investigations. 6); It would be possible to avoid many of the Investigations described earlier if the standard samples were used for the correct­ ness of the results. The standard samples supposed to be equivalent in composition to the analysed objects» 7). The developed methodological approach made it possible to solve readily the analysis problems of different metallurgical production objects. let DEVELOPMENT AND APPLICATION OP A NEH ELCTROTHERMAL VAPORIZATION SYSTEM , AES-21 W. Funk, A. Golloch, M. Haveresch-Koclc University Duisburg 41 Duisburg, FRG

Electrothermal vaporization systems are versatile auxiliary equipments in atomic emission spectrometry. In the past many different systems hive been described and an informative review was given by Matusiewicz

(1) H. Matusiewicz, J.Anat.Spectrom. 1(1986) 171 (2) W. Funk, A. Golloch, E.Thiemann, Steel research in press.

115 OPTICAL ATOMIC SPECTROSCOPY WITH HOLTlBLaCEHT CAPABILITY Heinz Palk |*Bg-£g SPBCTRO Analytical Instruments, Kleve/ PRG '

Simultaneous multielement procedures are used in analytical atomic spectroscopy if high sample throughput has to be achieved or only a limited sample amount is available. Atomic emission methods such as arc, spark» ICP, glow discharge and FANES are capable to do multielement determinations connected with a large dynamic range of typically more than four orders of magnitude. Additionally to optical emission spectrometry (OES) several attempts has been undertaken to use atomic absorption spectrometry (AAS) in a simultaneous multielement mode. One approach for this goal is the SIM A AC system introduced by Harnly et a.1, which uses a continuum source in connection with a high resolution spectrome­ ter. On the other hand, stability and reliability of line source AAS can be preserved and multielement capability can be achieved, if modern optical concepts are applied. Results with such an approach will be presented. Recently, in OES the concept of a separation between evaporation, atomisation and excitation has been used to form "TandenT-sources. Ely separate optimization of the elementary processes going on in these sources considerable improvements of the analytical performance in multielement OES has been achieved. FANES introduced by Falk et al. and recently FAPES described by Sturgeon et al. are practical examples. The analytical figures of merit of the spectroscopic methods outlined above will be discussed in detail and compared with each other.

1M THE EFFECT OF ACETYUACETONE ON THE DETECTION UMITS AES-23 IN ICP-AES SPECTROMETRY FOR VARIOUS NEBULIZATZON TECHNIQUES V.G*laa,F.Buhi>tFabia Institute of Chemistry» Sileslan University» Katowice, Poland

The effect, of the acetytacetone on the detectability of •leiMnts in aqueous solutions has been studied. It has been established that a decrease in the detection limits of investigated elements occurs both in case of the pneumatic nebulization using Meinhsrd-type nebulizer as well as in the сам of thermal nebulization taking place on the porous Class frit (12 in the presence of the sufficiently heated argon as a carrier gam. It has been observed that in case of the thermal nebulization an important effect on the lowering of the detection limits is due to the pH factor of the sample. The latter nebulizer is characterized also» besides good detectability, by a very low consumption of the sample, ca. 30-50 де/min in continuous flow of the solution into ICP plasma. The latter fact is conected with a very high nebuUzatlon yield of the applied nebulizer in case when the aqueous solution» of the sampler contain 15% of acetylacetone. The nebulization with the use of pneumatic nebulizers is not so efficient.

1-Galac W.Buhi F^S Fraoenius Z.Anai.Chem. 1989. V.334. P.646.

197 CONTRIBUTION OF IBB CHAHGE-TRAffSPER PROCESS 10 THE EXCITATION MECHANISMS IK IIO-JBT PLASMATRON ' ' S.B. Golovko, E.V.Smirnova Institute of Geochemistry, Siberian Branch of the USSR Academy of Soiencea, Irkutsk, USSR Argon plasmas such as the direct current plasma (DCP) and inducti­ vely-coupled plasma (ICP) are widely used as emission sources for ttie analysis of a number of elements [11,2 3 . However the publications dealing with excitation mechanisms is the discharge are sparse. The reoent papers [3,47 describe the charge-transfer process in the argon ICP : Ar+ + X »X+ + Ar +AE. The aim of the present work is to study the effect of charge-transfer in the DCP cf two-Jet plasmatron, which in contrast to such sources as ICP and three-electrode DCF possesses the greater power (~10 Mf). The experimental results were obtained from the two-jet DCP I 5J in argon atmospheric (SO A). Argon is plasma forming and transferring gas with current speed 3.6 and 0.8 1/roin, respectively. The mixtures were prepared from graphite matrix with addition of the iron and chrome oxides. The behaviour of the relative intensity atomic and ionic lines of iron and chrome were investigated. For this lines the so-called Bolt- ипапп-Saha funotions log | vs E, have been plotted, where n is the density, g is the statistical weight. The ranges of energy excitation E, of the studied lines t 4-55-7.13 eV (Pel); 4.77-6,07 (Fell); 5.49-

7.57 (CrI) and 5.86-9.40 (fell). In the regions of energies E» + S±

(BA - ionization energy) below 15 eV all points of Boltzmann-Saha plot lie on the straight line, corresponding to LTE values (IIAE).Fcr ionic lines with energies, close to energy of argon ionization (15-16 eV), the anoaaleous enhancement of intensity,relative to eqillbrium values, is observed. This deviation from Ij^g increases with distance increase from the confluence of jets, along plasma axis.It may be inferred that such an anomalous behaviour of ionic lines near the 15-16 eV limit is connected with the contribution of the charge-transfer process to the exoitation meohanisma.Note that this process is not resonant. Although oross-seetions decrease with ДЕ increase, the charge-transfer process may occur even with a large energy difference. References 1. Decker H.J.// Speotrochim. Acta. 1980.Vol.35B.S,19. 2. Barnes R.H.// ORG Crit. Rev. Anal. Chen. 1978.Vol.7.P.203. 3. Goldwasser A., Mermet J.M.// Speotrochim. Aota. 1986.Vol.41B.P.725- 4. Mullen J.A.M., Raaumakers I.J.M.M., Ьшв-. щ А.О.А.Р. et al// Ibid. 1987.Vol.42B. P. 1039. 5. Zheenbajev Zh.Zh., Engelsht V.S. Two-jet plasmatron. Frunze". Ilim> 1983. 202 P. 1W BLBMaNIAb AHALYSIS 0? GEOLOGICAIi SAMM.B SOLUTIOHS " BY UIDUCTIVBLY-COUPLfiD PLASMA MASS SPBCTROHBTRY IABS"25 S.M.Chernateky, V.A.Bloknln, V.V.Qorkovoy Institute of Analytical Instrumentation, Academy ot Sciences of the USSR, Leningrad, USSR D « Ya • Cnopor ov Geological Institute, Academy of Scienoes of the USSR, Uosoow, USSR

The mass-spectrometer for quantitative elemental analysis of liquid samples by Inductively-coupled plasma mass-spectrometry (ICP-as) has been built. The mass-spectrometer consists of the following main parts: the system of зашр1е Introduction, the plasma system of Ionization utilizing the high-frequency atmospheric pressure argon plasma, plasma-mass spectrometer interface, the modernized quadrupole mass-anallzer, the differential system of vacuum pumping, the computer-controlled system of mass-spectrum scanning, Ion current measurement and processing of mss-spectroeetric data. The performance of mass-spectrometer is demonstrated by the quantitative analysis of geological sample solutions. The element's concentrations In a range of 0.001-100 ug/ml with the relative accuracy of 5-10 % are determined during the analysis. The results obtained are compared to the parameters of commercially available Instruments. The general analytical characteristics of ICP mass-spectrometer: dynamic range, sensitivity and detection limits are reported.

IM DEVELOMEHT OF UTOnCTIVElY COUPLED PLASHA AES-26 ATOIIIO-EMISSIOH SPBCIBOSCOPY (REVIEW FOB 1967-19S9) L" V.V. Gusarsky, 7.Л. Osipova, L.H. Tlmofeeva ИРО VILS, Moscow, USSR The first disoharge of induotively coupled plasma in ite modern font ma achieved in 1942 by Babat f ij . For analytical purposes, plasma of a high-frequency disebarge was for the first time used by Greenfield in 1964 [г] end by Fas- eel in 1965 [з], who has disooTered detection Units for 20 elements and named the discharge "inductively coupled plasma" (ICP). Ihese authors were intensively developing the method for the next 5-10 years, using it for analysis of various objects. Later, nany other investigators were engaged in development of the method. For the first time, ICP data were generalized in a separate chapter of the book [4] and in the review [5]. There are, so far, about 3000 origi­ nal papers on the ICP problem, among them 125 reviews and Several mo­ nographs. Xhe present review includes systematized and generalized data on the following problems. evolution history of the method; development of the mechanises of discharge initiation and combustion; plasma generators and burners, investigation of the discharge spectrum; spectral atlases; auperim- positlons and interdependence»; sample preparation for analysis; in­ troduction of the analysed material into the discharge; atomizers for aerosol preparation; nature of graduation dependences; instrumenta­ tion; sensitivity of the method; analysis of metallurgical, organlo, biological and other materials; utilization of plasma in aaaa-apeet- rometry. General conclusions and prospects of the method are given.

References

1. Babat G.I.//Veetnik eleotropromysnlennoBti. 1942. I 2. p. 1. 2. Greenfield S., Jones I., Berry C.T.//Analyst. i964.V0l.e9>> 1064. P. 713. 3. Wendt R.H., Faasel v.A. //lnalyt. Chen. 1965. Vol.37. P. 920. 4. Ousareky T.T,, Freedmen G.I.//Emission Spectroscopy of Aerosols in metallurgy. Hosoow, 1974. P. 101. 5. Guaaraky V.V.//Zavod»kaya Lmboratoriya. 1968. Vol.34. P.. 1463.

IT* ANALYTICAL APPLICATION OF ATMOSPHERIC MIPs lES-27! Gy.Heltai University for Agriculture, Department of Chemistry, GSdollo, Hungary

Microwave induced plasma (M1P) discharges have been of growing intertest as radiation surces tar analytical atomic emission spec­ trometry (ACS) since it became possible to operate them at atmos pheric pressure fl,2,3J. These MIP discharges may ba sustained at relatively low power (40-200 w) and low gas consunption (n,0S- 2 1/min argon or helium). The HIPs are promising sources for AES because highly energetic species, particularly in the helium MIP promote the exictation of elements with high excitation energies (f, CI, Br, I, 0, S, N, P, C) and at the same time other elements may also be effectively excited providing a high flexibility of determination. The analytical application of the MIPs, however, is not free from difficulties. The concept of local thermodynamic equilibrium cannot be accepted for the KIPs, that is the rotatio­ nal (gas) tenperature is much lower than the electron temperature. (43. The limited thermal energy and the relatively small volume of the plasma cause diffuculties with sample introduction, desol- vation, evaporation and etomlzation. Consequently, MIP sources were previously applied for exciting gases nr dry aerosols as produced by electrothermal evaporation, by hydride generation, 01' as element specific detector for gas chromatography | 4 (.Excitati­ on of wet aerosols as produced by pneumatic nebulization became possible when torches were developed which were able to produce a toroidal (ergon and helium) or a suspended (helium) MIP. These MIP-structureB are favourable from the point of view of sample introduction and made it possible to elaborate powerful mul- tielemental analytical techniques. Thn main llmitntlnn nf the analytical application is the sensitivity of MIPs to the alkali- nes- Г* I-

R*f«Теплая

1. C.I.M. Beenskker, Spectrochin. Acta. 197S.Vol.31B.P. 4B3. 2. C.I.M. Beenekker, Spectrochim. Acte. 1977.VM.32B.P. 173. 3. J.P.J. Ven Oalen, P.A. De Lezenne Coulander and L. De Gal an, Spectrochim. Acta, 1978.Yol.33B.P. 545. 4. J.P. Matousek, B.J. Orr and M. Selby, Progr. Analyt. Atom. Spectrosc. 19B4.Vol.7. P. 275.

171 TEMPERATURE PROFILES IN U-SHAPED AR-STABILIZED ARC AES-29 I .Holelaitner-Antunovi6*, G.Anuria and M.Tripkovic Institute of Physics, P.O.B. 57, 11080 Zemun Institute of Physical chemistry. University of Belgrade,Yugoslavia U-shaped Ar-stabilized d.c. arc is a very stable spectrochemical light source, convenient for the analysis of solutions. The deteeta- bility of a lot of elements is satisfactory and comparable with the detectability in ICPU3 The aim of the report is to complete the diagnostics of this exci­ tation source. For this purpose the radial distribution of emission was observed in side-on direction. Four emission ionic lines of tita­ nium have been choosen between 322.4 and 324.2 nm. (r) Till 322.4nm The common characteristic of the line distributions in this exci­ tation source is that maximum of emission is shifted from the plasma axis. The radial distri­ bution of one of the titanium lines is presented as represen­ tative in Fig. After smoothing the experi­ mental curves and calculations 2 3 Г (mm) of the Abel inversion, the Boltz- mann plot diagrams are plotted and the corresponding excitation tem­ perature distribution is observed. The experimental results have shown that titanium can be used as thermometric element only for the plasma region of 1.8 to 3.2 mm radius. The temperature in the whole plasma core was measured applying the same method on the relative in­ tensities of continuous radiation in spectral region from 341 to 490 nm. The influence of matrix element potassium {0.26 % aqueous solution of RC1 is used as buffer) on the temperature profiles, is considered too. Bafervno* 1. Marinkovic M., Antonijevic v,//Specti.ochim.acta.1980.V .35B.p.l29. USE OF HOUSEHOLDER'S ORTHOGONAL TRANSFORMATIONS IN NUMERICALLY STABLE LEAST SQUARE ESTIMATION OF PARAMETERS IN REGRESSION MODELS CORRECTED FOR A MATRIX EFFECT |.__ "

A.A.Ivanov. V.I.Mosichev Central Research Institute for Structural Materials "Prometheus", Leningrad, USSR

It is suggested to use Householder's orthogonal transformations in regression estimation of parameters of models corrected for a matrix' effect observed in atomic emission spectrometry. Algorithm developed for study of mathematical calibration models takes account of additive and multiplicative matrix effects which are responsible for parallel bias and charge of slope of initial calib­ ration curve, received in absence of influencing elements. The mathe­ matical model may be represented in form

( + 1 V ¥VA f-V^" * f/AtW «»

Estimation of inflluence coefficients ^*A: • £k* corresponding to influencing elements of matrix with concentrations С. С, is per­ formed by building Householder's transformations and their application to system of equations (11. Due to orthogonal transformations do not change Euclidean norm. procedure is numerically stable and insentitive to error accumulation and uncertainty of the input data. Pseudoinverse matrix is calculated in algorithm in implicit form, allowing to solve the tasks with deter­ minant close to zero. BASIC-program is developed for microcomputer of spectrometers HFS-6. DFS-40. Examples of account of matrix effect are represented for emission spectrometry of steels. The results obtained are compared with those of another numeric methods.

174 ROBUST REGRESSION PROCEDURE FOR CALIBRATION OF ATOMIC EMISSION SPECTROMETERS 118-31

A.A.Ivanov, V.I.Mosichev Central Research Institute (or Structural Materials "Prometheus". Leningrad, USSR

The method based on the use of robust statistical estimation of ca­ libration parameters is suggested.The mathematical model of calibration is V - Xjl + S . where Y - a vector of signals. X - ntf'-.rix of in­ dependent variables. j9 - error vector. £ - vector of parameters, to be estimated. Iteratively «weighted least square method with special choice of ro­ bust initial values J84 for the parameter estimates is used to receive

T T the solution J»t . given by /^ - ( X W X )"*XW Y . Huber's f£ - function with tuning constant a - 1.5 is used to cal­ culate statistical weights for each standard sample selected for calib-

ration: ^ ^ ТИ* -Xt^j/S I f r- f x . |xU • Ь ( yi "X tA,/ S lа,В1 ^п x.lxl> a '•• A robust measure of acale S is the median of the non-zero absolute values of the residuals S - med (< I y^ - XLj^l )/ 0.6745 ] . After each iteration, solution Je4 is used to obtain new weights, and ite­ ration continues until convergence criterion chosen by spectroscopic is satisfied. Suggested procedure may be used for calibration in wide concentrati­ on intervals of components, to be analised. In this case composition of standard samples may differ considerably, and outliers are possible in experimental data, with the result that parameter estimate become erroneous in traditional least square regression. Г - function prevents parameter estimates J» from the influence of outliers, but information corresponding to outlier participates in evaluation with small weight. Examples of practical appliance of robust calibration procedure are described for spectrometers MFS-8, DFS-40 used for spectral analysis of steels. BASXC-programs for microcomputer are developed to perform calculations.

174 FEATURES AND METROLOGY OP MULTIHLBMENTAL SPECTRAL AES-32 ANALYSIS BY THE EXTERNAL STAHDARD METHOD ' ' T.I.Ivanova, Yu«A.Tkachev Institute of Geology of Komi Science Centre of the Urale Department of the USSR Academy of Sciences, Syktyvkar, USSR

1. The high conditions Identity of synchrotron spectra excitation of investigated sanple and comparison sample (CS) in two series-connected radiation sources, their aynchron and approached fixing on photographic plate by Teplyakov-Bohlov method permit to convert to the external standard method in spectral analysis. 2. The same line in the spectrum of investigated sample and in the comparison sample spectrum is used as analitical pair. It permits to make analysis simultaneously on many elements (20-30) and use the natural standard samples (SS) of composition as operating standard. 3. The different-accuracy of content attestation in »S required the generalisation of the least squares method to construct a graduated graph. Its angle coefficient is suggested to calculate from the formula

2 2 2 a b = {Z*i4l*l - Ew$*i Cwiyt)/(Ewi* i - £ wixt) t where w.* 04/V£tf i, 08{ж o*3j + 0?Ei i o*y - the measurement error of analytical signal у , Caci - the attestation error of content «i, in standard i . 4. The content In a sample is calculated from function, the inverse of regression equation of analytical parameter on the content. The analysis correctness is determined from the parameters estimation error of graduated graph, and reproducibility is estimated from the measurement error of analytical signal. Th analysis aggregate error is calculated from the formula

where S2x - dispersion describing SS scatter in the contents. 5. For precision neasuriments and for analysis and attestation of new SS in particular it is offered to use it as CS at the totality survey of attested SS. Every pair of SS-CS is suggested to photo­ graph twice by changing places. The graduated graphs to construct froa average of two analytical parameters. The content in a new SS to calculate at zero analytical parameter. 6. The suggested nethTda ware utilised for SS black shales analy­ sis of M8SB-1 (0SA),whioh was kindly granted by professor R.Covwiey. The received results correlate well with attested ones: So Zr Ti Cr V Qa Co Ba 08Л 121.23 43*45 222T±183 48119 26841113 16±4.4 241.4 733±96 AUTH 121.7 86+20 гОвО^Га» 480±36 27201350 181.7 221.4 740180

176 AUTOMATED SPECTROGRAM WITH PHOTOELECTRIC SPECTRUM AKS-33 RBOORDIHG ИЖ SPECTRAL ANALYSIS A.Y.Iohutov, Yu.S.Nagulin, K.Yu.Hagulln, V.V.Turkln G.I.Chuvlna, V.A.Chumakova Kazan State University, CDO "Photon*. Kazan, USSR

A high level of non-conventional diffraction grating and micro­ electronics fabrication technology allowed to make a new DFS-458 - spectrograph for speotral analysis. As shown in Pig. the device is based on the optical system using concave non-conventional diffraction gratings and position- sensitive detectors.

Мопйог Com­ Buffo- Qigi t»—— f— ш/fi-toe. putet me/noiy Uzet ptinttoQ

PtoowmmaSie. putse a-enetatoi. Block diagram of a spectrograph

The algorithms for devioe control and measurement processing are developed. The software allows an user to take account of features of a specific probe analysis by inputting his subprograms into it, Speotral and energy characteristics of photodiode linear position - sensitive transducers and charge-coupled devioe transducers are in­ vestigated. Toe results are compared with literature. The effect of detector cooling and temperature stabilization on its astrological characteristics are investigated. Estimations of measurement errors of hollow-cathode lamp radiation intensity are checked. The possibi­ lity of use of the device for speotral analysis is considered.

II* ELIMINATION OP INTEHFERENT EFFECTS OCCUR ING IN HYDRIDE GENERATION ICP AES BY SASD METHOD

I.Jaron and L.Pszonicki Institute of Nuclear Chemistry and Technology, Warsaw, Poland

It has been found that the signal cf the analyte obtained by the ICP-hydride techniques are deformed when othrr elements forming hydrides are present in the sample. The effects of such elements on the determination of selenium and arsenic were investigated. It was found that these effects were not observed when the hydrides of the analyte and of the interferent elements were introduced into the plasma separately at the same time. This suggested that the interference effects occur in the condensed phase during the hydrides generation.

The usefulness of the standard addition and successive dilution method {SASD method) I1J for elimination of these interference effects was examined. Preliminary results indicate that the SASD method is not only effective for the elimination of interferences of this type but it also enables the verification of the obtained results.

Reference

l.Pszonicki L.,Skwara W.,"Standard addition and successive dilution method. Evaluation and verification of results in AAS analysis.". Та1anta,(1989) in press.

12.3«K.4I3 m ATLASES OF SFBCTEUM LIHBS IK ANALYTICAL BMISSIOH I ABS-35 SPECTROSCOPY !lfl__- S.K.Kalinin, V.II.Ferevertun, S.L.Terechovlcb Inatltute of Geologioal SolenoesiKazSSR Academy of Sciences, Alma-Ata,USSR Atlases belong to reference manual» of principal use,essential in speotral analytical work.In a oompaet and convenient for» they repre­ sent data on relative distribution of analytical lines,their inten­ sities, shape and width. Authors oomplled a comprehensive series of atlases ooveriag a broad region of optioal speotrum /1-37 which comprises: 1. Atlases for spectroscopic analytical types of equipment: atlas of spectron lines for the quartz-prim spectrograph (2040-695o£) glass-prism spec­ trograph (3718-9110A),grating spectrograph (2280-6430A) and vacuum spectrograph (64-2095A). 2. Atlases of pure element epeotra-iron,mer- oury,oarbon, copper, plumbum, sink, cadmlum,blamuth, stibium;bydroear- bon flames and heated gee systems containing nitrogen and oxigen. These editions inolude photographic Inagee of speotra,wlth basic characteristics of spectral lines given directly on the photoinages as well as in supplemented tables with the most reliable printed data summarising many years of experience in utilisation of emission spec­ tra for analytical purposes. Spectra are represented on 20:1 scale whioh suit the use of projectors with the same scale of multiplica­ tion. Methodological issues have been resolved - principles of speotrum line selection,source of excitation,standard conditions for acquisi­ tion of speotrograme,preparation of standard mixtures.A method is sug­ gested for comparative estimation of apeotral line intensities In gra­ des, based on their presence in the speotrum of samples with a preset element content. Atlases of spectrum lines provide reeearohers with essential infor­ mation pertaining to apeotral studiee.ehioh is Important for the Iden­ tification of spectra as well as for the development of speoifio ana­ lytical teohnlque for researohes relating to composition of substances. References 1. Kalinin З.Ц., Zamiatina СМ., Perevertun V.K., lerekboviob S.L. Atlas of spectrum lines for the quarts-prism spectrograph. Alma- Ata: Kauka, 1966. «5 p. 2. Kalinin 3.1. at ml. »e spectrum: 2320-2350 1. M.:3tandarty,1986. 42 p. 3. Kalinin 8.K. et ml. Atlas of speotrum lines for the grating spec­ trograph. Alma-Ata: тайка, 1990. 62 p.

I» ORBATION OF THE SLKUKNT CONSTiraiTION BIOLOGICAL HBFSHSNOE uiipgPTtTa OK <""» BASIS OP *™ SDIUIffiAHBOUS ICP ATOMIC AB8-36

A.B.Kamensnikov, P.I.Slavin АН-Union Research Institute of Optios-Fnysloe Measurements, Gosatandart, Moscow, USSR Analytioal method based on using the simultaneous ICP atomic •mission spectrometer ia the most suitable In creating the refe­ rence biological materials of elements constitution. This conclu­ sion baa been made after an «11-round consideration of its possi­ bilities. She analytical oharaoteriatioa of this method proved to be the most perfect. Moreover, automatization possibilities are the best, it permits to determine all the method parameters by spectrometer software.

Fur* Spectrometer Biological Certifi­ Analy­ chemical eartificatlon sample cation sis reference method program­ method materials me of analysis method

Certification Certification Measurement of the of tha analy­ of tha ele­ spectrometer sis method ment consti­ tution T Aoouraey Certificated Beference oharaoteriatioi analysis materials of spectrometer method

Creation aoheme of tha biologioal reference mate- riala for element constitution

9!his method has been examined In the production of the natural reference blood serum and artificial urine materials on the basis of using ICAP-61 spectrometer (Thermo Jarrell Ash Co.,USA). AES ANALYSIS OF HIGH PURITY SOLIDS USING HALQNARC SOURCE T. Kantor* end Qy. ZAray" -m

•Analytical Research Group of Hungarian Academy of Sciences, Technical University of Budapest, Budapest» 1521, Hungary

**Hungalu Engineering and Development Centre Budapest» 13B9, Hungary

The combination of electrothermal vaporization and arc excitation

determined in geological samples with the use of Na or Ar atmosphere in the graphite furnace. The extension of the applicability of this source is possible by halogenation of sample in the furnace. This can be performed conveniently with diluted halocarbon vapour, and the ETV- arc source which makes possible the introduction of halocarban vapour is called "halonarc" C2J. An overall information on the detection power ensured by the halanarc has been obtained applying multielement standard solutions and determining background equivalent mass (BEM) data for 34 elements* ВЕН values in the 1-5 ng range were found for several elements (e.g. Al* B, Cr, Cu, Fe, Mo, Ni, Ti, V) using a medium dispersion quartz spectrograph C2J. It follows that detection limits at O.i ppm level can be obtained applying 10-50 mg solid sample, provided distillation of traces takes place in a relatively short time (less than 60 s). The halanarc source, which is applicable to both solution and solid samples, is depicted in Fig* E3J: 1 graphite sample boat; 2 graphite tube (horizontal part)| 3 graphite outlet tube; 4-5 graphite holders; 6 glass chamber] 7-8 water cooled braes bodies; 9-10 stoppers with 0- ringst 11-12 isolating parts; 13 base plate (aluminium); 14 graphite counter electrode. The switching of the furnace power supply

IN

Ш Ar.CCl-

Schamatic Df the ETV-arc combined source with halocarbon vapour introduction ("halonarc")

References 1» Preusa E.//2. angew. l*linerologie.l?ai. v.3. p.e. 2. Kantor T.//VII Polish Spectroanalytical Conf. and X. CANAS. Torun, Poland, 19SB. 3. Kantor T.//Hungarian Patant. Rag. No.4091/88. Sponaored by tha Hung. Acad. Sci. 4. Zaray Gy., Farkas A., Varga 1., Kantor T.//Pr*aanted at thia Confaranca. 5. Sehafar H.//Angew. Chsnie. 1976. V.BS. P.779. 6. Bainrohr E./ZMikrochim. Acta.l9B9. V.I. P.121.

IS! MUbTIFUNCTIONAL AUJOCIiAVES FOR SAMPLE PREPARATION TO AES-3B SPECIAL ANALYSIS Yu.A.Karpov, V.A.Orlova State Scientific Research and Design Institute of Rare Metal Industry» Moscow,USSR Most materials and substances oannot be investigated by means of spectral analysis directly without previous ohemlcal sample treat­ ment. Generally the chemical sample preparation Includes sample decom­ position, unnecessary component separation and sample transformation to the form optimal to the analysis technique applied. Commonly used operations of the probe chemical transformation posess significant disadvantagess process duration, pollution by rea­ gents, losses of components under investigation. Рог that reason a wide range of analytical investigations based on novel automatic spectral instruments require the use of autoclaves. However tradi­ tional autoclaves provide solution of just a particular problem each and cannot Improve radically the efficiency of sample preparation. One of the most promising ways to solve this difficulty is to de­ velop multifunctional analytical autoclaves where all necessary pre- analytical chemical sample prooessing operations are oarried out in consecutive order. Within this concept framework a series of multifunctional analy­ tical autoclaves baa been developed, including autoclaves for parti­ cular probe component selective dissolving, autoolaves with the rea­ gent self-purifying, autoclaves carrying out all the stages of im­ purity concentration up to obtaining the ready concentrate in a gra­ phite oell or on the spectral eleotrode, and autoclaves for impurity transformation into gaseous phase with the extracted gases direct de­ livery to the spectrometer. A number of autoclave application methods either Independently or as a complex laboratory for autoolavie sample preparation baa been developed for the analysis of high purity materials and substances, biological objects, mineral resources and complex synthetics.

IU OPTIMIZATION OF EMISSION SPECTRAL ANALYSIS IN THE I. I VACUUM ULTRA-VIOLET REGION I*88"39! Z.Z.Khamzin Kazan Slate University, Kazan.USSR One of the common emission sources for analytical purposes in the vacuum ultra-violet spectral region is various spark discharges. The use of discharges initiated by activating pre-breakdown processes in sample electrodes appears to be proalslng, since not only are the breakdown conditions facilitated in this case, but a stable disharge development and burning are thus ensured CI). A study of various elements' spectra and of temperatures in a discharge cloud shows that for each ionization stage there exists a definite temperature range, where the number of ions of a given stage is maximal and it is always possible to improve the conditions of exciting the chosen spectral lines by optimizing the experimental techniques. The analysis should be regarded as a multi-factor experiment, while optimization carried out to improve the sensitivity will consist in finding the signal optimum range. The experimental results on determining the optimal excitation conditions of the following spectral lines of nonoetals in carbon steels are presented: С1-1Э6.07na, Sl-143.33nm, Pl-177.S0nm, P1Y-S5.07nm, Silli-120.eSnm.The experiments were made with a DF5-29 vacuum spectrograph with 2400 lines per mm and a curvature radius of lm. Both condensed and a low-voltage discharge with a high-voltage ignition were used. A truncated cone-shaped magnium rod was used as one of the electrodes. The discharge contour parameters, discharge voltage, interelectrode gap and initial electrode temperature were variable. The response surface has been investigated for the linear model. It is shown that line Intensity can be increased 2-5 fold by the right choice of factor values. An appreciable effect of Initial electrode temperature on emission intensity has been found. This may be due to the fact that the physical mechanisms of pre-break-down processes are based on such temperature dependent phenomena as electronic emission and desorption of electrode adsorbed molecules. They also largely determine the development and characteristics of a discharge cloud.

Reference 1. Davletshln E.Tu./VZh.Prlkl.Spektrosk. ig87.Yol.46. P.711.

tas SPATIAL PROFILSS OP ATOM AHD IOK HUMB3R DBWSITI3S | IK THB ANALYTICAL ZONB OP AH ARGOK ICP |AB8-4Q M.A.Kartasheva, S.Ya.Petrov ntate Optics Institute, Leningrad, USSR

Spatial profiles of Zn and Cd «to* and ion nueber densities in an argon ICP ware evaluated by the absorption spectroeetry. The JY-38P analyzer мае used in our work. Operating conditions were the following: generator power - 1 kw, carrier argon flow - 0-65 1/ein, plasea gas flow - IS 1/ein, observation heigt 10 and 16 ям. The plasea torch ieage travel relatively the entrance slit of the spectroeeter was per f orated by a rotating silica plate. Resonans transitions of Zn I«II and Cdt,IX were used for Measuring the atoe and ion ground states nueber densities.

The obtained atoe and ions densities lateral profiles were transforeed in radial ones by the Abel inversion procedure* The results of eeasureeents snow that the sueeary < n* + ru > concentration of atoes and ions is about sf 10»» иг* and slightly changes in the analytical zone depending on the observation heigt and the radius. This concentration decreases strongly after the distance about of г» - 5 ее fro* the axes of the discharge. The local atoe and ion densities profiles are in strongly dependence

on the distance free the axes of the ICP source» nm « n. at

the axes, when r-0 and n* < n. for all the r greater than re.

The data obtained in this work together with electron nueber

density( excitation temperatures, spectral line eeission spatial characteristics сшп be used for the evaluation of non-UTE phenoeena and excitation Mechanises especially charge transfer- between analуto atoas and argon ions. Furthseore the sueeary atoes end ions concentration value can be used for the nebulizing systee effeciency exploring.

184 BAKIHG THE RBPBREHCE DATA POR THE PROBLEMS OP THE I АТЮЛ. ATOUI0-EKI3SIOH SPECTROSCOPY I—_ A.H.Kuohenev, Yu.U.Smirnov Новее* Poirar Ingeneering Institute, Moscow, USSR By the use of the atomic-emission spectroscopy one can find the principal information about the chemical composition of the investi­ gated substance in the speci.ral linos emitted by it. For the soluti­ on of the quantitative problems of atomic-emission spectroscopy it is necessary (besides the knowledge of 'be macroscopic parfaueters of he discharge used) to have the information about the atomic con­ stants, characterising the processes of atoms excitation in the dis­ charge. Although the principal meohaniam of the emission spectra ex­ citation in the discharge is the nonelastio electron-atom collisions, the information of the important atomic constants - the oross secti­ ons of these processes — is very limited up to now*

The experimental system has bean created and the experimental me­ thod has been elaborated allowing to make systematic measurements of eleotron-impact exoitation cross sections for almost all elements in D.I.Mendeleev's table. The extended orossing atomio and electron beans are used, and the gasfull oell method is used while investiga­ ting non-condensed gases. The refractory elements are evaporated by electron-beam heating. The use of the great volume of electron-atom interaction space has permitted to considerably inorease the experi­ ment informativity without the inorease of the atoms concentration in an atomic beam and current density in an electron beam, and it has also allowed to Improve the spectral resolution.

By the beginning of 1990 the excitation cross sections for the atoms of 48 elements had been measured, including the most refractory and widely used metals in scientific researches and praotloal appli­ cations. The measurements are made for the spectral lines located in the spectral region of 190-850Ш», and the dependenoe of the excitati­ on cross sections on the electron energy is registered in the energy range from the excitation threshold up to 200eV. She eleotron energy partition width is 0.9-1.OeV. The results received give the possibi­ lity to quantitatively interpret the emission atomic spaetra by ma­ king analytical investigations.

IW SPECIROHmiC METHOD OP ISOTOPE COaTOSITIOH AHALYTICAL П7Г7Л AKS-42 COHTROL IM BIOLOGICAL, AGROCHailCAL AND ECOLOGICAL SIUMSS ' ' WITH STABLE ISOTOPES G.S.Laseeva Institute of Physics, Leningrad State University,Leningrad USSR Spectrometry «ethods of determination of isotope composition of nitrogen, oxygen, hydrogen and carbon are widely used at performance of biological, agrocheaical and ecological studies Kith use of t8N, 19C, ,e0 and *H. Method of eiission spectroaetry, proTiding precision of isotope con- position determination, sufficient for majority of experiments with tracer has the following advantages. Optical analyzers use siaple re­ liable and cheap equipment, which needn't high qualification level of personnel and in conduction of autoaation they provide great efficiency of determinations in routine analyses. Minimal quantities of analyzed gases (up to 0.2 mg of nitrogen and carbon) are sufficiently lower than those in commonly used Bass-spectrometer, Finally, use of autono­ mous spectra excitation sources (high frequency non-eleotrode discharge) in optical analyzers allows to perform a complex of analytical problems using the same spectrometry installation (nitrogen isotope analysis both enriched and depleted tole U, determination of1S N and ,8C in one analytical cycle, etc.), that is rather difficult for mass-spectro- metric analysis methods. Leningrad State University Institute of Physics has developed a cou­ pler of speetrometric methods and equipment for isotope control in bio­ logical, agroobeaical and ecological studies with stable isotopes, namely: basic "N, l8C, 1*0, *H determination methods in pure gases (HB, COg, CO, HgO), universale method of probe preparation for selection of analyzed gases and on their basis - different variants of control methods for specific problems, solved with isotope tracer. In paper under consideration the following variants are described: isotope ana­ lysis of depleted to(e H nitrogen, determination of complex ,BN- 18C- *H - tracer, local determination of isotope tracer in plant samples with their destruction by laser. the method is applied in agrochemical experiments with labelled nit­ rogen fertilizers, in biochemistry, plants physiology, genetics (nitro­ gen fixation, photosynthesis and protein exchange, light sensitivity, substance transportation in the plant, growth regulation, etc) and GOO- logy (water pollution, nitrates storage in agricultural products).

IM VARIABLE RESOLUTION IN JOB1N YVON ГСР SEQUENTIAL ASS-43 SPECTROMETERS: A NEW STEP TO ENHANCE ANALYTICAL

RESULTS

Joel Leduc Alain Lcmarchand ISA Jobin Yvon, Longjumeau

Selectable entrance and exits slitt arc now available in a new and unique slit assembly.

Both the entrance tod exit slit plates contain four different slit widths, in addition to an

infinitely large (2шт diameter) alignment aperture. The slit widths available for the

entrance are 10, 20 & 30 urn and the exit are 12,25,50 & 100 urn. Selection of the proper

width for each slit and for each individual clement in each sample matrix is under computer control. In this way, the slit widths may be optimized for any matrix or sample type. For example, if there is an interfering spectra) line adjacent to the one of interest, high resolution is necessary. In this case a 10 um entrance and 12 urn exit would be selected and ibe monocbromator would be stepped across the line of interest, thus avoiding the possibility of interference from the adjacent line. On the opposite extreme, if there are no interferences or background changes, the widest slits might be used. This results in two advantages: first, the highest precision would be obtained because no stepping is necessary and the system is behaving similar to a simultaneous one; second, because scanning of the spectral line is not necessary, lime would be saved. The purpose of the other slit widths is to give flexibility for any intermediate situation. These are only two of the five possibilities of the MULTI-MODE OF ANALYSIS which are available with SELECTABLE SLITS. Other possibilities use Gaussian and Simplex mathematical data handing for the various slit combinations. No other sequential ICP system has this advantage of individually optimizing the optical resolution and the mathematical handling of the data for each element.

V Iff DISPERSION MATERIALS STANDARD REFERENCE SAMPLES IN | 1 ATOMIC-EMISSION SPECTROMETRY DEVELOPMENT, APPLICATION I AND METHODOLOGICAL SUBSTANTIATION

D.G.Lisienko, Yu.I.Korovin, M.A.Combrovskaya, v.N.Muagin Urals Folytechnieal Institute, Sverdlovsk, USSR It has beei. shown that while producing standard reference samples (SRS) for atomic-emission analysis of pure dispersion materials with impurities eontent 1-10"' - 1-10"

188 INTRODUCTION OF THE GASEOUS HVDRIDES OF SELENIUM AND TELLURIUM INTO AN INDUCTIVELY COUPLED PLASMA OF LOW POWER ( ! KW ) •

Alopez-Molinero, 0. Berrlobero, JJUechon, J.R.Castlllo Dep. Analytical Chemistry, University of Zaragoza, SPAIN

The well known analytical performances of Inductively coupled plasma -atomic emission spectrometry obtained in single and multielemental determinations at major, minor and trace levels have consolidated the state of the technique as an analytical method used in routine. The construction of solid end simple spectrometers, with low consumption of power and gases has contributed to this status. Neverthless, in these systems, the introduction of gaseous samples as hydrides have many difficulties. in the present work. Selenium and Tellurium hydrides have been introduced into a commercial ICP spectrometer of low power (P.E. plasma 40), coupled to a home-made hydride generator, previously designed and optimized. The developped methods of analysis have been applied to Se and Те determinations in soils of agricultural interest. in this context a commercial spectrometer has been fitted to receive the gaseous hydrides and byproducts of the hydride reaction obtained in a continuous flow mode from the generator. And so , the nebullzation gas (in the standard apparatus) has been used as carrier gas, without change of the common values of presion and flows; the spray chamber has been modified to reduce the diffusion of gases. The analytical parameters of the Selenium determination can be characterized by: a L.D. 0.006 дд/mL, with a linear range in the response from 0.015 to 0.500 ug/mL A precision (as S.D.R.) of 9.2* was obtained for 0.1 дд/mL. Great difficulties have been found with Tellurium hydride , because of its Inestability, which decompose to Tellurium elemental. in this case the hydride introduction can be accomplished using a shorter conduction. The determination of Se and Те In soils have been carried out with a previous elimination of the mineral content (Fa and Cu Interferes seriously ) by ionic interchange chromatography.

References (1) Thompson п.; Pahlavanpour В.; Walton S. J.//Anslyst 1978,103,566. (2) Wang x.; Barnes R.M.//Spectrochimlca Acta 1986,4 IB, 9,967-977. (3) 0. Barriobero; J.M. Lechon,Thesis,t990, University of Zaragoza.

1M METROLOGIC ATTESTATION OF THE METHODS FOE EMISSION SPECTRAL iXS-46 AHALYSIS OF ECOLOGICAL OBJECTS A.F.Losevs, V.I.Usachova, I.A.Loseva Rostov State University, Rostov-on-Don, USSR In developing the methods for quantitative emission epeetral ana­ lysis of natural waters, suspensions, bottom sediments, soils and hy- droblonte the most important and obligatory stage is their attesta­ tion which aims at determining aocuracy (A) within the given measure­ ment technique and at normalizing the analysis procedure. In the process of attestation the methods it has been found that determination accuracy increases «hen one appliess diffraction spect­ rograph, palladium as an internal standard, graphite powder as a buf­ fer, chemical composition of the working standards similar to that of the samples analysed and also calculation of element composition using relative Intensities. The paper presents the results of the attestation of the methods for the emission spectral determination of eight elements (Hi, V, Co, Cu, Mo, Fe, Tl, 51, in the concentration range of 1.0 - 80.0 mkg/L) in natural and purified waste water, using a set of standard and refe­ rence samples prepared on the basis of standard samples of GS0H1I (SOV- 2P, S0V-3) type. Using the results of 20 independent determinations of the element concentrations in each reference sample parameters of re­ producibility and correctness of measurement have been calculated by means of the dispersion analysis scheme. It has been found that for standard deviation of a measurement result is within 0.05 - 0.25; the systematic error is negligible, the accuracy determined (Д ) doesn't exceed the given standard of accuracy and its dependence on element concentration is of a linear character Д • 2-( .At + Aj'C), (see the table). Results of the evaluation of the determination accuracy Element Accuracy characteristic Element Accuracy characteristic А-г- (.3,+ ЛагС) Hi 0.584 + 0.100-0 Ho 0.692 + 0.152-С V 0.412 + 0.118-0 Fe 0.740 + 0.110-С Co 0.774 + 0.102-0 II 1.054 + 0.110-C Cu 0.912 + 0.130-C Bi 1.462 + 0.080-С

Che results obtained can be recommended for the standardisation of the emission spectral determination of elements In natural and puri­ fied waste waters.

IN CARBOH-COHTAIIUHG АМШИГОНВ нвшк АЯАИЗШ? FOR VACUUM I1JBS_47 UbTSA-VIOLBT SPECTRUM ?1Ш> RAMAMOH "ОРИКА-Ю-ObBD" L 1 L.H.iioskvin, YU.X.Turkin, L.E.Oardashnlkov Leningrad State University, Leninrgad A.A.Khrulev, A.B.Pedoeeenkov, O.H.fraktuev Kurohatov Institute of Atomic Energy, Moscow, USSR The discharge in quartz capillary with external electrodes in heli­ um flow under atmospheric pressure is the souroe of radiation for spe­ ctrum analysis in analyser "0ptika-1O-GLED". Excretion of anatytical spectrum part is oarried out without special optical means because the radiation is registered by selective photoreceiver with entrance open­ ing Bade of crystalline magnesium fluoride and tellurium rubidium pbotocathode, which has speed in the basic range from 150 nm to 230 nm where resonance lines of carbon 0-156.0 nm and C-165.7 nm are located. Outside this range, the speed of photoreceiver is lower and drops dra­ stically. Resonance lines H, о, и", Be, He, A, Kr, Xe are located out­ side the basic speed range of photocathode. These circumstances ensure the selectlveness of analyser regarding carbon-containing gases dis­ sociating in the discharge forming atomic carbon. Analyser test shows following results. In the concentration range from 3 mln-1 to I50mln"' the speed with respect to each of the components! CO, CO,, CH^ - in bleary mixtures with helium is the same if the error is not more than 20$. In the same concentration range it is equal to the speed with re­ spect to total concentration of the same components with the same er­ ror. Thus this instrument can be used as gas—analyser for total con­ tent of mioroadmixtures of carbon and methane oxides In helium, whioh works In continuous conditions. Measurement le possible In a wider range up to 0.3%, but in auoh case the speed tc separate components is different. When using instrument for determination of each of the com­ ponents chromatographic sample division is used. In suoh case the ins­ trument is used as high-speed selective chromatographic detector. Specifications ot "Optik»-1O-0LBD" t power consumption 60 »| power source 220 V, 50 BBJ weight 4 kg; sisaa 120X160X400 mm.

1*1 ISOTOPIC-CtfflOKATO-SPRCTRAb AHALTSIS OP PDHg «ORGANIC

GASES

V.K.N«mete,A.A.PetroT,A.A.Solo»loT,V,H.№ntov Institute of Physics, Leningrad Stat* University, Leningrad, USSR

The analytical scheme of the method eneludes: dosed introduction rare stable isotope of determining element into the analysed gas spe­ cimen; attainment of homogenious isotope Molecules distribution in the analytical mixture obtained; its physico-chemical transformation, representing either Isotope balancing in all eleaenteontalniug mole­ cule forms or cryogenic-adsorption concentration with further chromo- tographic separation of Impurities; and, finally, spectroscopic deter­ mination of isotope composition of the determining element in the mix­ ture and calculation of the sought content.

Dozed Introduction of rape isotope on the early stage of analyti­ cal procedure provides slsmltanlously monitoring of possible distor­ tion of the sample composition at different stages of the methods as a whole and measure for quantatlve determination of impurity content by calculation.

The method allows to determine hot.; total content of such elements as H, И, О, С at the level 0.1 - 19 ppni, and their different molecular forma < Я , • , CO, 00 > OH t at the level of I - 100 ppb. Toe method 2 2 г \ does not require the application of comparison standard sample» on the basis of analysed gases.

1«S POSSIBILITIES AW) PECULIARITIES OP 0, MOLECULE SPECTRA r 1 d AES-49 FOR MEASURING ISOTOPE COMPOSITION OF CARBOH MICROCONTEHTS' ' IK OASES

V.M.Nemets, A.A.SoloViOV, V.N.Funtov Institute of Physics, Leningrad state University,Leningrad, USSR

It Is suggested to use Cg molecule spectrum of the Swan Sys­ tem with wavelenght of 563.5 nm for spectroscopic determination of

carbon Isotope composition. Excitation of C2 spectrum In the RF plas­ ma discharge In mixtures of methane, carbon oxide and dioxide with helium, neon and argon has been Investigated. Influence of oarhon- eontalnlng molecules dilution and variations of total gaa pressure in the discharge on absolute and relative intensity of analytical spectrum isotope components had been studies. It had been established

that c2 molecule spectrum Is excited mostly intensively In the mix­ ture CO and He at pressures 4-6 kFa. Substitution of helium by neon or argon leads to decrease of lntensivlty. In mixtures He and (Ж or

He and C02 bands lntenslvlty also decreases. Pressure influence is expressed In monotonous increase of the spectrum lntensivlty at pressure Increase, transition through maximum and alow decay. The value and position of maximum depend upon the degree of dilution of carbonoontalnlug; component» by gaa dlluter. Character of the C_ spectrum absolute lntenalvit; changes at pressure variation is simi­ lar in mixtures of CO, CCg and СНц with helium. Significant influence of discharge conditions upon relative spectrum Isotope components intoneivity is not found.

I3.3aK.4I3 l«S * NEN COMBINATEO ELECTROTHERMIC-HOLLON CATHODE RADIATION |._ __ АИ-50 SOURCE. 1. THE PRINCIPLE AND DEVELOPMENT OF THE METHOD ' L. Papp Kossuth Lajos University, Department of Inorganic and Analytical Chemistry, Впвдасу A new radiation source is developed which gives 4-6 tines greater radiation intensity, technically can be produced and used easier than the FANES - combinated simultaneous multielement - radiation source. The investigations carried out with this source •re evaluated by e computer system connected to a multichannel spectrometer having a wavelenght nodulated background corrector. It is suitable for the study of fast, partial processes in this source Cas veil as other atom and radiation sources). On the basis of the study of partial processes we showed that the combination of the electrothermlc and hallow cathode radiation sources (the super­ position of their power) increases the emission intensity of spectrum lines in a high degree, that is it gives -ore desirable absolute detection limits from micro volume (S-lO^ul) solutions than the previously known radiation sources. THEORY AND PRACTICE OF METHOD OF CROSSING CORRELATION ASS-51 LINES IN EMISSION SPECTRAL ANALYSIS OF NON-ORGANIC GASES

A.A.Petrov. E.A.Pushkareva* Institute of Physics,Leningrad State University, Leningrad 'Kazakh State University, Alm-Ata, USSR Method of orossing correlation lines (CCL) for account of variations of analysed gas Mixtures and conditions of their gas-charge excitation in eaission spectral analysis is developed. Basic Methodical procedures:

a) establishment of corrected analytical signal Y0 as ordinate of

the crossing point of the standard conditions curve (a0), built on the correlation plane Y - Z (where Y-analytical signal, Z-additional correc­ ting signal, maximally reacting on the changes of the experiment condi­ tions, account of which is to be performed), for chosen standard analy­ sis conditions at variations of determining component concentration C, with one of the lines (ax) of the correlations between Y and Z, formed by way of "third component" variations and other working conditions at discrete set of given values of concentration С (Fig.a).

b) the next determination with a help of standard graduating curve Y0-

F(C), built for standard experiment conditions, by corrected value of Y0, the sought concentration Cx of the determined probe component (Fig.b).

At practice Cx determination is fuifiiedby joint solving of equation system, describing correlation lines and standard graduating curve, and also - dependence of parameters of these equations on the С concentra­ tion and on the varied experiment conditions. The work presents CCL method theory and results of its application for determination of monoatomic (argon) and molecular (nitrogen) components of gas mixtures at wide and non-controlled variations of their composi­ tion (He, Ar, Xe, Na, Ha, Og) and working conditions (pressure and cur­ rent), consisting in the decrease of total analysis errors from 50-300JC up to the level of occasional errors of ph'otograpbical registration 3-Sji. У

С». А) a. 3 Гц. а

iw ANALYTICAL POSSIBILITIES OF COMPUTER HANDLING OF ATOMIC ГТГГТГ SPECTRA IAEfr-5 zL2 E. PlSko Geological Institute, Komensky University, 842 15 Bratislava, CsFR Apart front the use of computers for controlling the operation of spectrometers, as well as, for the performing and optimization of ca­ libration - evaluation procedures [1,2] leading to the conversion of measured spectral line intensities in corresponding concentration va­ lues, practically all spectrometers used for 1CP OES have the possibi­ lity to scan spectra in narrower or broader spectral range, A sub­ sequent computer handling of recorded atomic spectral scans has till now been used mainly for the study of possible spectral interferences [3j, whereas their application for the solution of other analytical problems has been in comparison with molecular spectroscopy [4] rather seldom and corresponding software normally does not belong to standard producers' equipment of spectrometers. Following computer handlings of spectral scan records and their analytical applications are used: Differenciation or integration, subtraction and addition. The determination and use of appropriate multiplication factors is discussed and the comparison of results ob­ tained by computer handling and by direct measurements performed. The improvement of analytical information by subtraction of struc­ tured background caused by molecular bands (spectral lines of Gd, V) or of at other correction procedures [5,б] used interfering spectral lines (influence of Ca on Eu, of Fe on Co, of Cu on Bi), the simpli­ fication of spectral evaluation by eliminating the influence of line rich spectrum of matrix (impurities in pure rare earth elements) and improvement of appearance of spectral lines and consequently of the detection limit by successive addition of spectra [7] are shown as examples for the broad analytical applicability and. effectivity of computer handling of spectral scans in atomic spectroscopy.

References 1. PlSko E. // Proc. Metrology in Chemistry, Tatr. LesnS (CSSR), 1989. 2. PlSko E. // VII Semi-International Spectroscopy Symposium, Samsun (Turkey), 1989. P. 64; Journal of Science (in press) 3. Boumans P.W.J.M. // Proc. XXVI Colloquium Spectr. Internationale, Sofia (Bulgaria), 1989. Vol. VI. P. 9. 4. Hirschfeld Т., Coates J.P. // Computerized Infrared Spectroscopy: FTIR and Oispersive Elsevier Sci. Publ. Amsterdam 1989. 5. PlSko E. // Acta FRN. Univ. Comen., CHIMICA (in press) 6. Plsko E. // Chemia analityczna (in press) 7. Plsko E. // Zeitschrift t. anal. Chem. 1967.Bd. 225. S. 107.

IN MULTICHANNEL Ш13310Н SPECTROMETERS РОЯ SIHULTAIJBOUS •USS-53 MUMIBLBMEHT SPECTROMEIRIC АЯАШИИ S.V.Podmoohenakaya Leningrad Optical-Mechanical Enterprise, Leningrad, USSR Leningrad Optical-Mechanical Enterprise provides multichannel emission spectrometers for simultaneous multielement apectro- metric analysis of solid samples.Spectrometers are equipped with the type DBK-3 computer for automatic monitoring and data processing» ДФС-51 vacuum emission spectrometer is designed to produce apectrometric analysis of steel and iron, МФС-8 spectro­ meter - for analysis of non-ferrous alloys, ЛФС-44 spectrometer • for the identification of materials giving complex spectra, МФС-7 - for oil analysis.Specificatiens are given in the Table.

Specifications Itreasuring Дф С-51 МФС-8 ДФС-44 ЯФС-7 unite Wavelength nm 175-340 2ОО-40Оя7170-550"7 200-400, range Reciprocal linear nm/mm 0,44 0,55 0,27;0,36 0,55 dispersion Number of channels 24 24 40 24 Fhotomulti- pller tubes ФЭУ-39 ФЗУ-171 ФЛУ-171 ФЭУ-171 axcitatim ИЬС-6 source* "' УГЭ-4 „и.УГЗ-4 ИвО-29 Ж) Wavelength range may be extended up to SOOnm in accordance with the users requirements. я»)И6С-6 - aperiodic argon discharge,frequency up to 300 im­ pulses per second;VPJ-4 - universal multimode excitation source, diiect current arc,alternate current arc,high voltage and low voltage sparks, frequency up to 500 impulses per зесопй;Уд-4Н- 5ГЭ-4 with supplementary rheostat for arc current 25 А; И6С-29 - alternate current arc. The software system provides formation of different analytical programmes,automatic calibration,correction of the calibration, automatic calculation of the results of apectrometric analysis in й concentrations.

117 APJUCATIONS OF THE "HALOHARC" IN AES TO THE .„_ „, I AES-54 ANALYSIS OP HIGH PURITY ACIDS I _ M.R. CataeuB Portuondo , T.Kantor , J. S.Mlnoso Gomez , M.Alvarez Prleto Institute for General and Analytical Chemistry, Technical University of Budapest, 1521 Budapest, Hungary Institute of Materials and Reagents for the Electronics, University of Havana, San Lazaro у L, Havana City, Cuba

The results obtained with a version of a combination of a graphite furnace and a graphite are reported in (l) are presented. The halocarbon vapour were introduced into the furnace where its thermal decomposition takes place. The furnace was designed for app­ lying 0,2 ml volume of solutions and a high dispersion grating spect­ rograph was used for recording the spectra. By halogenatlng the samp­ les in an Ar + CC1. furnace atmosphere, the capabilities or the sys­ tem for the analysis of high purity acids were investigated. In order to determine the conditions for the analysis, the follow­ ing parameters were studied: - Argon flow rates of the glass chamber. - Flow rate of the argon which oexrled the CCl^ vapour. - Heating pretreatment for the purification of the heated graphite parts of the furnace (Including the crucible). - Condition» for the drying of samples without significant loss of the determined elements. - Evaporation rate of analytical elements. Comparison with the background equivalent concentration reported for the conventional ICP spectrometry shows advantages for the des­ cribed system.

Reference 1. Kantor T. Hovel applications of halogenatlon reactions In atomic spectrometry // To be published.

m

9 USE OF The. COMPLEX OF SPECTROSCOPIC MONITORING MUTHODS Ш POWiE SEMICONLUCTOR LEVIOBS TECHNOLOGY ' ' A.Z. Razyapov, CO. laidinov, V.M. Mazarov All-Union Electroteohnieal Institute, Moscow, USSR

A specific character of power devices design and technological features-deep diffusion layers, thick metal coats, phase alloying re­ gions, diffusion from surface sources, a complex of technological operations as applied to grinded surface, extensive outlet p-n-junc­ tion regions with the given configuration and so on cause the neces­ sity of traditional approach modification* This paper considers analytical aspects of using the complex of spectroscopic methods in combination with methods of mass-spectromet- ric analysis of elementary and impurity composition. The impurity level of silicon grinded wafers in different clea­ ning processes and interdiffusion during alloying process have been investigated by methods of atomatic emission spectroscopy (with dif­ ferent excitation sources), atomic adsorbtion spectroscopy and X-ray microanalysis. We have also studied concentration profiles of deep diffusion layers and efficiency of chemical and plasmo-chemical pro­ cesses of removing polymer coats. The approach to complex atomisetion for traditional methods of analytical spectroscopy has been proposed. The quality and quantity correlations of spectroscopic analysis results for liquid samples and impurity composition of high-porosity layers of electro-chemical silicon, used as an adsorbent, are estab­ lished» This can be assumed as a basis for liquid object analysis by methods intended for solid-state materials. Recommendations are made to optimize technological surface treat­ ment operations and the cleaning process for silicon wafers and structures under the conditions of uninterrupted cleaning medium re­ generation, to decrease essentially the high-pure substances consump­ tion and to improve the ecological purity, Efficiency of using electrochemically formed high porosity silicon layers as a basis for creating comparison specimens is proved by experiment. We have made the conclusion about the efficiency of the complex of spectroscopic analysis methods as applied to solving a number of problems in power semiconductor devices technology and evaluating the quality of technological media and materials.

1И REGULAR!ZATION ALGORITHMS OF PROCESSING OF AES-56j EXPERIMENTAL. DATA IN ANALYTICAL SPECTROSCOPY

M.Kh.Salakhov Клглп Stat* University, Kazan. USSR The possi Ы 111 i es of a set of algor i thms and of processi ng experimental data of programs using a personal computer are duscussed. The most common tasks requiring the processing of spectroscopi с data are the f ol1 owlng: fi1tr ati on of analyti cal signals, detection and separation of superimposed analytical signal, background correction and signal correction, signal deconvoiution, signal differentiation. Abel's and Radon's inversion, etc. The above problems are inverse problems. Inverse problems aim at determining causal quantites when effect values are given» i.e. the cause is found from the effect. In general, these problems can be described by an Integral eguation of the for»

Kp * f, <1D where p is an unknown function С cause), f is the given function CeffecO» С all owing for random for random errors)» and К is the 1inear operator. These ргоЫems are so-called ill-posed problems. This term means that the calculation of such problems is extremely sensitive to small errors in the initial data. A small, typically uncontrollable variation of data leads to л large variation in the result. An analysis of solution methods for 111-posed problems shows that the involvement additional.

References 1 Tlkhonov A.N. and Arsenin V. Ya. Methods of solving ill-posed problems. M.'.Nauka. 1870. г Grachev I.D. . Salakhov M.Kh. , and Pishman I.S. Statistical regularlzatlon when processing an experiment in applied spectroscopy. Kazan 1080.

200 THE AlfiOBIIHMS OP BESOLVIHG COIIFUSX SPECTRUM IHTO I 1 AES-57 С01ШШИТ8 III JUJAIITICAL SFECTHOSCOFI \*"^-?r N.K.Shcherbakova, U.Kh.Salahkov The Kazan State University, Kazan, USSR The nain problem which researcher must solve after obtaining the experimental spectrum is that of distinguishing the useful signal from the experimental data. For example, in analytical spectroscopy it is usually necessary to reeolve complex spectrum into elementary components. That problems are the ill-posed ones and their simple so­ lutions are determined by the a* priory information included in the algorithm. Here the problems of resolving of complex epectrum into components are analysed and grouped according to the presenae of a priory information. The algorithms for the following cases are wor­ ked out. 1. The complex spectrum is the additive sum of elementary compo­ nents. a) The regularised algorithm of determination the n-th order deriva­ tives. That algorithm makes it possible to carry out the prelimi­ nary analysis of spectrum structure and to minimize the experimen­ tal error. b) The regularithed algorithm of resolving the complex spectrum into the components having lorentz form. The number of components is known. 2. The complex spectrum consists of the unadditive elementary com­ ponents. a) The resolving algorithm of parameter determination of signal reso­ nance lines in amplitude-polarizetion coherent active Raman spectroscopy (CiRS). The number of resonance linee is known. b) The algorithm of determination the parameters of Voight profile. The regularized method of differentiation of experimental spect­ rum is used here. She statistical regularization method /3/ is used for setting rid of the ill-poseness. That makes it possible to obtain the solutions which are not so sensitive to the experimental error. The principle advantage of that algorithm is that unlike the widely used method of least squares the initial approach to the solution is needless here. Reference I. Grachev I.D., Salakhov li.&n. ,Fiahman 1.3. The Statistical Regula­ rization when Processing the experimental Data in Applied Spectro­ scopy. Kazan, 1966.

201 RECENT ADVANCES IN TANDEM ON-LINE SEPARATION Г~ TECHNIOUES FOR IMPROVED SAMPLE PRESENTATION 1. 5 TO ANALYTICAL PLASMAS A.Sara-MedelAMeneridez. J.E.Sanchez-Uria. С VaMes-Hevia, J.F.Camuftae AguUar Departamento de Quimica FfBica у AnaWca. FacuHad de Oufmica. Univereiaad de Oviedo. SPAIN

The concept of "tandem on-line continuous separation" techniquee offers a •xnmrful tool to atomic spedrometrie imttodotogies (1). The combination in a single on-sne configuration of two. or more, separation unite (usual/ based on dfflerent separation mechanjerne) has proved to be an alternative sample presentation to the Inductively Coupled Plasma. ЮР. which couM overcome many selectivity and sensitivity problems posed by modem uHratrace analysis (2).

Several continuous separation devices (based on solid-liquid, liquid-liquid end gas-liquid separations) have been used in our laboratory during the last three years. The combination of two of them rn a single configuration (of the Flow Injection Analysis, FIA, or Continuous Flow type) to provide a "tandem on-line continuous separation" device to be coupled to the atumioer (Flame. ЮР or MIP plasmas) will be discussed.

АррйсаВопв of such continuous sample pieserrMiori/pretieBJment to the plasma ЮР will be JHustratod with the determination of hydride fonrring elemente (particularly As. Sb and Se) in real samptas with extremely high selectivity and sensHWy.ln the light of the successful determination of sulphur in stasis by MIP, the use of similar sample presentation techniques to a Microwave Induced Plasma, MIP. win also be dealt with.

The use and convenience of "tandem on-Kne continuous separation" techniques tor indirect detonranalions (e.g. non-metals, drugs) with analytical plasmas wi be finaty addressed.

(1) Menedez Garcia A.. Sanchez Una J.E.. Saru-Medel. Kll J. of Anal. At Spectrom.tOeo.4(7). Poet. (2) Sara-Medal A.. Menandez Garcia A.. Sanchez Una J.Eir Anal.Chim. Acta fin press)

202 THE 3PARKIHG AS A STATISTICAL PROCESS

Iron and Steel Institute, Dnepropetrovsk, USSR

As a result of the action of single high voltage condenser1, sp rk discharge the only crater is formed on the metal probe surface £J. By beginning of spectra registration the whole sparking spot area must he covered by craters. In the available publications there is no information about crater distribution on the spot surface. Mean­ while the knowledge of distribution kind is important for the furth­ er perfection of quantitative spectral analysis» The calculation results of pre-sparking time value estimation ha­ ve proved the failure of the even distribution hypothesis. To deter­ mine the distribution kind, the spectrographs equipment with analy­ tical spark gap projection on the spectrograph slit plane was used. The experiment was based upon the assumption that intensity of radi­ ation of some space layer above the probe surface is proportional to the number of craters being formed &]. During the experiment the special precautions to eliminate the distorting factors were being provided. In the following calculations it was taken into account that the intensity distribution on the projection is one-dimensional representation of really existing two-dimensional crater distributi­ on on the spark spot surface. It was stated finally that crater distribution follows the law of Gauss with confidential probability of no less than 0.9?* Signifi­ cant deviations from Gaussian distribution were observed only by ap­ parent defects of the surfaces treated by discharge, when the spark epot had been losing its regular form, or when using the auxiliary electrodes with extensive working surface f}J. In the last case the general picture seems to be a superposition of a number of point "centres" each following a Gaussian distribution.

References

1. Buravlev Yu.M. Vlijanie sostava 1 razmerov proby na rezul'taty spektral'nogo analiza splavov. Kievi Tekhnika, 1970. P. 81. 2. Walters J .P., Goldstein Б.A.//Spectrochim.Acta. 1984.Tol.39B. P. 695. 5. Severin B.H., Kopyl L.V.//ZU. Prikl. Spektrosk. 1976.Vol.24.P. 508.

203 ON THE DESIGNS OF EXPERIMENT IN SPECTRAL ANALYSIS AES-60i USING REGRESSION EQUATIONS K.N.Jeverin, L.V.Kopyl Iron and Steel Institute, Dnepropetrovsk, USSR

Pho factors limiting the use of regression equations £\J have be­ en investigated. The main ones are the inconvenience of calibration stage caused by the necessity of using a great number (30 - $0) of probes of known chemical composition, low calibration efficiency as a consequence of significant correlations /27 existing between con­ centrations of components, irregularity of concentration distributi­ on ГЦ, the lack of agreement between total set of probes and that for operative control, impossibility of calibration before the ana­ lysis. All these factors are the consequence of the insufficiency of experimental design consisting in selecting the probes necessary for calibration of a random number, formed in this way the experi­ mental design that is the general chemical composition in this case does not satisfy the demands of maximal coverage of concentration range, even distribution and absence of significant correlations. The experimental designe of well-known native (production of ЙС0 ЦНИИЧМ) and foreign (MBH catalogue) complete sets of standards for spectral analysis of ferrous materials have been examined. It was stated that all the sets do not satisfy the demands listed above. Therefore their applications in spectral (X-ray fluorescence for in­ stance) analysis with regression equations are a priori useless. The search of optimal designs is a complicated mathematical pro­ blem. Only some solutions with partially minimized matrix of corre­ lation coefficients are found and known at present. In this work the optimal designs for the systems with 12 compo­ nents have been found out by using the methods of combinatorial ana­ lysis and theory of groups. Their matrix of correlation coefficients is minimized to the level of no more than 0.105. The use of such de­ signs opens the way to achieve the пупНшв! efficiency of the correc­ tions for intercomponent effects with minimal number of standards.

References 1. Lavrentiev Yu.G., Kuznetsova A.I.//Zavodsk. Lab. 1979.7ol.45. P. J15. 2. Nalimov V.V., Chernova H.A. Statisticheskie metody planirovanija ekstremal'nykh eksperimentov. U.i Hauka, 1965. P. 17. }. Hald A. Statistical Theory with Engineering Applications.N.Y.i J. Wiley and Sons, Inc., 1952. P. 522.

204 ABOUT З/ЗТЖ APPROACH TO IHOROAUIC KUbTICOMKmHJT MIXTURE ANALYSIS Ы MKAHS OF INDUCTIVELY-COUPLED PLASMA-ATOMIC EMISSION

SPECTHOKEIRi IAES-61 ;

G.I.Sbmanenkova, fi.V.Sokolov, U.S.Hots, V.P.Schelkova, L.V.Kolesova МКЙШЕТ, VIIIIP, Moscow, USSR The usage of inductively-coupled plasma makes it possible to inc­ rease atomic emission analysis of multlcomponent mixture applicabili­ ty firstly because of good reproducibility of results of this analysis

( Sp> 0.OI-0.O2 while concentration of the component to be determined

5 is equal or greater than 1 pg/es?) and low On value ( 0.01- O.L»g/em ) as well as because of employing spectral analytical complexes equipped with polyohromators and computers. In many oases realisation of the po­ ssibilities of this technique is limited by the lack of reliable and sufficiently simple methods of taking into account mutual spectral in­ fluences of all the mixture components to be determind and by the lack of systems approach to the choioe of the analysis conditions. For that reason a procedure for inorganic multicomponent solution analysis has been developed. It includes qualitative estimation of the composition) optimisation of spectrum excitation conditions, the cho­ ice of the determined components oontents in the standard solution and correction of the results taking into account mutual spectral interfe­ rences. Hethods of qualitative estimation of the mixture composition and following correction with due account of mutual spectral interferences based on vector representation of the speotra end on the principle of additivity have been worked out. The software realisation of these me­ thods has been developed. Conducting the analysis and obtaining the re­ sults on the content of twenty components In a single probe takes about 40 seconds. The developed procedure has been applied to the determining of 20 compounds mixtures containing all rare earth elements. The reproducibi­ lity of the results and the regression of the statistical discrepances has been rated on the bases of artificial mixtures where the estimated components varied from 0.1 to X0*g/cm , and the corresponding ratio from 1:1 to I: 100. The obtained S_ value was 0.0I-O.I depending on the content. Signi­ ficant systematic error term was not revealed for P-0.95. In accorda­ nce with the proposed procedure! there were analysed samples of mine­ ral resources taken from many deposits, the processed products and other compound solutions.

205 THE PROCESS ОН THB SLBCTHODES OP LOW-VOLTAOS SPARK DISCHARGE AND THE EMISSION SPECTRAL GAS DETERMINATION AES-62I IN MSTALS S.A.Skotnikov OHUBttSH, ICoscow, OSBR

The metal melting and its direct crystallisation occur» under the influence of the powerful low-voltage spark discharge. The Impurity distribution coefficient must be less than one ( K<1 ) and the dissolubility temperature coefficient oust he negative for the analysis* high ssnsitlTity.Tho dissolubility negative temperature coefficient is also determinant for the gas transition into the discharge plasma by the spark heating of the melted me­ tal. For the gas transition from the pores it is necessary to melt the pore side. The intereleetrode gap is considered to be the homogeneous thermal source for the offered meehanieaa. the energy flow den­ sity on the metal surface creating the melting and boiling condi­ tions for the 18 metals was calculated for this ease. The calcula­ tions are well correlated to the experimental results. The fusion depends on the electrons output work from the metal and the melt surface tension» But we shall mention, that all the effects are taking plaee at the sample's surface. The single low-voltage spark discharge of 10MH induction and 300-400 (HF capacity creates an erosion cratsr up to 5-Ю depth. This was shown by prophilograpby of the erosion spots on the No, Ni, 7, Zr, Fe, Cr, Ti, Ft, W, Re, Ag, Cu polished specimens. The destroying of the surfaces streng­ thened by the chemical-thermal treatment is even smaller. The gas- -aetal interaction kinetics.are the main problems of the spectral gas determination in metals. This method is suitable for studying the processes of nitration, cyanation, nitroearburation as well as oxidation, corrosion etc. Each spectrograsm shows not only the changers in the gas con­ tent, but the content of other elements taking part in the studied process as well. lbs determination of the erosionsl inclusions elemental compo­ sition ( nitrides, carbides eto ) on the polished surfaces of the erosion-resistant metals and alloys ie a separate problem.

206 NEBULIZERS MID TESTS FOR ICF EMISSION SPECTROSCOPY

W. Slavin and J. Ivaldi Perkin-Elmer Corporation, 761 Main Avenue, Косwalk, OSA The performance of pneumatic nebulizers Cor the inductively coupled plasma was studied. The parameters we studied included the precision of the analytical signal, its stability, the signal to background and signal to noise ratios. The test protocol was chosen to provide a performance index (PI) for the nebulizers in order to rate then. The PI is based on the average short-term RSD's measured over extended periods of time* The measurements were used to test reliability across different lots of nebulizers and to investigate the consistency of performance. Also, the effects on performance of replacing the removable cross-flow tips was studied. The test protocol included the use of Triton X-100 surfactant in the standards to eliminate potential variability of wetting in the spray chamber and to insure the smooth transfer of the sample liquid through the pump and capillary tubing leading to the nebulizer. The PI for cross-flow nebulizers was typically between 0.5 and 1.0% and always less than 1.5%, expressed as RSD. Babington nebulizer designs have been widely used for intro­ ducing samples with high dissolved solids into ICP emission spectrophotometers. To obtain a fine aerosol, the hole through which the gas emerges as it impinges on the liquid sheet must be narrow in diameter, very smooth and symmetrical, and the solution must be effectively channeled over the hole. Vee-groove nebulizers use gravity to move the liquid over the hole. When vee-groove nebulizers are well-made they will not clog when concentrations of salt in excess of 10% are sampled. Using the Performance Index (PI) conditions, vee-groove nebulizers of several different designs were tested both with simple aqueous solutions .and with solutions containing about 10% NaCl as well as the analyte elements. The precision with vee- groove nebulizers and toe salt varied upwards fro* about 1% RSD. The requirement for better precision and store consistent and uniform precision necessitated design changes. Several designs were built and tested including that of Sharp 111, which he called a conespray nebulizer. The precision and signal stability obtained with some of these designs will be reported and discussed. Reference 1. B.L. Sharp//j. Anal. Aton. Spectrom., 3, 613 (1988).

207 OPTICAL EMISSION SPECTROCHEMICAL TECHNIQUES FOR ROUTINE ANALYSIS 0£- METALLIC INDUSTRIAL PRODUCTS j IASS-64 . Jv. Slickers Spectro Analytical Instruments GmbH, 4190 Kleve, FRG

Optical emission spectrometers have become the most favorable to^ls for the routine analysis of industrial products.

ОЕ-spectrometers using spark-like discharges in an Argon atmosphere are predominant for the analysis of metals. Total analysis time is often less than 1 min for double runs, average and print out. Precision for dissolved elements are mostly better U.5 X rel. Using light guides for the transmission of the analytical light from the light source to the spectrometer allows the contruction of very flexible systems regarding optical resolution, wavelength range and usage of optimum spectrum lines. The number and magnitude of interelement effects has been drastically reduced.

HEPS and SEREPS allow the analysis of "bad" samples, PINS the determination of dissolved and undissolved portions of elements and SAFT achieves LOD which are similar to those obtainable with globular arc techniques, Adapters allow the analysis of small samples, thin wires etc.

The tendency of process control is the use of analytical tools near the production furnaces. Because of the fast sample preparation and analysis time the transport time between the process area and the central laboratory has become the most time consuming step. Container Labs containing sample preparation equipment and self-controlling spectrometer are in continuous development and several of them are already in routine operation. The total time from introducing the sample to the final result (2 runs) is already < 100 s today. < 60s is the goal for the next future.

206 THE ROLE OP KAS3 TRANSPORT IB MATRIX EPPECT AES-65 III TWO-EbECTRODB DIRECT PLASMA SOURCE FOR ATOMIC EMISSION ANALYSIS E.V, Smirnova, S.B. Golovko Institute of Oeooheralstry, Siberian Branch of the USSR Academy of Sciences, Irkutsk, USSR The two-Jet plasraatron with two non-consumable electrodes С13 was employed for spectral analysis of complex geological samples С 23 . Among different possible matrix effects the interference from easily ionizable elements (BIB) was best experimentally studied С2 3 . The estimation of the different processes associated with this effect and the discussion of some experimental data are the subjecteof the present work. Taking into account that the examined plasma is olose to looal thermodynamic equilibrium Г 33 the Intensity enhancement I/I, with EIE addition (symbol "o" refers to samples without EIE) may be expressed through three functions: if(n), $(x) and

210 STUDY OF MATRIX EFFECT IN ICP ifiS-68

M.Tripkovi6 and i.Holclajtner-Antunovid* institute of Physics, P.O.B. 57, 11080 Zemun Institute of Physical Chemistry,University of Belgrade, Yugoslavia

A very important effect from inductively coupled argon plasma researches is the influence of an excess of different atoms on the behaviour of the emission of trace elements. Further suty of the influence of non-easily ionized elements as well as easily ionized elements* as a concomitant, on emission intensity of analyte is done, in order to gain more information on the mecha­ nism of plasma processes .

The influence of addition of K, Ba and В on analyte signal emission was followed in dependence on analyte channel height. The effect was investigated considering the ionization state of analyte as well as its ionization and excitation potential. The influence of various concentrations of matrix element on analyte line profile is compared with the same effect in U-shaped Ar-stabilized d.c. arc.

The results of the report make possible to predict the influ­ ence of various matrix elements (depending on their physical proper­ ties) on the detectability of analyte elements and to choose the experimental conditions which minimize the matrix effect. This is of special importance for the analytical practice.

Reference

1. Tripkovic M., Holclajtner-Antunovic I., Radovanov S.//Proc.XXlV int.Symp. on the Phys. of Xoniz.Gases,£arajevo (Yugoslavia), 1988, p.432.

211 COMPACT MULTICHANNEL AUTOMATED EMI3SI0If liPjiCTHOANALYZilK . ABS-6°. V.V.Turkin, A.P.Dyomin, P.P.Sultonbekov I 1 Institute of Applied Optics, Kazan, USSR

A spectroanalyzer is intended for rapid determination of elements in liquid and solid sapmles by emission spectroscopy in plant condi­ tions directly. {Che use of a cirouit as a polychroraator based on a concave non- conventional diffraction grating and multi-element photodetectors allows to analyze information of 2000 measuring channels simultaneous­ ly that extends analytical capabilities of the speotroanalyzer. An excitation source is an arc generator with electronic control of igni­ ting - and - quenching phase for increasing radiation stability.

A spectroanalyzer has a block-modular construction with a set of attachments for sample feeding to analyze liquid and solid samples. It is equipped with a remote sampler connected with a device by a fiber-optic cable. Personal microcomputer as a part of the system controls the spect­ roanalyzer and processes spectrophotometry data.

Analytical capabilities of the spectroanalyzer are determined expe­ rimentally while analyzing motor oil samples and rejecting titanium alloys. Concentration sensitivity while analyzing wear products in motor • oils is no less than 10"* ',» in the measured concentration range of 10 % to 10" %, thereby relative mean-square error of analysis reproducibility doesn't exceed 15 %. Time for determination of 30 elements doesn't exceed 2 min.

:l

212 THE SALT MATRIX EFFECTS IH THE ICP-AES IAES-70 O.V.Varvanino, B.S.Chudinov I.V.Kurehatov Institute of Atomic Energy, Moscow, USSR It is well-known that the level of non-spectral effects In the ICP-AES are lower than in other sources, nevertheless the interfe­ rences due to high salt concentration in analyte solution may lead to deteriorate the accuracy of analytical results particularly for the materials with complex and variable composition. For estimation of the possible value of expected error and the permissible matrix salt concentration the influence of the salts (SOZ and CI") of various metals with variable concentrations (up to 0.1 Ю on the analytical signals of 15 elements was investigated. All experiments were performed using the direct reading spectrometer JY 32P.

The following conclusions can he made: 1. The presence of the salt concentration above 0.01 И leads to non-uniform depression of analyte signals. Aa salt concentration lower 0.005 M it ia frequently observed enhancing of some element signals normalized to water solution. 2. The bias of signals depends on the -nature of the matrix metal. The effects decrease with growth of ionization energy of a matrix oation (excepting BIE) at the equal molar salt concentration. 3. She influence of transitional elements is higher than the effects of the alkaly metals and much higher than acid matrix effects. 4. One type of the salt matrix effeot - the calibration curvature (self-matrix effect known for Ca) is observed for many salts. 5. Change of the operating parameters of the ICP compensates the observed effects only for small group of elements. Their dependence on four operating parameters is different for matrix cations with different B, . Thermodynamic and dynamic factors connected with described effects will be discussed.

213 IHBIHODS OP CORRECTION OF SHIIQUAHTITATIVE ATOMIC- lAES-71 : HJISSION ANALYTICAL RESULTS OS GEOLOGIC SAMPLES BY APPLICATION OP AM AUTOMATIC SPECTRA INTERPRETATION TECHNIQUE

I.E.Vssil'eva, I. V.Emel'yanova Institute of Geochemistry, Irkutsk, USSR The semiquantitative atomic-emission analysis (SQAEA) of geolo - gic samples implicates different techniques of introduction of pow­ ders into the arc, the visual and automatic spectra interpretations. The visual interpretation method using an appearance-enlargement of the spectral lines and the automatic one with the application of the device ACS[1] for the powder insufflation technique were compar­ ed for the silicate rocks from the acid to the basic composition. The accuracy of the SQAEA results in a considerable degree is depe­ nding on the accounting for the matrix effect and the mineral forms of elements. These factors determine the changes of the magnitude of the limit of the detection of the element analysed on the suitable analytical line and the parameters of the calibration curve. The software of the automatic spectra interpretation technique includes en approximate determination of the petrogenic elements co­ ntents in the sample analysed, an estimate of effective ionization potential [2] and the choice of an optimum average calibration curve for each element determined in this type of analytical matrix. The feasible coincidences of analytical lines are accounted for by com - periston of the element contents with those obtained for spectral lines with similar limits of detection, but for different interfe - ring elements and similar matrixes. Рог the analytical lines on the blackening curve with small sensitivity an analytical parameter is used, which employe the intensity and semiwidth of the line. The accuracy of the automatic spectra interpretation technique was estimated by comparing its results with ones obtained for quan­ titative analytical methods and with the data of National Standards of rocks for the wide element range and did not exceed 20-4096. References

LSelyashov D.K., Emel'yanova I.V. //J.Appl.Spectr. 1988.Vol.48. N. 5. P.849-851 (in Hussion). a.Smirnova B.V., Vasil'eva I.E., Petrov L.L., Lontsikh S.V. // J.Anal.Chem. 1986.Vol.41, JJ. 8. P.1361-1J70 (in Suasion).

2I4 THE PEODUCTION OF STANDARDS FOB SPECTRA! ANALYSIS | 1 ОТ ЗШШЬ ИГ РОТОЮ MBDAIMJRGT |AIB-7g | V.A.Vodopoenko, P.N.Ostrik Iron and Steel Institute, Dnepropetrovsk, USSH

The spectral analysis of microalloying elements contents in steel is rather difficult because of the non-availability of standards ha­ ving wide range of those elements concentrations £\J'. It is inexpe­ diently to produce the sets of standards optimal with respects of their composition number by conventional steelmaking technology and it is impossible sometimes because of the low solubility of microal- loying elements and their segregation trends during crystallization. The problem, of homogeneous distribution of a substanoe in the matrix of another one significantly different in physical and chemi­ cal characteristics may be successfully solved by powder metallurgy. Using these methods we produced the standards material containing microalloying elements (cerium, magnesium, calcium, cobalt et al.) in the wide range of concentration ( from thousandth to tenth of percent). She apectrografical investigation on microalloying elements dis­ tribution homogeneity was made using dispersion analysis /i/. In ad­ dition the material distribution homogeneity was studied using X-ray microanalysis. The metrology estimation of the investigation results has satisfied the requirements stated for industrial standards (COD) and state standards (Г00). We have received the good agreement of standards in eat analyzed on apectrographic (PGS-2) and X-ray fluorescence (AHL-8440, VHA-20) installations. She set of standards containing cerium in the concentration range from 0.002 to О18 % was produced end certified. line worlc on production of standard sets and their certification on the other mieroalloyiag elements is in progress now. Hefersnoea

1. Referense materials; HBH, 1987. March. 2. Hetrologieheslcoe obespeehenie kontrolja sostava materialov chorno;) metallurgii. Sprav. led./ Pliner lu.L., Vinnilc V.I., Semen- Ico 5.G. i dr. 2-е lad., pererab. i dop. II.: Metallurgies, 1986. 288 s.

2I5 VAPORIZATION AND EXCITATION PROCESSES IN HOLLOW |AES-73 j CATHODE DISCHARGE

J. Borkowska-Burnecka and W. 2yrnicki Institute of Inorganic Chemistry and Metallurgy of Rare Elements, Technical University of Wroclaw, Wroclaw. Poland

Study of vaporization and excitation processes in discharge with hollow cathode has been undertaken here in a view of maxi­ misation of analyte signal, decrease of background, increase of the ratio of signal to noise, optimization of the discharge (plasma) parameters end better understanding excitation processes and matrix effects. A demountable lamp with hollow cathode made of copper (which has shown to he a better material than traditionally employed graphite [ID was used to excite samples of various lead compounds {e.g. halides, oxides). Argon or helium flowing continuously through the lamp were the carrier gases. Spectra were recorded photoelectrically by means of monochromator M300HR cooperating with computer system (Bentham). Samples without and with compounds of potassium which had baen added as an easily ionized element changing the electron density of plasma have been studied. Intensities of lead lines (being a product of decomposition of different compounds) and line intensities of argon, helium and potassium have been investigated versus time under various experimental conditions. Lines invol­ ving electronic levels with different energies have been measured to investigate a relationship between populations of Pb (the ana­ lyte signals) and populations of the carrier gas atoms and the electron densities. Mechanisms of excitation and possible chanel reactions are discussed.

Reference

1. Nierzwa J.. 2vrnicki W. // Anal. Lett. 1988. V.21U). P.115.

216 SIMULATION OP EMISSION SPECTRA OF SOME ANALYTICAL EXCITATION SOURCES - CHOSEN PROBLEMS | [AES-7>рд t 4

W. ayrnicki Institute of Inorganic Chemistry and Metallurgy of Rare Elements, Technical University of Wroclaw, Wroclaw, Poland

A simulation of spectra excited in sources used in electroche­ mical analysis seems to :« very important and promising utility of application of microcomputers in spsctrochemical measurement field. This could be a step towards to performance of a quick multielement analysis of very complex samples, testing for possi­ bility of overlapping analyte signals, determination of contribu­ tion of the overlapping spectra, easy correlation between plasma parameters (temperatures, densities of species and electrons] and measured analyte signals.

An approach based on the assumption of a partial thermal equi­ librium has been used to describe plasma. Model applying more than one temperature has been employed to express relative and and absolute populations of excited states of analyzed species. Profiles of lines has been related to plasma properties and pa­ rameters of optical recording system (resolution of the system).

The spectra have been simulated for argon plasma containing traces of water and some elements. ICP and hollow cathode dis­ charges have been considered. The program for graphical presenta­ tion of emission plasma spectra hae been written in TurboPae- cal 5.0 for the IBM PC/XT/AT compatible computer. Relation between possibility of spectrum simulation and our present knowledge on spectroscopic data for atoms and molecules, plasma parameters, spectral characteristics of detectors (sen- sivity versus wavelength), geometry of plasma (spatial distri­ bution) has been discussed and presented.

217 DETERMINATION OF MICRO ELEMENTS OF STANDARD ROCK SAMPLES BY ICP-AES TECHNIQUE USING THREE DIFFERENT DECOMPOSITION METHODS , jAES-75

A.Bartha, E. Bertalan, P. Fodort K. Ikrenyi

HUNGARIAN GEOLOGICAL INSTITUTE, PO.BQX. 106, 1442 Budapest * UNIVERSITY OF HORTICULTURE, 1114 Budapest, HUNGARY

In Hungarian Geological Institute very common task to analyse the micro element content of different rock samples.Three different decomposition methods were compared analysing the different types of rocks:

- Decomposition by LiB02 fusion in platinum crucible

- Decomposition in high pressure teflon bomb by the mixture of HCL- HN0,-HF acids

- Decomposition after evaporation by the mixture of HC1-HC10, acids in platinum dish

About thirty COMECON rock standarosCsilicates, sedimentary rocks, ores and sulfide ores) were analysed in the laboratory of University of Horticulture by a Thermo Jarrell Ash ICAP 9000 Simultaneous ICP spectro­ meter. The decompositions were made in the laboratory of Hungarian Geol. Inst. Some trace elements were analysed in the laboratory of Hungarian Geol. Inst, too by a Geoplasma B3Y-2* Jobin Yvon sequential ICP spectrometer.

The problems of different decomposition methods and our analytical system are introduced.

ne THE IMPULSE-SPECTRAL METHOD TO DETERMINE THE HYDROGEN AMOUNT IN TITANIUM ALLOYS AND ITS USE FOR HYDROGEN REDISTRIBUTION STUDY IN THE VOLUME OF METAL I 118-76 V.B.Bichaev, V.I.Mosichev Central Research Institute for Structural Materials "Prometheus". Leningrad, USSR

The results of investigation on the optimization of hydrogen de­ termination conditions in titanium alloys by atomic-emission spect­ ral method with spectrum excitation in low-voltage impulse spark discharge are reported in this paper. The application of controlled atmosphere, the constant tungsten counter-electrode of needle type

impulse discharge initiation by means of "volt-addition"p precise system for interelectrode space control, light spectral apparatus and photoelectric system for analytical signal amplitude registra­ tion as well as discharge circuit parameters optimization make it possible to improve considerably the service and metrological cha- raracteristics of the method mentioned above. The analysed area of injured metal ranges from 0,7 to 1.2 mn in diameter and from 0,05 to 0,08 mm in depth, respectively. This method enables to perform layerwise analysis of the surface area of metal to a depth of 0.05- 0.2 mm with step 0,03-0,04 mm. The error of single determination is characterized by the relative standard deviation value 0,05-0,10 according to determined hydrogen concentration. It is possible to estimate the hydrogen amount on the parts of different shapes and sizes. The performance of this method is 40-50 evaluations per shift This method enables to study the hydrogen redistribution in the vo­ lume of metal under the influence of such destabilizing factors as temperature gradient, mechanical stress, electrical fields and so on. In this paper, the titanium-hydrogen system study in the tem­ perature-concentration transformation from solid solution to hydrid phase in metal volume data are presented. The extreme mode of hydro­ gen distribution in this range was revealed.

lit DETERMINATION OF HICRODIPURIIIBS ID XENON DIPLUORIDK BY THE ICF AES METHOD AES-771 A.V.Bobkov, S.V.Varvanina, A.Yu.Sergeev, E.G.Chudinov I.V.Kurchatov Institute of Atomic Energy, Moscow, USSR The xenon difluoride, a new analytical reagent, opens wide possi­ bilities in analytical practice conversion of the components to be determined into the gaseous phase, discharge of aome matrices in the gaseous form. It provides less time consuming and better quality ana­

lysis in transforming refractory materials into solution. XeF2 evol­ ves intenslly the atomic oxygen from the water, oxidizes and dest­ roys organic compounds in water solution which often hinder the sub­ sequent phases of the analysis, also it can be used for fine modifi­ cations of the compounds. In the medium free of water and under rela­ tively soft conditions (at temperatures lower than 250°0) xenon dif- luoride reacts with variety of compounds, fluorinates them without complication of the sample matrix composition. It displaces oxygen from any oxygen-containing compounds. Use of XeFg is most effective in determination of the platinum group metals, in determination of B, F, S traoes in different materials. Although the reagent is amenable to purification, in its introduc­ tion into the analytical practice, especially in the analysis of high-purity substances, the control of impurities, in particular,he­ avy metals is needed. For determination of the mlcroimpurities of

4 6 20 elements (n-10" -n.10" %) in XeF2 the ICP-AES is used. A high re­ activity of this compound increases the risk of contamination and In its conversion into the solution a special approach is needed. All operations were carried out in a box with polymeric coating and nit­

rogen bloudown. The process of XeF2 decomposition in the diluted so­ lution HHOj is accompanied by heating up and this may result in los­ ses of the solution due to splashing. The increasing of the solution volume are reduced these effects but the level of the blank solution enhance. For losses to be avoided and the contamination level to be reduced, the organic solvent (acetonitrile) containing water additi­ on 5-fold excess relative to stolehiometry of the reaction with lePg. The mixture was held for a night and then evaporated to dry­ ness. The residue was dissolved in the diluted acid and analyzed in the spectroanalyzer JY32. In order to control accuracy of the analy­ ses simulators were used, which were introduced to each sample ana­ lyzed and into the blank solution. The technique has been used for controlling the technology of XeS, purification.

220

•- HIGH SENSITIVITY TRACE ELEMENT DETERMINATION AES-78 IN LIQUID AND SOLID MICROSAMPLES BY ICP-AES A.A.Boitsov, Kh.I.Zilbershtein, M.A.Kartasheva, G.N.Moshkovich Institute of Silicate Chemistry, Leningrad, USSR Trace element determination in small volumes of different liquids is a very urgent problem for many fields of modern science and technology. The ICP-AES analysis methods are undoubtedly promising for these purposes (see for example [i]). We have elaborated some ICP-AES methods of analysis of aqueous solution microvolumes and their dry residues using the JY-38P sequ­ ential ICP spectrometer. Our earlier version of microvolume analysis method [г] consisted in a pulse injection of microsamples into the pneumatic nebulizer by means of interruption of continious pure water flow. Now we used a peristaltic pump (as in [3]). The influ­ ence of different kinds of nebulyzers (including Babington one) and spray chambers on analytical performances of the experimental device was studed. The most efficient was the demountable concentric nebu- lyzer with the two-tubes all-welded spray chamber. We obtained in this case the best line to background ratios and the lowest detec­ tion limits for small solution microvoluies analysed (20-50 micro­ liters), that were introduced into the ICP at a very low solution uptake rate (0.05 ml/min). A new variant of solution microvolume dry residues analysis method differs from the described in [2] by the possibility of automatic pulse insertion of special form graphite rods with dry residues into an ICP along the optical axis of the spectrometer. The method provides a more effective use of sample and lover detection limits (of about 10"u - 10"12 g). The elaborated methods are used for nicrovolume analysis of some high-purity and unique liquids. Referenoes 1. Alexander P.W., Finlauson R.J., Smith and Thalib A. //Analyst, 1982.Vol.107. N 1280. P.1335. 2. Zilbershtein Kh.I., Kartasheva M.A., Moshkovich G.N. //ICP Inf. Newslet. 1984.Vol.9.P.688; Zh.prikl.Spektrosk. 188вУо1.44.Р.359 3. Krasilshchik V.Z., Sukhanovskaia A.I., Chupakhin H.S.//Vysoko- chistye veschestva. 1968. N4. P.151.

221 RELIABILITY 0? SIMULTANEOUS QUANTITATIVE DETSRMIUAMON AES-79 OP HICROKJSMNTS IH WATER3 BY A SPBCTROCHHJICAL METHOD BASED OH MATERIALS OP COHTROL BY INTBRHATIOHAL SERVICES OP SATER AHALY3IS QUALITY T.V.Khokhlov, H.P.Hilcltina, V.I.Latikainen, VSEGEI, Leningrad, USSR A highly informative STE-1 spectrograph of a new type is applied A synchronous photographing of dry sulphate residue spectra in wa­ ter sample and comparison sample is realized» She scheme of analy­ sis principally solves the problem of attaining a high determina­ tion correctness ffl • Proceeding from a relative value of the sample and comparison sample spectral line intensity, a prelimina­ ry content of microelements in the sample is determined. On the ba­ sis of these data and results of a general chemical water analysis, two standards are prepared. Calibration graphs are plotted from synchronously obtained spectra of dry sulphate residues of the standards and the same comparison sample» A precise content of mic­ roelements in water is established from these graphs И . Comparison of true contents of microelements in ВШ w-3/1 sample (IAEA) and the results obtained at VSEGEI mcg/1 [>]

Element 7e Mn 171 Co Cr V Cu Pb Od

True -125.800 9.560 2.000 2.240 2.020 2.000 9.060 10.000 3.980 values Results 2. IOC obtain» ,113.000 9.900 1.900 2.000 1.700 8.300 12.000 4.700 at VSBG

Similar results, confirming the reliability of a simultaneous quantitative determination of other microelements, have been ob­ tained in the course of studies on Standard Reference Samples at the US Geological Survey. References 1. Khokhlov V.V. Multi-element analysie in geology. L.: Bedra, 1986. 200 p. 2. Kholchlov V.V., Nikitina N.P., Latikainen V.I. Certificate no. 1188601,, 1985. 3. Report on Intercomparieon w-J/1 of the Determination of Trace Elements in Water. I1BA/ BL /9*. 1982.

212 SPBCTROUEIRIC ОЕТВНмШДИОН OF TUHGSTEH Г~~ | AES-80, IH HOBCOHDUCTIKO MATERIALS WITH USB OP ' MULTIFUHCTIONAL GLOW DISOHABSB LAMP

J.Csakow, S.Tyoochowici, Т. Китая Institute of Huclear Chemistry end Technology, Warsaw, Fbliuod

In the paper the epectrometric method for determination of tungsten in nonconducting, powdered materials with use of cold flat cathode in multifunctional glow discharge lamp has been described. The spectra were registered on spectrograph P5S-2 with a speetrometric attachment and fine adjustment device for spectral lines (home made). A linear calibration curve (over 3 order) with regression coefficient r-0.9998 and determination limit O.OBS V were obtained.

& ПБТБИШГАМОМ OF BARE EARTH ELEMEHTS IK ROW-OFFS OP COAL ( 1 MIKES WATERS USING ICP METHOD AFTER CONCENTRATIHG |ABS''81 1 I.Yu.Davydova I.V.Kurohatov Institute of Atomic Energy, Moscow,USSR Goal nine bleed-off water is known to be a source of environmen­ tal contamination aa its content of Pe, Al, On and a number of other elements for much exceeds LAO. At the same time it is ready hydromi- neral raw material because oontains the rare and rare-earth elements in concentration varying from n to n.10yig/l. The purpose of the present work is development of the technique for REE determination by TCP method on the IY3BP monoderomator. From the variety of the known analytical REE lines have been se­ lected those showing the least effects of REE elements on each other and other elements. However we did not succeeded in excluding the superposition of the Fe and Al spectra and therefore a simple and express scheme of preli­ minary concentration and separation of REE from the matrix elements have been developed. The scheme is based on the known process of eoprecipation of REE and Ca oxalate since the bleed-off water contain about 200 mg/1 of Ca. However when the concentration degree is increased by 5-10 times the Ca content in the final solution rises up to 1-2 g/1, which redu­ ces the intensity of signals of the elements to be determined.In or­ der to obtain the quantitative REE precipitation with the non-quan­ titative Ca precipitation the coprecipitant, spectrally pure coal, was introduced. The concentration technique has been tested on the geological standard SGD-1A. Characteristics of the REE spectral determination and the results of the mine water analysis

Element Analytical о Defection limit. REE content in line, A /««A the mine water» МЯ/1 Md 4304.88 40 130-250 ± 68 Ce 4138.98 38 130-260 i 5?S Eu 4130.96 5 5-10 ±16» La 4087-96 7 30-70 ± Vf, Pr 3909.50 34 30-70 *1Й6 Yb 3695.10 11 10-25 ±122 3D 3593.56 16 30-50 ± 5* Tb 3510.10 47 10-15 ±15Й Gd 3423 .30 20 60-85 i ess

224 DIRECT ОВТЕЮаЯАИОТ OF HARE ЕЬЕИЕНТЗ.МЮНОСОНСЕИтАИОИЗ nZjTZ^ ИГ 1ШШ WATERS И ICP METHOD I . I.Yu.Davydova I.v.Kurohatov Institute of Atonic Energyt Moscow, USSR The technique for direct determination of Co, Hi, Cu, Be, So, Zn, Y, V against the background of the maeroooncentrations of Fe, А1, an, Hg, Ca in the bleed-off inter of ooal mines using IOP method on the 1X32 polyohromator has been developed• The ooal mine bleed-off water ia characterized by a wide range of the total mineralisation (0.7-16 g/1) and acidity (EH 2-е), with in­ crease in the water acidity the total mineralization increases at the expense of such elements as Pe, Al, Hn while the Ca and Kg concent­ rations ohange insignificantly. The metal ions constitute the salt background in combination with the enlous (30?T Cl~). The levels of the spectral interferences have been determined and the correction coefficients have been calculated. The actual detecti­ on limitв have been calculated with allowance for the matrix interfe­ rences and as well as the relative standard deviations in determina­ tion of the rare-elements have been calculated against the background of maorocooponents. The consumer is satisfied with the characteristics of the tech­ nique. 640 samples were analysed using the technique.

Characteristic» of spectral determination of SEE elements and results of their determination in mine water

Ele­ \ A £g/l Relative stan­ Concentration ment tab. actual dard deviation in bleed-off water, /fg/1 Co II 2286.16 4.7 11.1 0.01 63-2666 XI II 2316.04 10.0 9.0 0.015 148.0-3741 Be I 2494.73 2.5 9.0 0.16 200 V II 3110.71 4.3 5.4 0.10 4235 Cu I 3247.54 3.8 4.5 0.05 8-1217 Zn I 3345.02 - 3.6 0.008 58-3700 So II 3613.84 3.4 5.2 0.005 3-912 Y II 3710 2.3 2.5 0.008 3-912 "'FiW.j.K.Boumans. "line colaoldenoe Tables for mauotivlty Coup- led Plasma Atonic Emission Spectrometry". Vol.1, 2.

IS.3sx.4I3 Я8 AEPUCATICB <Ш АТС1СС aOSSXCB METHCC Ф AHAHOSIS I 1 ASS—83 MR AIK ЮТИТ CCKTROb I il Ye.V.Dyegileva,&.I.0taachova,^V.Heradovskaya,V.I.Kyle8hov Tomsk State Unlversity.Tomsk, USSR Impurity control of air basin oocupiee an important place In gene­ ral complex of steps towards environmental proteotion.Sor it's full provision it is necessary to acquire the data about toxic metals con­ centration in the air.wbich are present in the composition of solid aerosol partlcles.jfor the analysis seleotion of industrial and at­ mospheric aerosoles was carried out by aspiration method with A7A-XP and AFA-VP filtres according to the traditional prooedure of probe selection [1]« Principal attention was paid to the improvement of or- ganio base probes because of the filtre foregn material preseneei As for the atomic emission method,the probes'thermal ashing conduc­ tion is preferred.Thermal destruction conditions of filtre materiel have been investigated.Sample maximal decomposition is obtained in oxygen flow at 450-500 "0 in quartz microwave furnace,residual weight is 5 mg. In the process of this decomposition evaluation of several micro­ elements losses due to lighly volatile elemente'formatlon and convec- tional removals was carried out.Ashing is recommended for their elimi­ nation in the presence of absorption mixture,including graphite powder and sodium diathylditiooarbamate (DDK),10(1.respectively,which is pla­ ced at gaseous products outlet.Weter and hydrochloric acid vapours, escaping during filtre destruction wet the absorbent and oreate the possibility of or reaction on the solid phase and vapour gaseous mix­ ture interface between DDK and metal volatile forma,metal organic com­ positions being formed. On the base of this ivestigatlons the chemical atomic emission pro­ cedure of aerial aerosoles analysis was developed.lt allows to reveal 18 elements with complex organic base separatlon.excluding chemical decomposition.Ihie method is based on thermal destruction of filtre material in oxygen flow;effective absorption mixture is used;it allows to eliminate losses and carry out further summed atomicemiesion ana­ lysis of concentrate.

Reference 1. Kuravyeva S.I.,Kasnlna 17.I.,Proohorova re.E.//Beferesce - book for toxic matters'control 1л the slr.Hoscow (US8B),1988.,P.520.

m MECAL lUCHOIHFUKITIES ШГБИИНАТЮН IK CdTe AND HJITIAL I 1 PRODUCTS JOH ITS SINTHESIS ВТ ATOMIC EMISSION METHOD I

Ye.V.Dyagileva,Z.I.Otmechova,V.li.llaryanov1H.V.NeradovBkaya Tomsk State University, Tomsk, USSR Valuable electrophyslcal and optical properties of CdTe are stron­ gly dependent ой its Impurity composition.Thua it is actual to develop simple high sensitive and express procedure of analysis of Си,Те and compositions on its base.The combination of ion exchange with atomic emission analysis of Impurity concentrate on the ion exchanger base gives the opportunity to develop such procedures of high pure matter analysis.Cd,Te and impurities behaviour investigation on KU-2-8 and ADi-10 F ion exohangera out of hydrogen fluoride mediums with various concentration showed that it is possible to use ion exchanger mixed layer for the separation of Cd ,Ie macroscopic amounts and impurity quantitative selection in static conditions«Due to the good resolution of localized signals the separation of basic element amount excess only is necessary in most cases and it is the specific peculiarity of element traces separation and concentration in combination with con­ centrate atomic emission analysis.98% and 99% of Cd and Те separation leads to the fact that their residual concentration is 9 and 6 %,res- pectively,in relation to the ion exchange collector mass. The investigation of base residual amount effect on the impurity spectra line intensity showed that Cd presence reduces the determina­ tion limit of some elements.lt is connected with cadmium sulphide for­ mation as a result of cation exchanger destruction,having a sulpho- group and Cd in its composition.In contrast with organic matrix cadmi­ um sulphide dissociates at more elevated temperature.promoting the change of atom entrance conditions into discharge zone. For metrological characteristics improvement a new method of ion exchange concentrate preparation to the atomic emission analysis is of­ fered. It contains concentrate irradiation with continuous COg gaseous laser. Chemical atomic emission procedure of Те, Cd and CdTe analysis was developed on the base of these lnvestigationa.lt allows to reveal 24 impurity elements with detection limit 10~5 - 10~%тввв,relative Stan- dart deviation is not more than 0.25.

ш ATOHIC-SPECfRUM AH1LYSIS OF ОЛВВОН-BASED HATEHIAia V.A.Bgorova, L.i..Maehkovich, A.F.Kuteinikov, O.G.Homanova' ' HUGraphit, Moscow, USSB

Methods of atomic-emission) absorpsion, end fluorescence analysis have been developed fox carbon-based materials to determine microsco­ pic imparities and additives in case of their content from traces to some percent. The operations of introducing a substance into an arc source dis­ charge in case of the spectrum analysis of carbon-based materials and their effect on the analytical signal have been considered. The depen­ dence of the ere plasma parameters on the carbon material structure has been established. The effective plasma temperature data calculated using a computer are presented. The possibilities are shown of using the atomic-emission spectros­ copy with inductively coupled plasma (TCP) for the determination in a broad range of boron concentrations in a carbon-based material after its alloying in a glassy carbon crucible and dissolving boron. The de­ termination of boron from solution makes it possible to limit the ef­ fect of matrix and chemical form.

*» ЕганАсмш-Ашмас HOSSIOH пганвшигаои OF TRACE i АИШСГОЕВВ IB HIGH РПВ1Я ХНШШП1 I 1— S.Elnazarov, S.Bustaaov Tadjik Stat» University, Dushanbe, USSR The main direction of extractive-atomic emission methods per­ fection Is the uaa of selective extragents for the macrobasia ext­ raction with the following analysis of trace admixtures on a higu- purity graphite collector. The ala of the work ia the atudy of a large number of metals extraction with a cyclohexylbenxenedithiocarbamate triethylamnoni- un (OHBDTC) chloroform solution out of alkali solutions with radio-

nuclides: ««^jj. «V 2°7Bi, »f.. "со. *0», *ta, «Bfc, 12?Bb, 75Вл, 2°**1, 65Zn and a spectral analysis of metala (Al.Ba, Be, Oa, Cd, Ga, Hf, In, Ir, La, Me, Hi, Se, Sn, la, Ti, T, T and Zn)i it was eetisated that silver.and thallium, only mere extracted out of 1-4 И XaOB with CBBDTO, the rest studied elements with the concentration of 2.5.10"' - 8.0.10 mol/1 are left in the aqueous phase and their distribution coefficients do not exceed 0.001- 0.003. On this basis a method of extractive nacrobasis estimation and atomic emission determination of 26 metal admixtures in a high-purity thallium. A sample of thallium with a mass of I g is dissolved in 5 ml of concentrated HBO. at heating! after cooling caustio soda is ad­ ded to make the solution 1 К in HaOH. Thallium is twice extracted with toe equal volumes of 2M GHBMC in chloroform. Ihe admixtures (11, Au, Ba, Be, Bi, ?e, Oa, Cd, 00, Or, Kg, Hn, Bi, Ga, In, Ir, La, Sc, Sn, Tl, la, Ti, V, T, Zn and Zr) are esti­ mated in an aqueous phase after its special treatment in I8P-28 spectrophotometer. To estimate the exactness of the data obtained in the experi­ ments with an "introduced-found" technique, the metals were intro­ duced in concentrations not more than an order higher than their determination limits. Ihe exclusions were Al, Ba, Fe, Oa, Mg and Zn, the determination ranges of which were limited with the blank test values. Any systematic erros in the determination of the exa­ mined elements were not observed. A relative standard error for different elements is in the range of 0.15-0.50. She determinati­ on limits Obtained with 48-criterion at the concentration ratio 50 are equal to 7-5И0Г6 - e.SHOT8».

a» ATOMIC EMISSION SPECTHOCHEMICAL ANALYSIS OF HIOH-PURITY Pb, IIS ALKYL COMPOUNDS AHD Pb OXIDE ' ' A.A.Yemelyanov, V.F.Zanozina, A.D.Zorin, N.K.Rudnevskii, V.I.Sid­ ney, Б.A.Suvorova, I.A.Feschenko Chemical Institute of N.I.Lobachevsky State University, Gorky, USSR Various methods have been suggested and examined to transform al­ kyl compounds of Pb to analytically active form providing safety of mineralization, absence of impurities and main component losses, de­ composition sterility. Depending on the problem to be solved they are decomposed in nitric acid vapors in a special reactor or oxidi­ zed in the flow of oxygen under combustion conditions•

Decomposition products of high-purity alkyl compounds, as «ell as metal Pb and Pb oxide have been analysed by an atomic emission me­ thod. A series of investigations has been carried out for optimizing parameters of the product analysis for impurities by regulation of the processes in DC arc discharge. For this purpose the effect of electrode shape, ionizing and subliming additives, application of magnetic field to discharge and other factors have been studied. A direct procedure has been developed to determine a great number of impurities in Pb oxide, the end product of transformation of metal Pb and its allcyl derivatives with detection limit 1.W"5 -1.10"6wt.* The method has also been used for analysing the conoentrate after the main component separation.

So reduce detection limits of low voluble impurities in alkyl com­ pounds a vacuum distillation method has been used. A two-staged pro­ cedure of enrichment by matrix precipitation in the form of Pb nit­ rate has been developed for concentrating impurities in oxide and me­ tal Pb samples. Detection limits of "dyeing" impurities of V, Mi, Co, Cr, Cu, Fe, Mn obtained by chemical atomic emission method are 1.10"^ - 5.10"°wt.% depending on the nature of the element.

2И UHIFICAMD ATOMIC-a¥ISSI0H ЖВТКШ KB HOBLB l.tES-88 HBIAIS ВЖТЮНШАТЮВ I I.H.Gil'bert, L.H.Soabanove, H.L.Kovalenko, G.L.Buchbinder, G.G.Soldatenko •Bydrotsvetmet", Novosibirsk, U6SH At present determination of noble metals in wide range of concent­ rations in metallurgies! product» with complex and variable composit­ ion with high accuracy is the difficult analytical problem for deci­ sion of which many methods of analytical chemistry are used. One of the most effective methods for determination both the little and the main contents of elements is the atomic-emission spectrometry with inductively-coupled plasma (AIS-ICP). The possibilities of analysis of materials with complex and vari­ able composition by the ABS-ICP in many respects are defined by the properties of basis*s elements, their concentration, total salt back­ ground of the obtaining solution. Depending on the enumerated factors the background in the region of analytical lines is changed, the in­ clination angle of calibration charts is also moved and changed, work stability of torch-nebuliser system is lowered. In order to receive the stable solution with low salt background the express method for solid products dissolution of cupper-nickel production (dissolution time is 15-20 min) in rotatable quartz am­ poules with polytetrafluorethylene plug with using of mixture of re­ agents, containing the oxiditers-catalysts of dissolution process is developed. The basis'» elements effect on analytical signals value of noble metals was examined for the obtaining solution. For these pur­ poses Identification of elements spectra for identification of the latent superpositions of spectra during their registration in the first and the second orders account and correction of spectral inter­ ferences, stipulating by diffused radiation from the basis's elements and radiation from the strong and the weak lines their in the region of analytical lines of noble metals, assasment of lower bounds of the defining elements contents and other aetrological characteristics in presence of different amount of the basis's elements, choice of the optimal conditions for analysis (power, bringing to plasma - I.I kM, flows coolant - 12, auxilliary • 0.2, carrier - 1.0 1/min, height of observation son» - 15 mm) were carried out. As a result of conducting investigations the express AXS-ICP for determination Au, Ag, Pt, И, Ir, Bo, Bu in range of the following concentration: 0.005-5; 0.002-90; 0.005-20; 0.002-60; 0.02-30; 0.006-6; 0.004-4 mass percents, accord­ ingly is developed.

231 DETflRKIffATIOH OP METAL IMPURITIES И HIOH PURTTI VOLATILE |ABS_eo SOBSTAHCES BY ATOMIC HJISSIOH HSEBOD !

A.H.Gordeyev, I.Yu.Durinov, V.H. Shishov Institute of Chemistry of High Purity Subataooes,US3R Academy of Soienoes, Gorky, USSR The methods of atonic emission determination of the impurities of

Pe,Hg,to,Pb,Cr,Sn,Ni,Bi,Ti,Co,Cd,Al,3b,AgtCu,Ca,Zn,l»o,Ha.V in high pu­ rity volatile inorganic hydrides (SiH,,GeH.), halogenides (SiCl., GeCl., POCl,,BBr,,BCl,), organometallic compounds (EtgZn, JStgTe, HegCd) and

organochlorinesilaneB (Me23iCl2,Me3iHCl2) have been developed. The impurities were concentrated on a earbon collector by vacuum di­ stillation of matrix in a hermetic glass-teflon device [l]. The concentrates of impurities ware analysed by do arc speetrografic method with registration of the cathod layer of the dc are discharge on the difraction spectrograph CT9-1. Detection limits were 8.10"'- 6.10-I1g Й • She possible losses of impurities on the preconcentration stage have been studied. It has been found that if the rate of distillation is less than 1.10"* g/sm?s and impurities are periodically washed from the walls of the device the value of losses do not exceed 10 % (3i4J . The nurses of the background contaminations have also been studied. It has been found that the main contribution to the value of the back­ ground correction introduce air particles of the laboratory environment. In some oases an abnormal high value of the background correotion has been noticed. It is due to the interaction between the matrix and the material of the device [5, б] • With 100 g sample the detection limits of Impurities in the above- -aentioned substances were 1.10"7- 2.Ю-10 wt * . The value of relative standard deviation was 0,6. References

1. Gordeyev A.M., Crishnova H.D., Drjahlova I.A. et al. // Vysooochis- tye veshoheetva. 1987. Я 6. P.138. 2. Shishov Т.Н., Pimenov V.G., Gordeyev A.M. //Ibid. 1969. B"4. P.214. 3. Drjhlova I.A., dhlehov V.H. //Ibid. 1987. H5. P.166. 4. Shlshov V.M., Durlnov I.O., Belabsnov T.T. et al. //Ibid. 1988. N6. P.165. 5. Shlshov Т.Н., Drjahlove I.A., Voronkova T.T. //Ibid. 1988. N5. P.121. 6. Shishov Т.Н. //Abstraots. Till Tses. oonf. po metodam poluch. i ana- lisa vysococh. veshchestr. Gorky. 1988.Pt.1. 7.86.

S» шсвоыяшгаб DBTKHHIHATIOH IN BIOIOGICAL OBJECTS "ABS-9D WITH raOTOBLEOTHIO STSTHI MJS-8 I I.V.Gribovskaya, T.T.Uetyugova Institute of Biophyaics, USSE Academy of Sciences, Siberian Branch, Krasuoyarso, USSR Photoelectric system MJS-8 is primarily designed for quantitative emission analysis of elements impurities in metals. We used it to de­ termine the microelements! Pe, lln, Cu, Zn, Co, Cr, Hi, Ti, Al, Ag, B, Cd, Ho, Sn, Pb, T in powdered samples of biological origin. The objects to be analysed included: biomass of algae, plants, or­ gans of fish, animals, water, nutrient solution, blood. Analysis conditions incorporation: use of 20a a.c. arc and I5a c.e. arc produced by IVS-28 and UGB-4 generators respectively, 60 s exposure, water cooling for carbon electrode holders. Preparation of samples for the analysis incorporated evaporation of liguid samples in guartz dishes followed by ashing in muffle fur­ nace at 450°0. The samples of biomass were dried at I05°0 and also ashed. The samples and standards were mixed in 1:3 ratio with buffer and fed into the crater of the carbon electrode i 4mm, 4mm deep. To avoid emission of the sample in ignition the crater walls had 4 Imm hole 1.5 mm over the bottom. The buffer was carbon powder with 20$ HaCI steady burning of arc and sufficient determination sensitivity for the majority of the in­ vestigated elements was maintained by the buffer. The standards made on artificial matrix close to the average com­ position of matrix of the specimens to be analysed.

The standards bases included: KB^PO^, KgSO^, KG1, MgO, CaO, Si02, HaCI. The standards for samples of different kinds differed in ratio of above mentioned salts. The microelements were introduced into the standards in the form of oxides. She analysis technique used allow to reduce considerably the in­ fluence of the matrix samples and standards. Herewith, the microele- ments are determad with the sensitivity 10-10 -76 of the dry matter depending on the element to be determined and on the form of sample. Correctness of the analysis was verified with state standard samp­ les for biological objects SBIK-02 H 5169-85 (potato nodules),! 3171- 65 (wheat grain), M 3170-6? (grassmixture). She results converged within the limits of spectral analysis error up to 25*.

2» -«n AXOHIC BIISSIOH SFKTBOMM?BY WITH HIGH РНВДПИСТ [AES^T РЬАВМА-ШМТАИОН SODSCI HI ANALYSIS О? СНЮВШВ I AMD DTOEGAMC CHIOBM^OOTAIHIHG SUBSTAHCSS I.A.Iljichova, D.Ta.Choporov, I.F.DegteriJove, H.L.Antulskaye H> "СЕТОН", Geological Institute of the US6B Academy of Sciences, Moscow, VSBB

Methodic»! approaches to high purity chlorine analysis of the eon- tent of transition metals (about IO"Ti) Ъу atonic-emission spectromet- ry with high frequency induction plasaa source have been developed. The possibility of direct supply of liquid chlorine into plaena torch through a spraying system has been investigated. She possibility has been investigated of concentrating microimpu- rities in high purity chlorine by distillation of the base to obtain dry unvolatile residue followed by measuring the solution concentrate. In order to decrease the matrix effect «hen determining microim- puritiee in high purity AbCL,, BiCI^, KOH and purified brine, various •edifications of atomisers have been developed and used giving an op­ portunity to change the effectiveness of transfer of analysed solut­ ion. Optimal conditions have been selected to determine readily ionis­ ing eleaents under which «he detection limit is decreased 1.5-2 or­ ders. In order to obtain reliable values of transition metals content in the range of I* a computer software has been developed to handle basic data files and to process data using modified «calibration al­ gorithm and this software allowed to increase substantially (2-3 ti­ mes) the accuracy of analysis results.

2M HBTHOD OF SORBEST CONCENTRATE PREPARATION TOR f HBAVr-MBTAIB DETERMINATION USING ICP-AES AND lABS"9a BTA-AAS METHODS G.R.I»hmiyarova, G.V.kyaaoedova, I.N.Fetrovskaya, N. F. Starahlnova, В.И. Sedyldi V.I.Vernadeky Institute of Geochemistry and Analytical Chemistry, USSR Academy of Sclenoea, Moscow, USSR

Group concentration of heavy metals from ground waters was pro­ duced using complex-forming sorbent (POLTORQS-VTI-K). The cholee of preparation of sorbeut concentrate method (eluation, aorhent degra­ dation and sorbent formation) was determined depending on method of analysis, character and volume of analysing water. Sorbet)t POESTORGS- vTI-M was used as fiber and thick felt for concentration of Си, Я1, Zn, Co, Cd, Cr(III), Fb (while pH-6); Mo, Cr(VT), Nb, Zr, Pe(III), V (pH-2) from 11 of water. The first group of elements was eluated by 2 К НС1. For second group of hardly eluated metals a sorbent con­

centrate was degradated in mixture of TOO» and H202 under UHP-radiat- ioa (degradation time-Э mln.) In phtoroplastlo autoolaves. Eluate and concentrate war* analysed by ICP-ABS methods. For concentration of Cu, Hi, Co, Cd, Pb from small water volumes (5-25 ml) was produced together with ultrasound dispergatlon, sorbent suspension being for­ med in water. Sorbent suspension was analysed by using BTAAS method.

A number of methods was proposed for heavy-metal contents in water determinationt for sea, river, lake, snow, silt waters.

235 SFECTHOCHaCtCAL ASALYSIS 07 HIGH PURM! |IB»_QI АНТИГОНУ. OXIDE I W. Jaxa-Bykowalci Reaearoh Development C«nt«r Polam, ffareaw, Poland

There ia found a speetroehemlcel anthod of the contaminations de­ termination» In antimony oxide showing a high degree purity. The in- fluanea of oarrJer quantity on th« intensity of alaaants llnaa haa been Investigated. Measurement of arc plasma temperature of contaminated antimony ozlda baa been In 4500-6200 1С Following elements were determinedi MB, Pe, Cu, HI, Pb, Ba, As, Zn In concentration 100-0,1 ppm. Obtained antlnony oxide was mixed with graphite powder having a spectroscopic oarrlar and than they underwent the dlreot current arc out of the carbon electrode crater. She elaborated method allowa the simultaneous determination of 8 elements in antimony oxide of the results. Relative standard de­ viation la 0,13. For the analyala of antiaony oxide oonoernmg the content of the determined contaminations, there were applied various physical methods» Experimented examinations prove that the applied method ia free of the systematic error and the accidental errors In seme number of the methods oscillate In the limits of 10-30*.

IN APPLICATION OP IOP-AB3 POR THE RARB-EARTHS | OP петавшшиоя |iss-9» A.ir.Karyakin, I.r.Sltgonova, Yu.I.Pabellnsky Vernadsky Institute of Oeoohemistry and Analytical Chemistry, USSR Academy of Scienoes, Hoecow, USSR The literary analysis shorn» that determination of rare-earths, with the help of the induction plasma, possesses a great possibi­ lity when analysing pure substanoes and geological objects beca­ use the sensibility of their determination le high enough, compa­ red to the method of neutron activation. It is noted incedentally, that determination of rare-earths by means of induction plasma Is conduoted as a rule after their separation from oacrooomponents with the simultaneous concentration of rare-earths. The purpose of this work is a study of the processes of excitation of rare- -earths in induction plasma, transmission of the energy of exci­ tation between rare-earths and one order of the comparison with the elements of the other group. Theoretical reasons for the phenomenon is given, which is concluded in additional excitation of some said above Individual rare-earths by transmission of energy from the excited atoms of argon, which turn up to be in metestable condition state (depending upon general potential of excitement of the individual rare-earths). Existence of blow of secondary type In induction plasma is confirmed by spreading of contures of spectral lines of some rare-earths. The study of lnfluenoe of a sum of rare-earths on the inten­ sity of spectral lines of the individual rare-earths showed that the intensity of the last undergoes weakening or strengthening which depends upon general potential of excitement of the line of rare-earths, which displays dearly for the elements of the second group. The phenomenon is practically absent for the ele­ ments of the first group.

297 OTRBSS-HBTHOD OP ATOM-HUSSION DETEHMIUATIOlf | OP incHOELBiaras in BIOLOGICAL OBJECTS |AES-95 G.V.Kashkan, V.I.Kuleshov, V.H.Kumook, O.V.Baranova, E.V.Ivanova Tomelc, USSR The express-method of atom-emission determination of 14 vitally Important microelements In the animal's and human organs without macroelements separation Is developed (A.C. И 1434315). Complexity of mineral composition of biological samples and presence of macro- end mlcrocomponents require optimisation of each analysis stage. Ma­ ximum error Is lntroduoed by process of sample preparation. The low inertia! quartz tubular furnace Is proposed for express ashing of biological samples (tissues, bones, bloods, hair and so one). Its ashing time is 15 mln., whereas traditional asshing In muffle fur­ nace lasts about 10 days in dependence of sample type. The long ash­ ing Isn't eoonomio and dlstors results of analysis by evaporating of some microelements. The conditions of aton-emlssion determination of microelements in presence of basioal components are optimised. Balanced samples compo­ sitions were computed with computer BESM-6 for establishment of che­ mical formj!f macro- and microeomponents in range 300-3000°C. The

system, consisting of №C1, KH2K>4, CaCOj, S, IT, C, and one of micro­ element si ?b, ZB, Cd, Sn, Mo, Hi, Мл, Al, V, Cr, Cu, Fe, Co, was in­ vestigated. Computation allowed tc expose possible sources of metho­ dical errors. Demands to composition of basic elements in etalons and its preparation were preparation were preoised. The influence of separate macrocomponents of intensity of spect­ ral lines was Investigated by experiments. It is established that with concentrating more than 25 times, KjHPO^ essentially reduces analytic sygnal. Limits of microelements detection by this method are 10~*-10"^5. The ashing method, proposed in this work, la sufficiently effec­ tive, simple and can be used in atom-emission analysis of different objects on organic base both natural and artificial origin.

238 ANALYSIS OF HIGH-TEMPERATURE SUPERCONDUCTORS j ' AES-961 BY ICP ASS and XRF ANALYSIS I ——I

V. Kllaent Inatltute of Fhyalca EPRC SAS, 842 28 Bratislava. Czeehoalovakla

Sine» tha dlaeovary of hlgh-teaperature auparconductlvity (HTSC) In 1086 thara ha* baan great activity aaaoelatad with tha characterization of tha auperconductlng aatarlala. Racantly, auparconductlvlty with Те above 90е К ha* baan reported in tha Y-B«-Cu-0 ayateae. The auperconductlng propartlaa depend on cha- alcal coapoaltlon and alao on lapurltlaa in the** aaterlola. Therefore praclaa analyala for aeln eleaenta and trace aleaenta are important. Tha atoale aaiealon ICP apactroaetar 3Y70VHR waa uaad for datarainatlon of Y.Ba and Cu in tha aolutlona after diaaolutlon of auparconductlng aatariala in diluted HC1. Tha aalaalon line» 224.754 na and 233.527 na ware uaad for deteralnatlon of copper and baryua. raapaetivally. The alaulteneoue part of apectroaetar waa uaad for dateralnation of ytrlua (Л • 373.0 na) and alao for naaauring of 257.6 na Una of aanganaea. which waa uaad aa an internal «tandard. Optialzatlon of exporlaontal condition wa* don* to laprove accuracy and preelelon. Th* coaparlaon of background correction aathod and intereleaant correction aathod for Y-Ba-Cu- •0 and Bl-Sn-Cu-Ca-Sr-0 eaaplea waa dona to laprova praclalon and accuracy of analytical raaulta. We have uaad XRF analyaia for determination of Y, Ba and Си in 241 the HTSC aatarlala. Tha annular Ae nuclide waa uaad aa an ex­ citation source for X-ray production. The characteristic X-ray of eleaenta waa detected by Sl(Li) detector and X-ray apectra* wara ragietratad by 1024 channel analyzer. The synthetical stan­ dard* ware uaad for calibration. Tha influence of axperiaental condition on precision and accuracy waa axaainated. Tha bulk aaaplaa and thin layer aaaplae were analyaed and good agraaaent for both uaad aethode waa obtained»

J» ATOMIC-SMIESION DBTHMIBATIOtf OF HIHOB AES-97 Ba AND Sr COHCHJTRATIOHS IN BOCKS Z.A.Khokhryakova, V.S.Sukaev Institute of Geological Sciences, Yakutsk, USSR

She existing methods for Ba and Sr determination use Cr [1] and Bd [2] as an Internal standard. However comparison of no­ sology criteria shows that La is the aost suitable elenent for coaparieon of both the above elements. A method for Ba and Sr determination in geological samples in the concentration interval 0.O02-0.O2* is proposed. The follo­ wing analytical pairs were used 1 Ba II 455.40 nm - La II 455.58 nm and Sr I 460.76 na - La I 457.00 na.

The choice of a. buffer consisting of a mixture of coal powder with 15% quartz and 1% lastanum oxide is substantiated. Spectra were obtained on a KSS 2 spectrograph with a grating 651 ma-1. Reference samples were prepared based on geostandards. Analytical representation of calibration graphs and all calcula­ tions were made on computers using special programme.

Variance analysis of the proposed method was performed on a series of geostandards. Relative mean-square error of the determinations is 12* for Ba and 25% for Sr.

References 1. Busanov A.K. Bates for quantitative spectral analysis of ores and minerals.H.: Sedre,1978 (in Russian). 2. Bgranova 1.0. // Zhumal analitieheskoi khimii. 1934.Vol. 39. F.1421 (in Russian).

MO Inorganic Multi-Element Analysis Using Inductively Coupled Plasma Atonic Emission Spectroscopy According to the Contract Laboratory

Program (CLP) Quality Control Regulations |1B!_M |

Ing. Ad Klok, Ing. E.Uitbeljerse BAIRD EUROPE B.V. Produktleweg 30 2382 PC Zoeterwoude The Netherlands

Inductively Coupled Plasm» Atonic Emission Spectrometry (ICP-AES) is generally accepted as a useful tool for the analysis of major, ainor and trace elements in a wide range of samples.

Based on the Intrinsic analytical performance (e.g. profound detection limits, large linear dynamic ranges) ICP-AES is one of the major analytical techniques used In Quality Control (QC). The U.S. Environmental Protection Agency has formulated rules to which laboratories are restricted for specific QC analysis. The regulations are summarised In a Contract Laboratory Program (CLP).

BAIRD has incorporated these guidelines In the ICP software, Including the special presentation of the results, the recali- bration procedures and the use- of a random access sample changer. This presentation will explain the CLP software procedures and present the analytical results obtained from some typical samples.

I6.3aK.4I3 241 ANALYSIS OP METALS AT MACHINE WORKS AES-99 BY USINQ AUTOMATED SPECTROMETERS

A. A. Kozlov, V. S. Gorlov, a V. Mai lglna Gorky Automobile Plant, Gorky, USSR

The fundamentals of significant increasing of preoeaslon,speed and automatIon of metal industrial spectral analysis «ere created at Gorky atonoblle plant at the beginning of 60s due to assimilating the photoelectric registration of spectrum. The lst-generatlon quan- tometers and speotroaiialysers have automated the most part of ana­ lytical oyole having excluded manual photographic operation. The con­ venience of handling with electrical signals from photomultipliers contributed to the computerising of spectral analysts and caused fur­ ther large-scale automation of latest generation spectrometers. The active experience at the plant with built-in hardware and soft­ ware ( firmware and application programs) spectrometers proves that industrial spectral analysys is just the field where microprocoess and microcomputers provide the greatest advantage. 15 automated spectrometers in use at full power fast analyse a vide rang» oast irons,steels and non-ferrous alloys for its own foundry,for incoming tests of metals from suppliers,for routine mix- -up-control and metal sorting identification. Nowadays more than 90Z of all metals analyses (4 millions analyses annually) are made by automated spectral methods. As a rule all elements of interest including C,S,P are simultan- eosly determined in prepared sample of metal in 1-2 minutes with relative error l-3t.The results are put out in percentage and «ay be represented in a form acceptable to human-beings: ordinary electric tlpewriter.alphanumerioal printer,high-speed line-printer, display or other indicators. Much attention is paid to sampling and preparing standards for different metal alloys. The essential role in terms of metrologioal support of spectral analyses has been played by the ministerial atte­ station of plant analitlaal laboratories,the main part of which was sertlfloatlon of plant standards and automated spectrometers as un- standardised Mans of chemical composition measurement. It shoud be pointed out that carbon spectral determination with adequate accuracy in high carbon oast irons is a problem though some special methods lead in separate cases to suooess. APPLICATION OP IHDDCTIVELY-eOOTLED PLASM* ATOMIC j EMISSION SPECTROMETRY TO AHALYSE HIGH PURITY SUBSTA1JCES I*85"100

V.Z.Krasilshehik All-Union Selentlflc-Reeearoh Institute of Chemical Reagents end Special Purity Chemical», Moecow, USSR

The process of determining of trace elements In high purity mate­ rials is connected, as usual, with the realisation of the preconcent- ratlon operation for the alms of subsequent analysis of the concent­ rate. ?he problems of effective combination of chemical preconoentration procedure and ICP AES are discussed. The application of limitation of the rate of injection into the spectrometer nebulizer In the ranges 0,1-0,a ml/mln is reported to allow to analyse organic and Inorganic chemical oonoentrates with the volumes of 0,05-0,1 ml and realize pre- concentration factors in the ranges n-10 . Technological and methodological features of application of dif­ ferent preconoentration ways in analysis of a number of high purity substances by ICP AES are discussed. Experimental results are obtain­ ed by analysis of aluminium, alkaline and alkaline-earth salts with extraotlonal impurities reoovery in DDK-Ha/ohloroform system; sili­ con, boron, germanium oxides with matrlxs distillation as fluoride or clorlde in conditions of vapor-phase autoclave or flowing system; acids, organic solvents, organoaetallic oompounds with impurities preooncentration by evaporation. The conditions of analysing concentrates of small volume, obtain­ ed in the form of mixture (3>1) of acids HC1 + HHO, In the plasma source of spectrometer Plasma Speetromet (Balrd) are optimized. The methods proposed allow to determine a great amount of Impurit­ ies with deteotlon limit 10"' - 10-8& and error about 10$.

243 EXTRACTION SPEOTROQIMC DETHaCNATION CS BOHQjt Ui VARIOUS OBJECTS I USING DIM, ACENTS.raciTATION MECHANISM 1Я8-101 N.E.KuzmenKc,V.A.Panov.K.K.Khovalig.K.A.SeoenenXo.E.H.Schwartz Moscow State University,Moscow,USSR

An extraction procedure «1th t,3-diol agents is a powerful tool for the elimination of matrix Interferences in determination of boron by means of molecular emission flame and cavity (ИКСА) techniques as well as inductively plasma atomic amission spectrometry .A comparative study of extraction spectrometry determination of boron 1л this excitation sources with application of new superior agents : 2,6-dlmetfcyl-4,e- octanedlol and 2-methyl-6-fflethoxyl-3,5-dodecandlol (neorsln) has been carried out. In order to Improve analytical techniques and optimise determination parameters these combined extraction spectrometrlc procedures were explored In terms of analytical transport efficiency [11 as well as excitation meohanlsm C2J. The 3-component systems of dlol-alcohol-toluene were optimized for direct extraction flame determination of boron. Complex mechanism of excitation In flames and cavities has been suggested,- the overall intensity was a sum of thermal and chemllumtaescent ones t2].It was shown by quantitative consideration that, chemilumlnescent excitation was due to a dominant reaction: BO(xV) + 0{Ъ) -. BOg*(A2!y .As the result of this study It became possible to Improve MEGA technique and to reach i ppb detection limit,linearity of analytical curve in a wide concentration range and RSD of 0.01-0.03. Combined extraction spectrometrlc techniques were applied to the analysis of various alloys,wood and natural waters.

HeftrenoiB 1. Etmov V.A,, Snwnenko К.Л., Buyakor Yu.Ya.//J.Asalyt. ChUu 1989. Vol.44. P. 1382. 2. Buur V.A., Заапмоко R.A., Жвауакот Yu.Га.//Ibid. 1988. Vol.43. £.832.

S44 ВИРЕИПНАМШ OP НШХ MBTALS IN LAKE SBDJUBHTS BY \-~ 1 1ES—102 BHISSIOH SPBOTROORAIHY WITH AIR-JBT COHIRObLBD D.C.ARC Г^ A.I.Kusneteova, B.L.Chuoakova Institute of Geochemistry! Irkutsk, USSR The investigation of sediment element composition la part of ob­ servation programme on the Baikal lake ecosystem. Ям emission spectrography method la used for it* multi-element and economic cha­ racteristics. So improve tha precision and aoourecy of Ag, В, Оа, РЬ, Ко, Си, Co, Or» lit Tt Sn, 3c, In determination the approaches for gover­ ning the vaporisation prooaaa in the cavity of a carbon are «lac- trod» war» usad, Aa shown [l] , theae approaohea that accelerated the evaporation procaae in tha arc electrode ( the uae of the air- Jet controlled d.c.are and under-out type of electrode, sample dilu­ ting by alxturae resulting in formation of volatile oonpouda ate) reduce the dsffsrenoea in tha kinetics of basic processes taking place in the electrode between tha elements of different volatility. Shis, in turn, yields a better elnllarity in the behaviour of ana- lytea and the Internal standard and correspondingly reduces matrix affects in tha multi-element trace enalyels. Che metrologi3alchbreoteriatlos6.i*it of detection and precision) ara estimated using analytical raaults. the detection llnlt < in ppmi Ag -0.02, B-l, Oa -1, lb -2, Ко -0.3, Си -5, Oo -1, Сг 10.П-1, V -10, Sn -1, Se -1, &> -10) allow determination the above elements in the diatomic, pelltlo and aleurolltic sediments. In order to oheok the accuracy, the inter-laboratory coaparlaon of the reaulta of amission spectrography, neutron activation and atomic absorption analysis was made* It confined the absence of the aignifloant systematic bias.

Reference 1. Kuanetaova A.I., Horgolla Т.е.//J. of Anal. Atom. Speotrometr. 1988. Tol.3. P.973.

MS THE MECHANISM OP ANALYTICAL SIGNAL FORMATION IN DC P1ASHA i DETERMINATION OP REFRACTORY HETALS UNDER NEW METHOD OF *——— ADDITIVES INTRODUCTION CONDITIONS Yu.Ya.Kuzyakov.L.B.Pyatlgina.K.A.Semenenko Moscow State University,Hosoow,USSR

Formation of carbides usually complicates the determination of refractory metals In carbon-containing matrixes.This phenomenon leads to the decrease of the efficiency of various analytical techniques:AAS HGA.DC AES and ICP AES combined with solid probe accessories. A simple technique of multielement AES DC arc determination is suggested In this communlcatlon.The technique Is based upon the new method of additives Introduction - by means of saturation of graphite electrodes with additive Baits solutions. Complex mechanism of the additives (mainly alkaline earth chlorides were chosen) Influence on analytical signal was investigated. Considerable effect of the additives on the alternation of the mass-transfer path of the analyts was observed. DC AES determination parameters became close to optimal ones under conditions of electrodes saturated with additives.This result is In accordance with thermodynamlcal calculations of element species (the elements of IV-VIB groups of Periodic Table) distribution in DC plasma at various temperatures and electron densities. The acceleration of analyt transfer and the Increase of intensities of spectral lines under conditions of electrodes saturated with additives enabled us to apply an incomplete energies method and to Improve detection limits of IV-VI group elements up to 2 orders of magnltude.The linearity of calibration curves was extended to 3-4 orders of magnitude. Rather simple but advanced and useful techniques for Ti, Zr, Hf, V, №, Та, Ho, and w AES determination In a variety of carbon-containing matrixes have been developed. The application of this new analytical technique also eliminates the Influence of the difference In physical properties of graphite electrodes on the results of measurements.

2« ЛТШ1С aUSSIOR бРВСТйООННЦОАЬ JUTAMSIS OP Г— 1 LSS~IO& FmBO-CABBOH ALLOTS, PBODUCED BX UBIHOD |"—чи* OF ЕЫСТВОН-ВВАИ MEIWBG A.Lasarova, H.Oimitrov, T.Nieolov, V.Vasielyeva, G.Hladenov Institute of HeetronicB-BAN, Sofia, Bulgaria

The paper describee the method of qualitative determination of alloyed and admixtured elements in ferro-earbon alloys. Spectra exitated by ».e. arc, supplied by universal Bourses DBI-I and registrad with spectrograph PGS-2 (grating 651 line/mm,

blaze'4' '°° ""^ *"• selected the analytical spectral line and opti­ mised parameter of exitation and registration. We investigated the changes of concentrations of Cr, Hi, Mn, Si, V and Ho after electron- beam action on initial sample of alloy and also radial and longitu- dional distribution of thouee elements along sample. The statistical treatment of reaulta was produced according Il/PAC reeomendation, BSD was 0.I-O.2?. All procedure of aeasurment and treAtment was automised.

References 1. Kalugin A.S. Electron-been melting of metals. H., I960. 2. Kudelje E.S. Spectrochemical analysis of metals and alloys. K.: GIT1. Ukr. SSB, 1961. 3. Srasnobaeva H.H. et al. Handbook of spectrochemical analysis. Sofia; DI "Technics", 1970.

# M7 SCISSION SPECTROSCOPIC DETERHIBATIOH OF IHPUHITIES Iff ФДПЮВШГ OXIDE SBTGLE CRYSTALS ' ' S.S.Legeza Institute of Silicate Chemistry of the USSR Academy of Sciences! Leningrad, USSR Atomic eaiMion method* for determination of Cr, Kb, la, id, V impurities in WO, mingle crystals have been elaborated. Л method of direct spectral analysis in a dc arc was used to determine K, Cr, 7. She processes of burning down the elements from powdered WO, single crystals and from mechanical mixtures of pure WO, with oxides of the elements under determination were sho­ wn to be identical. Ibis permitted us to use the indicated mixtu­ res as standards. Analysis conditions. Powdered single crystals and standards were mixed with graphite powder containing 50 laCl in ratio 1:2 and exited from the orator of the graphite anode; a dc arc of 13 A; exposure time of 60 s; a DfS-23 spectrograph! photographic plates of Type II, A ohsmical-sDeetral method was used to determine Kb and Та. *»»^"<уч of sample preparation to »na^y»4a- Tungsten oxide single crystals were dissolved in hydrofluoric add in analytical autoclaves at high pressure and temperature. In the solution ob­ tained the extractlen-ohromatographic separation of the matrix was mate on the Polychromium-I. Threebutylphoaphate was used as extra- gent. Re-extraction of lb end Та was made using II Hgeo*. solution. The solution with impurities was evaporated on a graphite powder collector. Mixtures of graphite powder with oxides of Hb and Та were used as standards. Analysis of Impurities concentrate had been performed in a de are. The indicated methods were employed to analyse samples of WO» single crystals with impurities of 11, Cr, V, Kb, Та. It was shown that there are differences in concentration of the elements found by analysis and calculated by synthesis.

MS

m~ APPLICATION OP ХВГОСФГтаХ COUPLED РЬАВИА HUSSIOH AES-1106 | SPECTROMETRY FOR AHALYSIS OF WASTE PRODUCTS ДИВ RAW HAMHIALS СОИМИШЮ PHBCIOOS JtEIAbS B.V.Lindeman, V.A.Mertalshev, A.Z.flasyapov, ОЛ.ГагаЬаД eiMAMAZZOLOTO, Moscow, USSR Technological processes for treating waste products and raw ma­ terials to extract precious metals are being intensively developed at the present time. Optimisation of these processes and increasing of the efficiency of extraction require application of informative methods of analytical control which ensure high sensitivity and selectivity combined with acceptable accuracy and speed. Atonic emission methods of spectral analysis meet these requirements.

She report deals «1th the possibility of use of atomic emission spectrometry with inductively coupled plasma for identification of au, Ag, Fd, Ru is some types of waste products ( electronic scrap, photographic processes wastes, Industrial waste water ). Effective­ ness of the method for control of organic baaed materials or mate­ rials with organic components ( ion-exchange resins, electronic scrap ) has bean demonstrated.

Special attention is paid to ohenleal preparation of samples for analysis that depends on the type of material and the range of the elements being identified ( aleali-oxldatlon fusion, selective and autoclave dissolving and their coaMnstions with concentration techniques ). The results of the experiments and techniques of analysis for identification of Au, Ag, Pd, Hu in the above-mentioned wastes are given. Experiments were conducted with the use of simultaneous emission speotroaetre P-8210 with 10? source P-8490 ( Philips, «etherland ).

Mt SPKTTMb DETERHIHATICnr ОТ IRACB BLEMKHTS BY TJSIHO I j COLblSIOHS OP THB ЗВС01ГО КПП) IX HOLLOW CATHODE |AE8-407| DISCHARGE

S.Xe. Makaiaov, A.H.Rudnevsky Chemistry Institute, N.I.Lobachevsky State University, Gorky, USSR In connection with the problem of producing various high-purity materials the necessity to develop analysis methods characterized with high precision sad low detection Unite of impurities arises. One of methods with good prospects of atomic-emission spectral analy­ sis is a method with usage of hollow cathode discharge as on excita­ tion source, analytical characteristics of this light source can be substantially improved by optimizing speotrum excitation processes, for example, by magnetic or mloroware field superposition on dischar­ ge and by use of pulsed or combined power supply operation [1 ]. In a given work in order to decrease element detection limits in hollow cathode discharge the collisions of the second kind of atoms

or impurity ions with metastable cadmium and zinc atoms ( £0.2^ " well as nitrogen molecules in metastable (AsZjJ) and excited (X Eg) states are used. Cadmium and sine were introduced into discharge as vapors on evaporating from probes, and nitrogen was taken as an addi­ tive to a working gas - helium. The effect of eeleotlve enhancement of analytical line intensity for a number of elements the excitation energy values of which are close to those of metastable states was used In spectral analysis of dry residues of solutions and impurity concentrates formed by sample enrichment and in a diraet analysis of aluminium oxide. The detecting limits obtained were 10"9-10"12g that is 1-1.5 order of magnitude lass than those of usual hollow cathode discharge. Reference

1. Improved Hollow Cathode Lamps for Atomio Spectroscopy /Ed. S.Caro- 11. Chichester) Ellis Horwood LID, 1985. 232 p.

MO ATOKIC-EKISSIOH AHD ELECTRON РЕОНБ X-EAX ANALYSIS OF TOTAL |1W_

Ml DBTBRHDtATIOH OP TRACE ELEMENTS П» WATERS SI IHDUCTIVELY COUPLED PLAZHA ATOMIC EHISSIOH SPECTROMETRY WITH THE Г88"109 SORPTION ГКВСОИСЕНТКАТ10Н G.P.Panteleyev, G.I.Teyein, A.A.Formanovsky, F.P.Stershinova, E.M.Sedylch, H.M. Kuz 'Bin, Yu.A. Zolotov Vernad-ilqr Institute of Geochemistry and Analytical Chemistry, USSR Academy of Sciences, Moscow, USSR

The development of express methods of determining metals in natural waters is an important task in monitoring the environment. This is of­ ten achieved by employing a combination of procedures - preooncentra- tion and multielement determination.

A combined sorption-atomio emission with IOP method of determination Cd, Co(S), Cu(gJ), FetEI), Ып(И), Hi, Pb, Zn and Y in sea and river water using new sorbents with eonfonnationally flexible aminocarboxy- lic groups has been developed. Preconcentration пае carried out in a dynamic regime. The solution was pumped through a sorbent-contai.ning microcolumn with a volume of 0.16 ml. Pull recovery of metals was achieved over a broad pH range (3-8} with a solution flow rate of 10- 20 sorbent volumes per minute. Then the metals were eluted from the oolumn with the 0.5-5.0 ml of 2 (I hydrochloric acid. By means of 0.5 ti ННдОН the sorption properties were completely regenerated. The pos­ sibility of recovering ion as well as complex forms of metals from na­ tural waters has been shown.

The Jarrel Ash ICAP 9000 simultaneous plasma emission spectrometer with grating 1510 lines/mm was used to analyse the samples after pre­ concentration. The following conditions were suggested for determina­ tion of metalsi forward power - 1.1 let, sample gas flow, plasma gas flow, plasma coolant - 0.4, 0.6, 15.1 1/rain respectively, sample up­ take rate - 2 ml/min, plasma observation height - 13 mm. The detected limits of Cd, Co(Q), Ou(Q), РеСЩ), Un(J|), Hi, Pb, Zn and X for the method developed are (ppb)t 3.0, 0.3, 0.3, 3.0, 0.2, 0.1, 0.5, 1.0, 1.0, relative standard deviation at a concentra­ tion 5-times detection limit: 0.04, 0.02, 0.02, 0.09, 0.01, 0.02, 0.03. 0.02, 0.01.

HI DETBRMIBAWON 0? SULPHUR, PHOSPHORUS, SKLBHIUM AND ARSEHIC tEB-110| BY 3PBCTKUM LIBBS 07 MULTIPLE-CHARGE I0H3 ПС VACUUM ULTRAVIOLET V.li.Ferevertun, R.H.fathudinov Institute of Geologioal Sciences, KasSSR Academy of Solences, Alma-Ata, USSR A method has been suggested of quantitative speotrograpbio analy­ sis of powdered speoiaens (minerals,oree) for deteotion of sulphur, phosphorus, eelenlun and araenio by the spectrum lines of the mul­ tiple-charge lona Is the vaouum ultraviolet spectral reglon,wlth a unipolar low-voltage pulsed discharge in vaouum as a source of exoi- tation(current 12 kA, duration IS alts, spectrograph HP3-29, reverie dispersion 4 A/am). The analysis is carried out in two steps /i,2/.Step one - extrac­ tion of powder by the disoharge through a port In the oap of the hol­ low eleotrode,transfer end fastening of the powder onto the end face of the opposite electrode; step two - sample vaporisation and spectrin» exoitation. Ihe hollow electrode is a oarboc rod. Outside disaster of the bore Is 6 sn,lntenial diameter is 3.5mm, depth - 10amtdismetsr of the oap port is l,5oo.IH.ameter of the opposite aluminium eleotrode is 7so. Influence of the opposite eleotrode'a polarity on the intensity of speotral lines of lona of diverse multiplication factors (II-VII) has been studied» It has been found out that switching on the opposite eleotrode with the sample via anode results in speotral lines of ions with ionisatlon potential up to ieOeT,whereas switohing on via oatode results in ion lines of ionlsation energy up to TOeV.Por oaoh mode a relationship has been found out between ionlsation potentials and the disoharge current intensity at whioh lines corresponding to oertain states of ionlsation rsaoh marlanm intensitiea/3/. Influeaee of the powder particle aim on the analytical sensitivity and preoleion has been studied and conditions of sample preparation defined. Analysis is performed on the speotrun lines of ions S VI 93.3, P T 112.8,Se VI 88.6, As 89.2 nm.Analytical sensitivity: sulphur 3'10"3*, phosphorus and selenium 10~3»,srsenio lbs root mean aouare error doss not axoeed 15*. 1. Fsravortun V.H., Pathudinov M.«. // ZB1S, 196*. Vol.40. P.362. 2. PererertunV.il., Pathudinov B.I. // ZHP6, 1984. Vol.41. P.373. 3. PerevertunV.il., Iahohanova K.K. // ZH», 1975. Vol.23. ?.955.

m ANALYSIS OF RARE EARTH ELEMENTS BY ICP-AES METHOD AES-111 USING PHOTOGRAPHIC RECORDING N.Pliesovske, P.Sol tee Department of Chemistry, Faculty of Metallurgy Technical University, Kosice, Czechoslovakia

Connetion of the ICP source KONTRON 1000 (KONTRON SPEKTRALANA- LVTIK, GDR) to PGS-2 Spectrograph (C.Zeiss, Jena, DOR) мае applied for analysis of гэге earth elements (REE). Photographic registra­ tion has enabled, first of all, qualitative evaluation of REE spectra, investigation of spectral interferences for individual REE, and choice of suitable spectral lines.

The precisian of the method developed ranges from 3.5 to 5.5%. The concentration intervals of linear analytical functions are in the following regions: 500-0.5 yug ml"1 for Nd and Sm, 100-0.5

_1 ,ug ml for Gd, 100-0.1 ,ug ml for La, Pr, 500-D.05 ug mi for Tb, Dy, HD, Er, Tm, Yb, and 50-0.1 ,ug ml for Eu.

The expected precision of analysis calculated from the cali­ bration line ranges from 6 to 20*. The limits of detection reached are worse of an order of magnitude for light REE and Tm as compared with those obtained with photoelectric detection. For all other REE, the limits of detection are comparable.

In spite of the fact that the evaluating parameters of the photographic registration method are worse than in case of photo­ electric registration of signal, the former method is justified for analysis of complicated geological matrices containing REE.

IM THE ATOMIC EMISSION AHD ATOMIC ABSORPTION SPECTKU. |.__ ' AES-112 ANALYSIS OF CADMIUM TUNGSTATE I V.G.Potapova, T.V.Drusenko, Z.V.Shtitel'man Institute for Single Crystals, Kharkov, USSR Perfection of the radioactive and X-ray radiation detection tech­ nique is closely connected «ith using of new scintillation materials. Single crystals of cadmium tungstate are promising for such applica­ tion. When the technique of production of these crystals is worked out, it is important to study the influence of foreign impurities on crystal properties and quality for discrimination of dopants to rece­ ive the necessary properties of these crystals. It is found that the physical and scintillation oharaoterlsties of cadmium tungstate sin­ gle orystals become much worse, if even trace amounts of Ha, K, Ca, Fb, Pe impurities etc. are in the crystals. The methods of atomic spectroscopy were used to study the mecha­ nism of impurity entering and distribution in single crystals and also to estimate the quality of the initial material. lbs traoe amounts of Ha, K, Ca and Li, Rb, Cs, Sr, Ba dopants were detected by atomic emission, Mg - atomic absorption flame-photometry. The most effective solvent - condensed orthophoaphoric acid - was used for sample decomposition. The flame-photometric measurements were carried out with the spectrophotometer "Saturn". To minimize the er- rors of determination and shorten the analysis duration time the ther­ mal time characteristics of the sample dissolution, the influence of solvent, matrix components end buffer additives on analytical signals of the detected elements were investigated using flames of different gaseous mixtures. On the basis of the obtained results the conditions of sample decomposition, atomiser operation and registering system were optimised. Determination of Al, Cu, Fe, Un, Hi, Pb, Si, Ti and V was performed simultaneously by the atomic emission method'when the spectra vera excited in the alternating currant are and registration of the emis­ sion was made with a spectrograph DFS-8-1. Conditions were ohosen for fractional impurity distillation in the arc with tungsten carbidisa- tion directly in the electrode orator. Detection limits are as follows №): 2.10"5 Hn, Nil 5.10"5 Al, Cu, tu, Ti, V; (1-2).10"4 Li, Ha, K, Kg, Ca, РЬ; 5ИО"4 Hb, Si, Sr; 1.10"3 Ba; 3-Ю"3 Cs.

155 APPLICATION 07 SCINTILLATION METHOD FOR MULTL-ELEBMT AES-113 SPECTRAL ANALYSIS S.I.Prokopehuk Vinogradov Institute of Geochemistry, Siberian Branch of the USSR Acadeiu/ Academy of Sciences, Irkutsk, USSR The principles of scintillation method of spectral analysis, apparatus, experemental conditions with regard to the precision and accuracy of method for the determination of gold in standard samples,orea,rocks and plant ashes are described infl]. The aim of the present work is to show the use of this method to determine Au, Ag, As, Pt, Pd in dispersed substances. In order to increase the amount of simultaneously analysed elements spectro­ graph STA-1 is suggested to be replaced for the multi-channel spectrometer DPS-36, retaining the principles to recognize and record the analytical signal (number of pulses or their amplitude X The new set-up is employed to determine the concentration of above elements and to estimate the size of gold, silver, platinum and palladium particles within the range from 1 to 30_/ит. The analysis of elements is made by the lines(nm): 267.6-Au; 528.1-Ag; 286.0-Ав; 265.9-Ptj 340.5-Pd. The spectrum regions, free of lines are ueed as the background. The registering number of gold-silver particles provides the qualitative information on the concentration of silver in gold particles. The analytical signal is Integrated at high element concentrations in geological samples analysed. The determination of elements and estimation of particle size are made as a semi-qualitatively analysis. The detection limits (ppm) vary between 0.01-0.05 for Au and Ag; 20-30 for As; 0.1-0.3 for Pt and 0.003-0.01 for Pd. The relative standard deviation is 50.2-0.5. The accuracy and detection limit mainly depend on particle size, the chemical form of an element occurrence in the samples and the me a of sample analysed. The accuracy of the aethod is checked through standard' samples. The scintillation method is advantageous for analyses of geological samples for a quick, simple and economic approach.

Reference 1. Prokopohuk S.I., Ralkbbaum Ya.D., Lontalkh S.V.// Speotrocblm. acta. 1981. Tol.36B. P.1185.

256 DETERMINATION OF Т1ТАМЮМ AND OTHER ELEMENTS W SOLUTIONS FROM DIGESTION OF TITANIUM ORES WITH SULPHURIC ACID BV EhSSSION SPECTROMETRY |AES—H4

Aleksander Przepiera, Haciej Jabtortski, Marek Wiiniewaki APPLIED INORGANIC CHEMISTRY CENTRE

of Polish Academy of Sciences ul. tfalki fftodych 1

72-010 Police. POLAND

The determination of titanium and other elements presented in titanium ores and solutions in sulphate technology is of particular importance for the control of production processes. One of the most common applied analytical methods is based on the reduction of titanium with zinc. The second method is the colorimetric method based on the formation of complex of titanium. But none of these method is precise because of interference from other metallic ions in solution. A more rapid method of determining titanium and other elements is the emission spectroscopy ICP. The advantage of this method is quickness and very high precision. In our investigation we used the Philips ICP type PV 8060 to measure of titanium and other metallic elements concentration in digestion process. Results of this investigation presented in paper show very high usefulness of this method.

17.3ак.413 »7 ICP-ABS DBTBRHIHATIOH OF RARE BARIH ELEMENTS AFTER THi3IR ^ GROUP SEPARATION ВТ CODUTERCURREHT CHROMATOGRAPHIC I—— V.M.Pukhovskaya, M.Grodowski? T.A.Maryutina, B.Ya.Spivakov, H.H.Kuzmin, Yu.A.Zolotov Vamadsky Institute of Geoohemlstry and Analytical Chemistry, USSR Academy of Sciences, Moscow, USSR •Thermo Jarrall Ash Corporation, Franklin, HA, USA

ICP-AES it a vary convenient technique for working out various analytical methods including separation steps because of the possibility to check simultaneously the presence of a number of elements in the solution. This technique was used for the determination of rare earth elements (REE) in rocks after their preseparation from matrix elements by countercurrent chromatography.lt «as shown that quantitative preseparation of REG into a small volume of aquaus solution Has possible in the system: stationary phase (0.5 H di-(2-ethylhexyl)phosphorlc acid in decane) - aqueous mobile phase (3 tt RC1) under the selected conditions. The concentration of matrix elements in the solution under determination did not exceed 0.1 /Mg/ml and there were no interferences at the ICP-AES determination step. The use of an ICAP-61 polyohromator ("Thermo Jarrell Ash Corp.", USA) with special channels set of REE and matrix elements makes it possible to control all the steps of the analytical scheme used and to minimise the final analyt volume. There is an important advantage of simultaneous ICP-AES in comparison with sequental methods. The detection limits for REE determination are 0.001-0.03 /Ис/ml.

MS ICP-AES DMBHMIBAMOH OP HOBLE MBIAbS IH TBCHHOLOGIOAL PRODUCTS BY USE 0? ESPECIALLY PROFILED SPECTROMBTER |>Д-П6 • V.U.Puknovskaya, I.V.Kubrokova, M.Grodoweki, H.M.Kuzmin Vernadsky Institute of Geochemistry and Analytical Chemistry, USSR Academy of Sciences, Hoeoow, USSR •Therno Jarrell Ash Corporation, Pranklin, HA, USA

For correct determination of noble metals

an ATOMIC-EHISSIQN ANALYSIS OF AKSBIE WITH BOHHEACTIVE |AES-117

V.Q.Rezchlkov, H.F.Hovikov, T.K.Gruzdeva, K.K.Rudneveky, S.K.KollBh Research-Production Enterprise "Salut", Gorky, USSR High purity of arsine uaed for GeAs epilayers, aa well as Improvement of synthesis and purification techniques, require high sensitive end relatively short-term multielement analysis and associated sample preparation fully satisfies these require­ ments* Arsine analysis showed some disadvantages of the commonly used sample preparation methods. They are not only considerably labour- and time-consuming due to the necessary purification and purity oontrol of the used reagents, but also they have high control expe­ riment level for some elements and detection limit, respectively. Our method is free from these disadvantages and provides high effective and relatively short-term concentrating of metal impuri­ ties from arsine. This method is based upon preliminary arsine decomposition by electric charge with subsequent As evaporation as an oxide.» Arsine is injected into the chamber previously vacuum-treated up to I0I.3 Ha and decomposed by low-voltage pulse charge at U-300V, Ca40fuP and L»5/lH. Decomposition time is no more than 30s and decomposition degree is not less than 99*. Decomposition process is repeated until the desirable As mass is obtained. As ob­ tained Is mixed with 100mg of high purified carbon powder, contain­ ing 4 weighted % NaOl, and plaoed into the reactor for the subse­ quent evaporation. Shis prooess is carried out in purified air flow at 553K and 32kPa. Evaporation of 5g arsine lasted for .no more than 2,5h. As experiments showed, chosen decomposition and evaporation con­ ditions and reactor configuration eliminate metal losses and conta­ mination with impurities. Control experiment level is determined only by the purity of the used oarbon powder. Our method of concentrating impurities from 5 g arsine allows to obtain deteotion limits of impurities Uh, kg, И», Or, Pe, Hi, 'Ji.Al, Ga, In, Cd, Zn, Ca, Oe, Sn and Si n*(I0~8 - Itf"6) weighted %. References 1. Kusmln H.H. et al.//BLektron.Tecfan. 1974. Vol.6. H 3. P.94-97. 2. Basoblkov V.G. et al.//Ibid.1978. Vol.6, n* 1. P.125-128. TWO STEPS OP CONCENTRATING LOW VOLATILE METAL •118 IMPURITIES IN ATOMIC-EMISSION ANALYSIS OF TRIMETHYIflALLIUM V.Q.Razohlkov, n.P.Hovilcov, T.ll.Gruzdeve Keseerch-Jroduotlon Enterprise "Salut", Gorky, USSR Trimethylgallium of high purity used in semiconductor teoimology due to its high reactivity and low impurity content is suoh a com­ pound that is difficult to analyze* Therefore is metal impurity content analysis the stringent requirements are imposed on sample preparation which usually includes dealiylation and extraction concentrating of impurities» One of the effective methods of concentrating in terms of detec­ tion limits is vacuum distillation, which provides high degree of concentrating of low volatile metal impurities of minimum level of control experiment! However as our observations showed, distilla­ tion up to dry residue results in significant loss of most impuri­ ties. For sample preparation we used Its preliminary vacuum distilla­ tion with subsequent dealkylation of distillation residue and gallium extraction. Distillation conditions under which low vola­ tile Impurities concentrate for more than 80% in distillation resi­ due were chosen. These impurities are to, Hg, Pb, Cr, Ni, Bi, Ti, Al, Ga, In, Od, Cu, Zn. Distillation of trimethylgalllum (10 - I5g) was osxried out in special concentrator with the rate of no more that 0.04 g/m at 3 cm evaporation surfaoe up to distillation residue mass 0.5 -0.7g. This rate was provided by maintaining corresponding temperature of the ampule for a condensate and temperature of the ampule with the sample.. Distillation residue was completely dealxylized by isopro- pyl alcohol and 6H HC1. Gallium was extracted with bytyl aoetate as a complex metal acid. Hydrochloride solution, containing impu­ rities, was evaporated using 100 mg carbon collector with 4 weigh­ ted % Bad. Concentrate obtained was spectrographlcally analyzed at C*J-I with I0A dc arc. Aohieved detection limits of the abovementioned Impurities are n (I0"8 -I0"6> weighted Jt.

261

'*- ТШ ППЕНИНАТТОН OF PLATINUM QBODF ELEMENTS OSIN6 FISE-ASSAYIHG WITH COLLECTION INTO NiS BOTTOMS laBBWMq' Ivan Bubeska and Tomas Paukert Geological Survey Prague, Malostranaks a. 19, 11621 Prague 1, 0SJ8 For the determinataion of platinum (roup «lament» (PGE) in rook* at normal abundance levele, eom* separation and enrlobment prooedur* ia neoeeeary. One of the most broadly uaed proceaaea la firs-assaying and PGB extraction into a NiS button. The advantage ia that all the FOB and Au are collected. .The fS -.w mixture uaed contains soda, borax glass, aulphur and metallio nickel powder, nickel oxide or niokel oarbonata. To eamplea low in allies quart* baa to be added to accomodate bug and other heavy metala into the allioata •la*'. The aemple and flux are intimately mixed end fuaad at 1000 - 1200oC for about 1 hour. The NiS formed extract* noble matale from the melt and aettlea at the bottom of the eruoible. After oooling, the orucible i* broken and the button i* aeparated meohanloally from the •la*. After oruehing and pulverising, the HiS ia dlaaolvad in cono. BC1 and the undiaaolved noble metal •ulphide* are filtered off. Diaaolution of HiS ehould be aa com­ plete a* possible, ainoe praaenee of Hi in the final solution measured, cause* aerious interference» in ICP-MS, ICP-AES and QFAAS. The diaaolution should nevertheless be fast, otherwise loaaes of PGI and Au occur due to partial oxidation of their sul- phidea and dissolution in HC1. The filter paper with the undissolved residua may be then sub­ ject to MAA or the РОЕ sulphides may be dissolved in HC1 + H202 and the solution analysed by OFAAS, ICP-AES or ICP-MS. Limits of detection reported in the literature for these procedure» indi­ cate that for the determination of PGB at their normal abundanoy levels, ICP-MS is the method of preference with the sole excep­ tion of Ir. One of the disadvantages of the HiS button procedure i* that Hi salts frequently contain traoae of POI and since the amount of Hi added to the flux is ooamensurable with the cample mass, high blank values result. Purifying the Hi salts by bydrolytio preci­ pitation of Hi hydroxide in presenoe of excess nitrites and reducing the amount of Hi added to the flux, blank value» calcu­ lated on a 28g sample basis ware rsduosd to below 1 ppb levels for Bh and Bu, to about 1 ppb for Au and Pd and to below the limits of detection for Pt and Ir. Experimental conditions for msasurment by ICP-AES and OFAAS are presented and diaouseed. Besults on eamplea spiked either with PUB solutions or with the reference sample SARM 7 have shown that ICP-AES provides ac­ ceptable results for Pt and Pd starting from about 1 ppm levels and for Bu and Bh from about 100 ppb. The msasurmsnt of Au is impeded by a great memory effect. QFAAS enable» the determination at considerably lowar concentrations around 1 ppb for Au, Pd, Bu, Kh and 5 ppb for Pt and Ir. Niokel, which is usually in the range of 100 - 400 ug/ml in the analytical eolutiooa, however, affects atomisation signals of Bu, Pt and Ir and must be taken into ac­ count. BHVXROHHSnCAI. ANALYSIS BIT PLASMA JET ATOMIC ЕИГЗЗЮН i SPBCTROSOCPY |ABS-1gQ B.V.SaTlnova, V.V.Gubanova Vernadeky Institute of Geochemistry and Analytical Chemistry of the USSR Aosdemy of Sciences, Moscow, USSR lb* problem of environment pollution lead* to necessity of analy­ tical oontrol improving. Combined high-seleotlve express methods for the microelement determination, particular^ heavy metals, nave to be used for analysis of inorganic oompoeition of blologloal tieauee, aoila and dusts, praoipitatlona and alr,natural water* and technolo­ gical atooka. The report ie devoted to the reaulta of iaveatigationa oonnected with the poaelbilltiee of plaana jet AES for alanltaneona determination of micro- and macroelement» in various powder objects without previoue ohemloal preparation. The advantagea of plasma jet aouroe are; high plasms temperature (15000-20000°C), wide dynamic range, high stability of plasma, the possibility to vary experiment conditions» Tha main advantage is practically oomplete absence of matrix effect. Thus we triad to apply the plasma jet for multielement analysis of environment objjeots by methodical researches of natural •amplest dry remains of river and sea water, of dust, soil, hetero­ geneous lnoludings from samples of town soils. As a result of this investigation» the multielement technique for ABS determination of micro- and meoroelement» in small environmental samples (1-10 mg) has been developed.

MS C01BXSI OP METHODS USE» TOR BIOLOGIOib OBJECT iHAlTSIS |tMMgJ a.m".3*dykh, e.Hatusevitch, N.P.Starsbinova, I.H.Fetrovskaya, L.H.Bannjkh, L.A.Uchevatklna Veraadsky Institute of Oeoohemlstry and imalytloal Chemistry, USSR Academy of Sciences, Moscow, DSSB

The paper introduces a complex of methods used "for analysis of biological objects (food-stuffs of vegetable origin, such as juice», offloional herbs, "mimmjo", sea-organisms, fish etc») including organic substances decomposition and determination of 56 elements in the interval concentration from n.10 to nff. The conplet* decomposition of samples («eight of 1 g) and oxidation of organic substances was achieved during 20 Htnutes by two-stage treatment with mixture of ВЛ0» and HgOg under UEr-ra&iation. The Influence of some parametere on nlneralisation degree was explored* The determination of elements was produced on the interval of concentration n.10 - nX using multichannel spectrometer ICAP- 9000 (Thermo Jarrel IsluOorpO.

Xnterelement superpoeition as well as acid influence on analy­ tical signal was considered and evaluated.

4 The determination of As,Bi,Od,wi,Fb,Oo,llolSelSal!I!ef91 (10" - 10-6» was carried out using WIS method at the spectrophotometer, Model 30JO HOA-600 (Persia Олег). Relative standard deviation by determining elements by XCP-AIS was 0.01-0.031 ЛШ - 0.03-O.0O9. The rational approach eombinlag microwave deoomposition with 1X8- ICP and ХШ8 permits to get the whole eoope of information on chemical content* of invistigated sample from one probe.

2M DETEEMIHATIOB ОТ MERCURY USD OIHEE HALCOPHYL Г { ABS—122 ELEMBITS in HIGH HIRE, BATURAL AND WASTE VATEBS I ВТ AIDHIC-SFBCXBAL METHODS L.B.Shaballova, E.H.Oil'bert, G.L.Buchbinder, O.V.Rozhina "Hydrotevetmet", Rovosibirek, USSR Comparison of different atomic-spectral methods for determinat­ ion of mercury and other haloophyl elements in high pure, natural and waste waters was conducted. It's possible to determine mercury in the said objects with detection limits I?, 12 and I mkg/1,according­ ly, by the atomic-emission with inductively-coupled plasma (ASS-ICP), the atomic-absorption with electrothermal atomimation (ААБ-ЕТА) me­ thods after preliminary reduction of mercury up to elemental state and it's shift in the gaseous phase. Uodification of the method for the direct determination of Hg, namely a combination of the AES-ICP with preliminary shift of mercury in the gaseous phase and applicat­ ion of palladium modifier of matrix in the AAS-EIA lowers detection limit of mercury up to I mkg/1. However it doesn't enough such sen­ sitivity for determination of mercury in high pure and natural wat­ ers, Si-2-etbyl-hexyldithiophosphoric acid and petroleum sulphides were used for preliminary concentration of mercury. It was shown that mercury is quantitatively extracted in the organic phase even

v :V I: when ratio is org wat " 500. Elements Bi, Cd, Cu, Fb, Ag and Au are extracted together with mercury. Under optimisation of analy­ sis' s conditions of extracts by the AES-ICP and the AAS-BTA detec­ tion limits of mercury are 0.1 and 0.01 mkg/1, accordingly. Detec­ tion limits of halcophyl elements by the AES-ICP lie in the interval up 0.00008 (Cd) to 0.2 (Bi) mkg/1. Shift of mercury in the gaseouu phase after it's reduction up to elemental state in the organic phase lowers detection limit of mercury by the AES-ICP up to 0.001 mkg/1. Correctness of the developed methods for determination of mercury and halcophyl elements is proved by the obtained results of analysis of standard samples by geological service of USA.

M5 COMPLEX OF ATOMIC-SPECTRAL UMHDBS FOR ANALYSIS OF HIGH PURITY AlWIIHirai AND IT'S ALLOYS |™-123| l.B.Shnbanova, E.H.Gil'bert, G. L.Buchbinder, O.V.Hoshzina "nydrotsvetmet", Fovosibirsk, USSR In the last years the requirements to impurity composition of alu­ minium are continuously raised: nomenclature of the checked elements is expanded their permissible contents are lowered. The being methods for analysis do not satisfy the new requirements in full measure, be­ sides these methods are often loweffieient, labour-consuming, or in- accesible for plant laboratories. So development of complex of einple and efficient methods for high purity aluminium analysis, intended for the use of different equipment is the actual problem. Complex of ehemico-atonic-spectrel methods (atomic-emission with inductively-coupled plasma or flame, atomic-absorption with flame and electrothermal atomization),allowing to .define the regulating impuri­ ties is devised. On the basis of investigation of different dissolut­ ion processes of high purity aluminium: in HOI, НПО*, dissolution in HOI under effect of direct and alternating current and in presence of the catalysts (Hg, Pd, Hi) the most express methods for dissolution of high purity aluminium of different murks and its alloys are selec­ ted. Study of possibility direct analysis of high purity aluminium by IOP-iIS method shows, that because of wide-band aluminium radiation in range 190-830 nm definition of Co, Cd, Zn, Se, Те and other ele­ ments with necessary sensitivity can't be determined, it's necessary to separate the stated elements from aluminium. Without preliminary concentration from all regulated Impurities by the ICF-ilS method Si, Si, Ca, Hg, Cu, Fe, Mn are determined the lo­

wer bounds of the determinated contents (Cn) are in range I.10"'* +I.IO"6 percent. 6a, Cd, Co, 8n, Те, Zn, An, Fe, Cu, Pb, Bi, Bi defi­ nition are determined by the atomic-absorption method with flame and electrothermal atomisation or ICP-AIS after group concentration by solvent extraction with three-alkyl-bensilamannium chloride or di-2- ethylhexyl-dithiophospnoric acid, С « I.IO"'-I-IO"' percent. На, К and Id are determined by the flame-emission method directly or after preliminarprelimin y extraction by maeroeyclie extragents. С • 1»Ю"в-5«ГО"'' percent. ABALYSIS OP HIOH PURITY ARSBBTC WITH COTCBHTRATIOH 1ES-124 OP IMPURITIB3 BY DISTHLEJG OFP THE BASB I.R. Shelpekove, A.E. Roasin, T.A. Chsnyaheva, O.I.Shoherbakova Institute of Inorganic Chemistry, Siberian Branch of the USSR Academy of Sciences, HovosiMrsk, USSR The procedures for the analysis of arsenic desoribed in the literature [1,2] do not ensure simultaneous detection of several tens of impurities with detection limits of 10" -10 56 mass which are required at the present tine. We propose a variant in­ volving concentration of impurities by distilling off the base in the form of trioxide end an AES analysis of the concentrate (excitation of spectra In s i.e. arc ). The procedure proposed allows simultaneous oontrol of 34 impurities in high purity arsenic with detection limits of 10 - 10*8 mass * . Detection Unite of impurities in arsenic,%

Impurity °mfn Impurity cmin Impurity Cmin Ag 2.10"" Ca 4M0-B Pt 8 -10"Y Al (2-4)-Ю"7 Hf 2-10"6 Sb 8-Ю-7 Au 1Ю"7 In 1-10"7 So 4-10"7

-7 »•# В 1-10r7 Ir 2-10"5 Sn 2-Ю Ba 2-10"7 La г-ю-6 Та 2-Ю"5 Be 2-W8 Ke­ (2-6)-Ю-7 Те 2-Ю-6 7 Bl 1«10"7 nt! г-ю-8 Ti г-ю" Ca (1-4)-10"6 Mo 4-Ю"7 V 2 "Ю-7 Co 1-10"7 Nb 4-10-6 w 9-Ю-5 Or 2.10"7 Hi 9 MO-7 Zn (1-4>10*7 Ou 2-10-8 Pd 1-10-6 Pe (2-4)-Ю-7 Pb 1 -Ю"7

The random error of the analysis Sr * 0.12 k 0.35. The accu­ racy of the procedure was estimated by comparison with the re­ sults obtained according to [2] . Иге procedure is simple to realize. References 1. MaslovB A.I. , Trofimov N.V. , Romanovs L.V., Novoselovs L.M.// Zevodskaya Laboratoriya, 19B2.rol.4B, И 5. P. 6 . 2. Vlasov V.S., Popovs O.D., grasnlkovs C.V., Yudelevioh I.G. // Ibid. 1973.Vol.39. H 9. P. 1048.

287 METHODS FOR SPECTRAL ARALXSIS OF HIGH PURITY SOLIDS |iS3-125 ntVOLVDIG COSCBHTRATIOH OF IMPURITIES BY DISTILLHTO OFF THB BASB

I.H. Shelpakova, A.E. Rossin, T.I. Koayakov, T.A. Chenysheva Institute of Inorganic Chemistry , Siberian Branch of the USSR Academy of Soienoes, ffovoaiblrsk, USSR Concentration of impurities by distilling off the base has a num­ ber of advantages over the widely accepted extraction,the main of which are : the possibility of using larger samples, a reduction in. the number of analysis stages and reduced consumption of reagents. All this allows a considerable decrease in the detection limits of the Impurities, especially of the common ones. We propose atomic- emission, atomic-absorption spectrometry and spark source maas- spectrometry procedures for the analysis of high-purity cadmium, tellurium, zink, mercury, arsenic, antimony end tin ( the starting materials for the synthesis of AV, A2B6, A"B6 and solid solut­ ions on their basis ) Involving concentration of impurities by distilling off the base and allowing control of 30-50 impurities in the range of concentrations from 10 to 10"° mass %. For ma­ terials with a high vapor pressure vacuum destination is used and for those with a low vapor pressure - distilling off the base in the form of a volatile oompound. The procedures allow to oont- rol3P to 50 impurities in the range of concentrations to^-IO"9 mass 4 with a relstive standard deviation of 0.2-0.4 . Queei-equilibrium models are proposed for a physico-chemical analysis of the behaviour of impurities in distilling off the base which allow explanation end prediction of this behaviour. The specific features of the concentration of impurities without dissolution of the sample raise the question of the int­ roduction of impurities into s solid base-material for a metro- logieal estimation of the method. A procedure has been developed for preparation of samples of low-melting-point metals with pre­ determined impurity oontents of 10"' - 10~8 % in which a number of Impurities ore introduced into a material by electrolysis of a melt of this material[I].

Referenow 1. Shelpakova I.R., Hossln А.В., Kovalevskii S.V. et al. Author's Certificate 1328734 USSR ATONIC EMISSION ANALYSIS Of PRECIOUS HETALS AFTER SAMPLE STRIPPING WITH XENON DIFLUORIDE iBS-126 O.A. Shiryaeva, I.N.Vladinirskaya, N.N.Nikitin. E.G. Chudinov Giredawt I.V.Kurchatov Institute for Nuclear Energy, Moscow, USSR Complete revealation of all ICP-AES advantages shall need propar chaaieal sample preparation with minimal operation steps, but con- currently with eailmua of analysed elements being transferred complete­ ly In the solution. Probleas, related to transferring platinum element» Into solution are of coaaon knowledge, besides their complexes vary, thus Halting the choice of decomposition techniques, In particular due to the dependence of an analytical signal on the fore of element occurence. Unlike other methods induction plasam implies no depends « of analyti­ cal signal on the chemical fora of an element. Towards platinum ae tals tbia has been tea ted through introduction of platinum cis- and transdiamindieblorldea and certain oaaina coapounds (1У) into plasna. the obtained discrepancy did not exceed usual divergence between parallel detorainationa. While rather resistible to nost reactant», platinua aetala need highly raactiva coapounds for their tranatar into solution. Xenon difluorlde, which is distinguished among other fluoro-oxidixers by itsa higher availability and safety, was uaed to disolve aliaes of copper-nickel production, as wall as cakes, platinum metal concentre ratas, alloys and pure aatals with 10 to IB * of precious aatsls in their various foras and different oxydstion degress. Fluorination condition la such: eaaple aaaa of 0.01 - 0.5 g is in closed voluae; 3-6 fold exceaa of XeF_ and of the coaplex forming agent; 30 - 120 Bin. duration; ISO - 200"C teeperature. It was revealed that once bake is treated with water or diluted add, tne platinum elenesta get trans­ ferred completely only in presence of КНР,. In the absence of coaplex forming agent certain elements aay selectively transfer into the solu­ tion. This is ussd in the analysis of high-purity plstinua aatals. ICP-AES techniques wss applied for research of spectrum and otbsr effects related to the identification of platinua aetala and their imparities. Complex techniques was worked out to identify precious aetale in the procssaing products of mineral and secondary raw materi­ als throu n the xenon difluorlda-lnvolved chemical sample prepara­ tion.

2И ATOMIC-EMISSION SPECTROORAPHTC DETERMINATION OF RARE |.„ ' USS-127 EARTH ELEMENTS, YTTRIUM AMD SCANDIUM IB SOLID GEO- ' ' LOOIOAL SAMPLES WITH AM ARC TWO-JET PLASMOTRON V.I. Simonove, A.S. Cherevko, I.G. Yudelevieh, V.F. Ul yanovs, Л.Р. Tagiltsev Institute of Geology and Oeophyalca and Institute of Inorganic Che­ mistry, Siberian Branch of the USSA Academy of Sciences, Novosibirsk Siberian Research Institute of Geology and Geophysics and Minerals, Novosibirsk, USSR Determination of individual REE.yttrium and scandium in geological materials is complicated by the low concentration of these elements end the high level of interferences from the accompanying end matrix elements. In routine analyses it is useful to perform direct determin­ ation of REE using an arc two-jet plaematron featuring a high stabili­ ty of the plasma jet, a power sufficient to evaporate solid samples, low detection limits and small matrix interferences. A statistical treatment of the data from direct atomic-ют!ав1оп de­ termination of yttrium and scandium in geologioal standard samples showed the detection limits to be dependent on the composition and properties of the samples. In acidic silicate rocks they are as fol­ lows : 1«10"3Pr, n«W* La, Ce, Nd, Sm,Gd,Er,Tb j n«10"5 Eu,Dy,Ho, Tm, Lu, Sc; n«10 X, Yb %. in basalts, gabbro, dunites, magnetites, calcltes end other the detection limits are considerably higher due to the matrix interferences whioh does not allow "direct" determin­ ation of all REB. In order to determine low concentrations a scheme for a chemical concentration of REE, yttrium end scandium has been developed for use after the decomposition of the samples by acids ( HP, HC10., HOI and by fusing with Na.O,. The REE are separated from the accompanying elements in the form of fluoridea, oxalates, hydroxides. The SEE losses are minimized by co-preeipitating them with fluorides, cal­ cium oxslates, and iron and aluminium hydroxides. For some rocks ( for example carbonates, apatites ) a simpler scheme for concentration using "polyarsenaso" chelate eorbent is proposed. The completeness of the REE separation was controlled by НАЛ of the precipitates of standard samples of the rocks. The accuracy of the method was controlled by mesne of standard samples of the rocks and by conatructing ohondrit«-normalized curves.

ЭТО лише mission ВЕЕВИПНАИОН OP mansions ELKJENT JAES-128 OOMPOSIIIOH IN iLLOTS S.A. Skotnlkov, K.7. Smlrnov CHiiTiasH, BIOSOO», OSSR

The offered method rests on the effect of the inclusion* erosion without baee - metal melting in the initial stage of electrical dis­ charge effect on the conductive probe. Eroeion spots, formed on model specimen 07 high - Toltage «park, powerful low - voltage spark and alternative currant arc, have bean investigated» She light microscopy, scanning electron microscopy and X-ray microanalysis investigation me­ thods have been used. The following common regularities have been as­ certained while testing 42 model specimen types with different po­ sition of inclusions and particles. Independing to their materials' physical properties the projection in the areas influenced by the dis­ charge are exposed to the erosion. Inclusions with work function less than work function of the base metal are exposed to intensive erosion at whole surface. The inclusions with work function greater, than work function of the base metal aren't destroyed at all, or, if inclusions material is insulator, the inclusions boundaries erosion takes place.

Lines of elements cosing into composition of inclusions have been discovered on spectrograms obtained at erosion investigation. Lines of base metal elements have been suppressed. Therefore selected receipt of the inclusions substance in discharge plasma takes place. The estab­ lished effect permits to use exposition of 0,5 - 2 sec without preburn for determination of inclusions element composition in probe and to work out corresponding method. If the element presents only in one inclusion type, for example, In oxides, the method allows Quantitative determination of non - metallic inclusions composition. In this case the darkness density of analytical line of element, presenting in oxide is fonnd in the proportion to the logarithm of this oxide content in inclusions. The method has been used for element composition determination of rase earths containing inclusions in casts, nitrides and oxides In steels.

271 ATOItIC ailSSIOH Fb DETEHMIHATIOH HI TBB &ES—129 SUPEBCOHDUCIING Bi-Fb-Sr-Ca-Cu-0 EXSTBI L—-—— A.N.Souleva, Z.Ch.Hikolova, K.K.Konstantinov, " S.K.Atanasov Higher Institute of Chemical Technology, 1756 Sofia, Bulgaria * Higher Institute of Mining and Geology, 1756 Sofia, Bulgaria It was established that the addition of Fb favours the formation

of 110 E superconducting phase Bi2Sr2Ca20u,OIO+ (2223) АЛ However an unified approach concerning the effect of Fb on the 2223 phase formation and ite concentration in the syntbesised materials does not exist /2, 3, 4/. It is logical to expect that when the synthesis is carried out at temperatures above 820°C, the content of Fb dec­ reases, depending on its duration. Since the Fb content is less than concentration of the other components a direct atomic emission ana­ lysis with arc spectra excitation is possible for quantitative Fb determination. A direct current arc method for Fb determination in the supercon­ ducting Bi-Fb-Sr-Ca-Cu-0 bulk samples with initial concentration of Fb 6.93 mass.jt was developed. An universal pulse generator OBI - I and a spectrograph FSB - 2 (Carl Zeiss, Jena) were used. By dilution with carbon powder, addition of NaCl and selection of suitable ana­ lytical lines a good accuracy was achieved. The results of spectre- graphic Fb determination were compared with those obtained by induc­ tively coupled plasma analysis. On the base of the analytical results a correlation between the Fb concentration and the annealing time was established. fieferences 1. Sunshine S.A. et al. // Fhye. Bev. B. 1988. Vol. 38. P. 893. 2. Bamesh H. et al. // Appl. Fhys. Lett. 1988. Vol. 53. P. 2220. 3. Escudero B. et al. // Appl. Phye.Lett. 1989. Vol. 54. P.1576. 4. Eijima H. et al. // Jpn. J. Appl. Pbys. 1989. Vol. 28. P. L78?. QVARwa iixii.sinmjMii.i:x\Ja 111 sjauo-t-AtavAtu/o 130 uavnu AIUHJ.U—янлаолъл! orwunwvri V.S.Suknev, L.S.StUmeva Institute of Geological Sciences, Yakutsk, USSR Boron determination on ppm level in silicates by various analytical methods still presents a problem [1]. Thus, only 5 of 18 IGJSI geoatandards nave indicated usable values for boron [г]. Boron determinations in silicates by atomic emission is complicated by influence of the rotational structure of SiO band. Some techniques allow for SiO band superposition at

B20. < 100 ppa. The present study uses a method of fractional distillation from an alumo-silicate globule [?]. Such evaporation technique permits time-separation of the appearance of boron end basic components of silicate rocks and makes it possible to exclude mineralogical influence on analytical results. Comparison of the recommended values for geostandarde with our data leads us to conclude that revision of the standards with our data leads us to conclude that revision of the stan­ dards with < 11 ppm boron is needed. The bismuth line Bi I 289.8 nm and palladium line Pd I 9)2.7 nm were used as internal standards. Relative standard deviation varies within 0.12-0.22.

References 1. Oladney E.S., Curtis O.B., Perrin D.H. // Osostandaids news­ letter. 1984У01.8. P.4-3. 2. Standards for chemical composition of natural mineral sub­ stances > Methodical recommendations. Compiled by H.V.Amau- tov. ffovosioirek: IGQ SO AH SSSR, 1987. 204 P. (in Russian). 3. Tannant W.C. // Applied Spectroscopy. 1967.Vol.21. P.28S.

I8.3aK.4I3 273 A "UNIVERSAL TECHNIQUE" BASED OH OLOtf-DISCHARQB | ATOMIC EMISSION SPECTROGHAFHY |aBS-131 0. Stahlberg, V. Hoffmann Aoademy of Soienoes of the German Democratic Republlo, Central Institute of Solid State Physios end Materials Researoh, Dresden, DOS The arum lamp Л/ 1» reported to be a satisfactory exoltation source for quantitative emission speotrosoopy /2,37. He used it to elaborate a "universal technique" for semi-quantltatlve determi­ nations of many elements in various powdered materials within a oonoentratlon range between some hundredths and a few peroent of weight. The samples were nixed and briquetted with an excess of copper powder, supposing that in this case due to minor matrix lnfluenoes on analytical signals, individual calibrations for each material may be avoided. The aoouraoy found is to be charac­ terised by a factor of about 1.31 1. e. absolute deviations of the analytical results from true values are not greater than 30-35 % /4/. This will be illustrated for a let of examples.

References 1. Grimm V. // Speotroohlm. acta 1968. V. 23B. P. 443. 2. Ко J. B.// Speotroohim. acta 1984. V. 39B. P. 1405. 3. El Alfy S., Laq.ua K., Massmann // Z. Anal.Cham. 1973. V. 263. P. 1- 4. Stahlberg, 0., Ehrlich G.// Abstraota XXXVI CSI- Sofla (Bulgaria). 1989. V. III. P. 33.

»4 DETERMINATION OF CARBONATES CONTENT IN COMPLEX 4ES-132 SUPERCONDUCTING OXIDES

V. T. Sur ikov .N.I. Moskalenko, T. P. Lyampasova Institute of Shemlstry, Urals Division of the USSR Academy of Sciences.Sverdlovsk.USSR

Properties of complex superconducting oxides depend on'carbona­ tes content and its value can serve as an index of these qua­ lity. It is possible to determine carbonates content by oculometry

after carbonates separation as C02 from specimens, The alter­

native detector for C0S can be inductive-coupled plasma (ICP), exitating carbon atomic emission spectrum tll-The possibility of such using of ICF for complex superconducting oxides is conside­ red here.The intensity of carbon wave length 247.66 nm was mea­

sured by the spectroanalyser JY-38.The separation of C02 was fulfilled by acid dissolution of powders In gas-passing reactor,

supplied with hermetic loader for specimens.The transfer of C0( into plasma was fulfilled by argon stream 1.5 l/min.The libera­

tion of C0a is characterized by fast development and slow comp­ letion . Fo» more regularity and efficiency of this process simulta­ neity of dissolution all particles of sv»ey specimen.proper soa­ king and mixing powder with acid are neoessary.Diluted powdered

BaCOa ore complex superconducting oxides with well-known carbona­ tes content may be used for calibration.Analytical and metrologi- cal parameters of this method are discussed.

Referenoe

I.VuJicic G.,Vukicevic&,Steiner J.D. et al.//Spectrochim.acta.1988, Vol.43B.P.867.

276 „TONIC EMISSION" SPECTOM. &:ULYSIS OF HETEPOGBIEOUS 4BS-133 KATEIUaLS S.V. Tverdokhlebova, I.H. Spirldonova Dnepropetrovsk State University, Dnepropetrovsk, USSR

The heterogeneous materials ere distinguished by a high degree of segregation due to the lnhomogeneity of the phase composition. The letter is the cause for irregular distribution of alloying elements in a samplet which serves as one of the sources of random errors contri­ buting to the reduction of analysis accuracy of such materials. The"e- fore the sampling of heterogeneous materials has taken an Important place in the development of technique for their analysis. The scheme of sampling on the example of boron-containing alloys, allowing to obtain the representative probe for the spectral analysis, was developed. The guaranty of homogeneity of these alloys is achieved by using a cooling rate at their solidification of not less than 10З K/S followed by heat-treatment in the regime: homogenizing temperature - 1173...1223 K, heating time - 2 hours. Because the variation in the total mass part of analysed elements ranged from 1 - 10J(, the spark discharge was applied. The influence of deviation from the local thermodynamic equilibrium (LIE) in spark dis­ charge plasma upon the accuracy of analysis of boron-containing alloys was studied. It was found [l] that, by using the analytical pairs of lines with like coefficients taking into account the deviation of LTE, the accuracy of their analysis increased by 1.8 times. The application of analytical pairs, consisting of spectral lines of different degrees of lonisatlon, increased by 3 times the analysis error growth which is explained by the difference in directional distribution of the atoms and the ions of analysed elements. The standard samples and technologies of atomic-emission spectral analysis of a number of systems [2,3J of boron-containg alloys, con­ firmed by The Institute of Standard Samples of Central Research Insti­ tute of Ferrous Metallurgy, were developed and attested. The bond equations for the total mass part of analysed elements, taking into account the influence of phase composition and structure of these alloys upon the analysis results, were derived. The results of the study can find application in routine atomic- emission spectral analysis of alloys, notable for their chemical hete­ rogeneity. 1. Tverdokhlebova S.V.// The modern methods of spectral analysis and their application. (USSR). 1983. P.35. 2. Tverdokhlebova S.V., Tsikora I.L., Splrldonova I.M. et al.// Zavod- skaja laboratory. 1975. H 11. Р.1338. 3. Tverdokhlebova S.V., Bondarenko A.M.// Ibid. 1985. N 8- p-33»

I» miiisis о? ROCK atumss BI ЛОИЮ-БШБЗЮН SPECTROMBTRI r~—- ДЖ8— 13* MMHOD Я1ТЯ 1НГОСИОН FLiaU I 1J B.I.Tlkhomirova, H.I.Gulko, E.M.Sedykh,Yu.O.Tatsy, T.V.Shumskaya Y.I.Veraadeky Institute of Geochemistry and Analytical Chemistry, USSR Aoadtmy of Soienoes, losoo», USSR The method of silicate rock samples analysis was carried out using polychromator X0AP-9000, "Thermo Jarrel Ash"). The method In combination «1th atomic-absorption (AAS) and «lame-photometric (FP) methods permits to determine 8-aacro-and-12-aicro-elemente from one sample №?g). Parts of spectrum near the analytical lines «as investigated for 44 elements In solution and for large number of rock samples of different structure» The methods of calculation of spectral Interference «ere selected. Conditions of determination high-concentration microelementsOmg) of rock-forming elements «ere explored. Plane height (11mm) of zone of measurement «as determined «here matrix interference during microelements determination is minimal as «ell as height (15mm) of the greatest stability sons of measurements d'trlng microelements determination. Programme» are proposed for 15-elements determination using ICF-AB8 methods. Microelements determination programme included the calibra­ tion curve construction by using solvents, containing the arti­ ficial matrix of following contensei (mg/ml) - 0,6 -Al,Pe,Mg; 0Л5 - Ca, Ha; 0.1 - K,mh. Uetrologlcal characteristics of methods «ere evaluated using multiple analysis of standard sample of magnesial bazalt (СКВ). The correctness of received data is quite enough for decision of a majority of geological problems. Relative standard deviation are» for macroelements - 0.005- 0.010; for microelements - 0Л1 -0.10. The scheme is proposed for analysis of rock-samples by I0P-AE8, ЛДБ and 7P methods for 20 elements from one probe-weight.

M7 АТСШС-EMISSION METHODS FOR DETEHHIHATIOM OF MICRO HB-135 ELEMENTS IV BIOLOGICAL LIQUIDS WITH PRELIMINARY CHEMICAL CONCEUTRATIOH G.P. Troshkove, 1.0. Yudelevich Institute of Inorganic Chemistry, Siberian Branch of the USSR Academy of Sciences, Novosibirsk, USSR Determination of microelements in blood serum la essential for solving various problems In biotechnology, medicine, veterinary science, toxicology. Analysis of biological samples Is complicated by the presence of organic matrix whose decomposition is usually accomplished by wet ashing in s 14-13 И nitric sold upon heeting. After mineralization, the blood serum represents a solution of a com­ plex salt composition with Na and К contents at the level of n.mmola/1 and a concentration of Fe, showing a rich emission spect­ rum, at the level n«mg/l , Direct atomic-emission determination of microelements in blood serum is impossible without preliminary con­ centration which considerably enhances the possibilities of the di­ rect atomic-emission method. Suoh preliminary concentration can be accomplished either by extracting the microelements from mineralized serum or by removing the maorobase. We have developed different procedures for atomic-emission deter­ mination of microelements in blood serum using various concentration methods. Group concentration of Bi, Co, Cr, In, Vta, Ho, Hi, Ub, Pb, Ti end V on the polysrsensso chelate aorbent provides a practically 10056 separation of the elements ( pH » 6, the time of shaking with the sorbent 2 hr ). The procedure based on the sorption of micro­ elements from в mineralized sample of serum with the polyaraenaso sorbent allows simultaneous determination of 11 elements with detec­ tion limits 0.8 - 5.0 mcg/1 and a relative standard deviation of 0.14 to 0.24. To increase the number of elements being determined e procedure ie proposed with selective removal of the matrix. The solution of dibenzo-18-crown-6 in ft, J^'-diohlorodiethyl ether has been proposed as an extraction system allowing simultaneous separation of Na, К and Pe from solutions of complex salt composition. The extrection is performed from hydrochloric solutions in the presence of C10T . On the basis of a study of the chemistry of the processes occurring in the extractive separation of Na, К and Fa as well as of the behavi­ our of microelements in a selected system a procedure has been de­ veloped for extractive atomic-, emission determination of 22 ele­ ments in blood serum.

278 UETERISIiMIOH OF TUHGSTEK ADD SCAHDIUU USIilG ARC AS3-136) DOUBLIi-STREAM ИАЗИАТВОН X.Urmanbetov, S.Risbekov, A.Ghllimov, Z.Zheenbaev Institute of Physics, KirglzSSR Academy of Sciences, Frunze, USSR the tungsten and scandium axe the rare and duspersed elements.The limit of their quantitative determination at the direct spectral ana­ lysis of the Geological samples is n-10 • The needed, detection li­ mit of these elements in geological roots is 1*10~5 • 1*10"* S and lower. In this paper the direct spectral method of the pointed elements determination is suggested with the use of the ars double-stream plas- matron. She investigations «ere carried out on the effects of plasmatron power (I>50; 70) 90 A) and the work gas flow rate (G • 2.5: 3.5; 4.5 1/min) on the distribution of the line intensities of the investiga­ ted elements along the plasma stream using the geological probes of the known contents of the tungsten (3*10">) and scandium (1«10~* %). Ihe spectra were registered by the spectrograph DPS-13 with resolu­ tion of 2 A/mm,At the simultaneous determination of these elements the most suitable.lines are WI 429*46 nm and Sell 431.41 nm. Ihe line intensities of the tungsten and scandium reacted differently on the variation.of the power and work gas flow rate in the plasmatron. The tungsten line intensity decreases with the increase of the power and plasma-generating gas flow rate, and the scandium line intensity inc» reases to the some value. On the base as a result of these investigations the compromiseop- timal conditions for the quantitative determination of the pointed elements are choosen; they are: I«70 A, G»3.5 1/min at J- «58 . 2he statistic evaluation of the detection limit was made by the "idle" experiment method. At the pointed regimes of the plasmatron operation they arei 6»10"*S6 for tungsten and 5-10 for scandium. If the optimal regime is ehooeen for each element, the detection limit is 3'W*5* and 1M0"6 respectively. To approbate this method the considerable number of the rocks was analysed. Ihe standard samples and the rocks were mixed before the analysis with the buffer mixture in ratio of 1i2. Ihe analysis re­ sult aocuraoy was checked by the analysis of the standard samples of 30-1A and SGD-1A contents. The relative mean square-root deviation Sr for tue mentioned elements is 0.05 and 0.06 respectively.

tn OPTIMUM EXCITATION OF HIGH-PURITY ALUMINIUM -1371 L. vecaernyea

Research Institute for Telecommunication», Budapest, Hungary AES-methods are widely used to enalyaa high-purity aluminium ICP-AES-Spectrometry ia an up to date quick and reliable tech­ nique and well useable in aluminium and electronic industry. However, in case of samples with unuaual or unknown composi­ tion or/and a purity better than 4N the possibilities of this technics are not satisfying. A spectrographs method with optimized arc-type radletion- aource can give more information both In qualitative and quan­ titative analysis than ICP-AES-Spectrometry can. A reel "optimum excitation" -in spectrochemicel analysis- is only realised when an intenalty maximum of the selected ana­ lysis line la produced with a standard deviation minimum of the intensity values measured, We have published how the opti­ mum parameters of an arc-type radiation source can be deter­ mined by means of Excitation Characteristic Curves /ECC/. This method waa used to optimize excitation of selected lines of Cu,Fe,Mn*Si,£n impurities in case of three arc-type sources which were connected to a gretlng-epectrograph. An ICP aourca was connected to a sequential spectrometer and optimized by a regular way. It waa the fourth technique used. Radiation sources used: 1. o.c. arc with solid saaplee 2. D.c. arc with dryed in solution samples 3. DCP source with nebulized solution samples 4. ICP source with nebulized solution samples Limits of detection wera determined. The detection power of the ICP and DCP sources were very similar (aeveral ppa). Optimized d.c. arc sources were more powerfull. By asana of the evaluation of the recorded spectra we could get a view on the total metallc-lapurlty content furthermore, quantita­ tive measurements below ppa range.

280 SPECTRAL-ISOTOPE METHOD OF WATER CONTAMINATION CONTROL j . ЙЕ8-138 BY NITROGEN COMPOUNDS AND DETERMINATION OF NITRATES IN ^— 1 AGRICULTURAL PRODUCTS T.A.VoroshUova, A.I.Konakhina, G.S.Laseeva, V.A.Yakimova Institute of Physics, Leningrad State University, Leningrad, USSR Suggested method of nitrogen conpaunds differential determination in water is based on combination of technique of isotope dilution with spectronetric determination of nitrogen composition in balanced sample. The analysis procedure comprises dozed introduction into the solution nitrogen isotope in the fora of determining compound, separation of isotope-balanced compound from the solution into solid concentrate, transfer of nitrogen from concentrate into gaseous elementary nitrogen, determination of it's isotope composition and calculation of the content of determinated form of nitrogen in basic sample. Introduction of tra­ cer - inner standard - on the initial phase of the analytical procedure provide possibility of selective separation of determined form of nitro­ gen out of solution (owing to allowable losses of isotope-balanced com­ pound) and thus it eliminates influence of accompanying impurities. The method mentioned provide correct determination of ammonium, nit­ rate, nitrite and organic nitrogen in all types of water (due to ab­ sence of matrix effect) with sensitivity approximately one order lower than the limits of admitted concentrations for potable water and with accidental error Sr from 0.03 to 0.13 and are produced at the same in­ stallation - optical analyzer15 N. Task of nitrates content determination in agricultural and food pro­ ducts is solved at dozed introduction of tracer K)6N0, into extragent, used for separation of nitrates from the sample. Metrologieal validity of the method envisages possibility of it's application as certificated at estimation of well-known express methods (ionometric, photometric and others). Thus, the suggested method solves a number of important ecological control problems, connected with intensive use of nitrogen fertilizers and also with water pollution by sewage of industrial enterprises and cattle complexes.

281 ANALYSIS OF CERAMIC POWERS USING VARIOUS ICP-AES METHODS A1S-139

6y. Z*ray*, A. Ferltes*, I. Varga*, T. Kantor>

*Hungalu Engineering and DtvalopMnt Centre Budapest, P.O. Box 128, H-1389, Hungary

•Research Laboratory for Inorganic Chemistry Hungarian Academy of Sciences, Budapest

"Technical University of Budapest, Hungary

Ceramic pomder samples can be analysed by conventional ICP-AES Methods after time-consuming dissolution procedures. Direct solid sample Methods have been developed to simplify the вамр|в preparation step.

It is characteristic to certain solid saMple methods that the evaporation of the original saapls proceeds in the ICP. This principle applies to the direct sample insertion technique

In principally different solid sample methods the vaporization of the original sample is performed in a saparate furnace and the evolved product (vapour/aerosol) is introduced into the ICP source. Favourable conditions for a selective distillation of certain trace elements could be achieved with the use of solid C6] and gaseous [71 halogenatlng reagents. It is expected that the change of grain size ttt distribution is 1MS important with these electrothermal vaporization- dispersion (ETVD) methods than with ths slurry nebulization msthod.

Experimental results applying DSIO( slurry and ETVD sample introduction methods for ths analysis of alumina and silicon nltrids samples will be prevented and discussed.

Bsferenoes

1. Zaray By., Broekaert J.A.C., Leis F.//Spectrochim. Acta 1988. V.43». P.Z41. 2. Relsch H., Nickel H., Mazurkiewicz M.//Spectrochim. Acta 1989 V.4*a. P.307.

3. Ebdon L.t Wilkinson J.R., Jackson K-H.//Anal. Chim. Acta 1981 V.12*. P.4S.

4. Broekaert J.A.C.p Leis F.» Raeymaekers B.p ZAray Gy.t Spectrochiffl. Acta 1988. V.43». P.339. 5. Kin C.Ng.» Zerezghi П., Caruso J.A.//Anal.Cham. 1984. V.Se. P.417. 6. Nickel H., Relsch H., Mazurkiewicz M.//Fres. Anal. Cham. 1989. In press. 7. Park C.J., Hail Q.E.M.//J. Anal. At. Spactrom. 1987. V.2. P.473. THE rUXS ATOXIC-XJUSSIGB ШТВДЦХАПШ QI la, К AMD Ы IB НЮН-ИШ1ТГ Od, 9s, Eg, CdTe, AES-140i HgTe AID CdgH&^Te L.Y. Zelentsova Institute of Inorganic Chemistry, Siberian Breneh of the USSR Academy of Setenoei, lovosiblxak, USSR In flame atomic-emieaion determination of Яа, К and LI In the presence of the matrix elements the various interferences on the analytical eygnal due to the background radiation, the ehemieal interactions of the matrix «1th the impurities under determination, and also the mutual Influenoea of the determined alkali metals are possible. Atonic-absorption spectrophotometer Hltaohi I-вООО «as applied throughout all the experiments. She interferenoes of Те, Od, Be, OdTe, HgTe and CdgBgv^Te 'Hie matrix eoncmtratlon rang» of 0,5 to 25 QS/BL on the emission Intensities of la, К and Li were studied. The spectral hindranoes «все found to be absent for these matrixes. Analytical response due to Is, E and Li not turned out to ehsnge in the preaenoe of Те, Bg, Odle, HgTe end OdjjBRjJIe ocnoantrationa up to 20 mg/nL end that of Cd up to 10 mg/nL, oorrespondently. Cos dependence of the analytical sygnal on the oceoentretion of nitrio and hydrochloric aolds In the rang* of 0.1 N to 4.0 II was Investigated. As the hydrochloric sold eonoentratlon lnoreaaea, the alkali metals radiation Intensities significantly decrease. The mutual influences for Ha, E and.Li oootants of 2-10"* to 2*10 ug/nb mare shown to he absent. She sign! twin of the resonance radiation intensification due to the phenomenon of the depression of ionlsstlon was studied for trace eontanta of Is, E and Li. Radiation intensities may be Increased In 1.8| 1.4 and 1.2 times for la, E end Li, respectively, by means of 0.8 mg/mb of Cs addition (OsOl of analytical grade must he Used). In this osae the blank value was no more than 1«10*** ng/aL. The dissolution of Od, Те, Odle, HgTe and Са-Дц^е must be fulfilled In the mixture of nitrio and hydroohlorio solds in the olosed teflon glasses under room temperature. The lower limits of oonoemtratlon range are equal to V10"' nf/mL| 1.6»1CP' iig/mL and 2*10 ve/Л for la, E and LI, oorreapondently. lor dissolving of 20 ag of the aasple la 1 aL of the solution the limit» of the detection were, respectively, 5'10"S, 8«1CTS and 1'10"S.

2M STUDY OF THE HIGH TEMPERATURE SUPERCOHDUCTIHG FILMS S-141 COMPOSITION BY ATOMIC EMISSION SPECTRAL ANALYSIS

E.S.2olotovltskayat Z.V.Shtltel'man, E.I.Ропота Institute for Single Crystals, Kharkov, USSR In the prooess of developing the preparation methods for HTSO films It 1* necessary to know the local distribution of the auperoonduoting phase, as well as the total mass of the film eubstanoe and its every component. A unified method of atomic emission speetrographlo determination for the main components (excluding oxygen) of Y-5a(Sr)-Cu-0, Bi-Sr-Ca-Cu-O, Tl-Ba-Ca-Cu-0 films «lth various compositions and mas­ ses up to (2-5).10 g is suggested. In the soope of this method the object of spectral analysis Is a collector where the components of a film are concentrated after Its dissolving In acid. A reliable stan­ dardisation has been provided by artificial mixtures with different masses of the elements under Investigation, but preserving their sto­ ichiometric ratio. Spectra exoitatlon has been carried out by means of an a.e. are or two-jet plantation. The obtained spectra has been registered by OTS-B type spectrograph. The lines of alkali earth elements, yttrium, bis­ muth and oopper belonging to 230-310 nm range have been ohosen as ana­ lytical. The dependence of apeotral line intensity relation on the stoichi­ ometric lndloes of the oompound under consideration and mass of samp­ les has been studied for the main components. Thus, the problems re­ lated to the simulation of standard samples when a local analysis is neoessary may be solved. For 20-40jig samples a relative standard deviation of the obtained results does not exoeed 0.04-0.11 for smaller masses this value sligh­ tly increases and Is 0,14-0.18. Study of the compositions of films prepared by different methods allowed to reveal a nonunlformity of elements distribution In vario­ us parts of film and to determine correlational dependences of the composition and eleotrophyslcal properties of the HTSO films.

zw ATOUIC EMISSION SPECTROCHEMICAL ANALYSIS OF HIGH-PURITY ALKXL COKPOUNDS OP II-VI GHOUP ELHIBNIS ' A.D.2orin, V.P.Zanosina, O.A.Yemelyanova, M.L.Markova, I.N.Gaya- zova, I.A.resohenko, I.V.Portnova Chemical Inetitutu, Jf.I.Lobachevsky State University, Gorky, USSR High-purity volatile alkyl derivatives of II-VI group elements in periodic system have found a wide use in various areas of new tech­ nology. High-purity compounds should be obtained on the base of re­ liable analytical data. The most common method for determining metal impurities is speotral analysis. While developing spectral aaalyaia methods sample pre-treatment is essential, involving alkyl compound mineralisation to its inorganic derivative. Selection of mineraliza­ tion method is possible only if both physico-chemical properties of matrix element and impurity origin are considered. Various methods applied to organic compounds of II-VI group elements have been stu­ died: water hydrolysis, mineral acid decomposition, oxidation In li­ quid or vapor phase carried out according to oombuation method.

lo reduce detection limits mineralization products should be sub­ jected to a certain phyaioo-ohemioal action aimed at concentration of mioroimpurities. This is achieved by distillation of the main component ( Se, As, Si ), matrix extraction as oomplex compounds ( Ga, In, Hg, Sb ), base separation by deposition in the form of low soluble compounds ( Pb, Is ) etc. Impurity eoneentrate is ana­ lysed by an atomic emission method in DC are discharge. Studies have been performed to optimize spectral excitation conditions. Procedures have been developed for determining a great number of elements in alkyl derivatives of Zn, Od, Ga, In, Pb, Sb etc with detection limit of 1.10"5 - 1.10"8 «ft.*. s**

ATOMIC LASER SPECTROSCOPY ШСВОаИШПОВВЗ OP IBB НАМ AID DI3PHBBD BXHSRS I ^^ A.'.irtyukfaovioh, Yu.A.Bykov«ky, V.B.Oshurko, A.A.Chietyakov Moscow snglneering Physios Institute L.I.Zeatsova, B.V.Terentyeva, ULLyublmova All-Union Hesserob Institute of Uiunl Resources, •osoow, DS3H SB» determination of element's low contents ia necessary for geoobemical investigations, for solving the ecological problems, fox certification of standard samples witc micro- and ultramicro element's contents etc.?cr tbeee alas the luminescence methods are widely used. Up-to-date laser-luminescence methods help to reduce the detection limits significantly.

the unit with the excitation of the luminescence tunable dye laser in liquid phase based on the frequences mixture and multi­ plication baa bean developed. It has wide tunable range (266-700 as} which allows to analyst the significant number of elements. She analysis may be carried out at room temperature and at T»77K (the lowered temperature helps greately to raise up the selectivi­ ty and sensitivity of measurements).

As an example the results of Sa(IV) in the form of Z,3-diamino- naphtaline (ПАЯ) complex in liquid phase are given. The wavelength of exoltation has been Д «354nm. The lumineaoenoe «red' shift of different concentrations of complex In ootane and n-heptane, the luminescence spectra of the DAB oxidised products with different degrees of purification as well as the influence of these parame­ ters upon the selenium determination have been studied. At room temperature and with the wavelength Д«5б0па the unit showed the sensitivity not less than 1.10"10g/ml.

The possibilities of ion-exchange materials, including thobe obtained by laser ohemietry aimed to increase the unit's sensiti­ vity and element's determination selectivity have been discussed.

Ml ьшттяа DETJSCTION ЫНИЗ BY INTRACAVITX METHOD ALS-г V.S. BuraJtov, A.A. Gvozdev, A.Ya. Kovalev, P.Ia. Mieakov, P.A. Haumenkov, s.U. Raikov Institute of Physios, BSSB Academy of Sciences, Minsk, USSR

Conventional methods of atonic absorption analysis of elements have nearly reached their bounds of possibility. Further substantial increase in the density sensitivity or lowering the detection limits of the atomic absorption analysis is associated with the development of intracavity laser spectroscopy flj. In the present work, we consider the intracavity method sensitivi­ ty versus broadband dye laser generation dynamics, laser mode compo­ sition and spectral dependence of the active medium gain. The influ­ ence of impurity in the atomizer, distilled water and chemicals used in the preparation of samples on the detection limits is estimated (e.g. Ы - 6'10"ajug/ml, Yb - 7- W"4/us/ml). Ceasurements were taken on an automated intracavity spectrometer based on a flash-lamp pumped dye laser [2j. The laser pulse duration was 3jus. The substance was atomized in an electrothermal atomizer. The atomizer furnace length was 28 mm, its internal diameter was 6mm. The recording of the spectrum was made by a high-resolution spectro­ graph and by an electronic recording system based on a CCD linear video signal conditioner. The results obtained show the possibility of applying the intra­ cavity spectrometer for detecting superlow impurity densities. The factors limiting the sensitivity of the intracavity laser spectro­ scopy method are studied and means of their elimination are sug­ gested.

References 1. Lukyanenko S.F., Hakogon U.K., Sinitsa L.If.// Intracavity Laser Spectroscopy. Hovosibirsk; Nauka, 1985. 2. Burakov V.S., Gvozdev A.A., Kovalev A.Ya., Hiaakov P.Ya., Rai- kov S.H. Intracavity laser spectrometer 'Hinak-2'i/Zh. Pri- kladnoi.Spektroskopil. 1989.7ol.51. P. 712.

I9.3an.4i3 OPTOGAbVAlTIC SPBCTROIIEIRY И AIALMICAL RESEARCH Alfl-J R.V.Denisovat K.G.Proobrashenaky Institute for Pure and Applied Mechanics, Siberian Braneb of the USSR Academy of Soienoea, RovoalMrak, USSR

Optogalvsnic (OG) or laasr-enbanoed ionization (1BI) spectro - •etry proved to be one of the most sensitive and efficient methods available for analytical raaaarcb. This technique relies on the enhanced rate of ioniaation of analyte element following photo - excitation with a dye laser tuned to an appropriate transition «avelengths.Tbe rate of ionisation can be then electrically nea - sored, so no optical deteotion system is required, experimental practise «1th flames of atmospheric pressure often sheas detection limits of I - 3 order-of-magnitude superior over other flame baaed spectroscopic methods ZTi37- A detailed theoretical treatment of 06 signals ia very desirab­ le for the development of new analytical applications. We propose hare a generalised physical modal of flame OG effect. This model permits to obtain a much better agreement between the experiment and caloulatlons if oompara with "point ohargeH modal /V. The explanation of the saturation effeot la given and the ori- terlal conditions of it are oleared up depending on the probing •laotrodaa voltage. Soma problems of optimisation related to this technique are discussed in order to further improve the sensitivi­ ty for traoe analysis. Sea the details in preprint /4/.

References 1. Zorov I.B..Kusyakov Yu.Ya..Xovodvorsky 0.A.«Chaplygin V.I.// nassm. Gnesdstrr. 1987. ТоЫЭ. Р.1Э1. (in Russian). 2. Oohkin V.I..Freobraxhenaky П.С. .Sobolev V.B".«Shaparev H.Ya.// Soviet Physios Uspekhi.1986.Tol.14e. P.473. 3. Travis J.CTurk CO.,Be Voe J.R. at al.//Prog.anal. atom. epeotr.l984.Tol.7.P.199. 4. Bulyehev A.I..Denlsova >.V.,Ochkin 7.Я..Preobrashenaky H.Q.// Simulation of optogalvanio phenomena for the flames of atmos- pherio pressure.1989.Preprint I9.1ebedev Physios Institute. USSR.(in Russian). ISOTOPIC MEASUREMENTS USING LASER RESONANCE IONIZATION MASS Г

SPECTROMETRY (RIMS) l_ A*S"

J.D. Fuittt, R.J. Walker, J.С Travie, S. Kayo National Institute of Standard* and Technology Galthersburg. KD, USA 20899

Resonance Ionization Mass spectrometry (RIHS) la distinguished froa other Inorganic analytical ашаа spoctrometric methods by the uaa of tunable lasers for highly efficient, species-selective ionization. The laser ionization technique, resonance ionization spectroscopy (RIS), was the logical climax of several years of studies of multi-photon ionization, originating with fixed frequency lasers [1J and expanded upon with the advent of tunable lasers to include the affect of intermediate resonances [2). The notable accomplishment of single atom detection vae demonstrated by RIS [3] and RIS was subsequently clained to be applicable to nearly «very alaaent in the periodic table [4]. When the resonance ionization source is combined with •ass spaotroaetric dateotlon, isotopic measurement is possible and dual selectivity (oast and clement) la achieved.

We have a RIHS system baaed on a thermal atom source and a tunable dye laser that la pumped by a Nd:YAG laser. Wa have concentrated on 1-color, 2- and 3-photon ionization echemes that are generally applicable across the periodic table (5). We have applied our RIHS instrument to a number of analytical problems where quantification la accomplished using Isotope dilution aass spectrometry (IDMS) [$]. Thia technique reduces the analytical problem to one of accurate isotope ratio measurement. Equilibration of the spike isotope with tho aamplo la required through chemical means as ia some purification of the analyta element from the matrix. RIMS is well-suited to accurate and sensitive isotope ratio measurement since interferences and backgrounds can be vary much reduced. IDMS may be considered the internal atandardizatlon technique that relies on cha best Internal standard, an isotope of the element to be meaaurad. And, since RIHS ia elementally selective, it will be the only Internal standard available. The precision in isotope ratio measurement has boon consistently demonstrated as 1-2%.

The application of RIHS to three analytical problems will be discussed. Wa have made extensive measurements of Os and Re in geologic materials. The analytical problem is to measure the concentration of both Ra and 0s in rocks at the parts-par-

billion level and the isotopic abundance of li70s, which has been produced by the

decay of "'Re (half-life of 4.35 x 10" years) [7]. Since k"0e ia a minor isotope of natural osmium (in general)* accurate isotopic meeauramsnte for this isotope are required at the pica-gram level. The selectivity of the laser resonance ionization

process Is used to distinguish the >0*Re and li70e isobars for both the rhenium and osmium Isotopic ratio neasursnants. The selectivity is also used to correct for hydrocarbon interferences at very low count rates. Hydrocarbons are ubiquitous in the mass spectrometer and are ionised by the laser. Since hydrocarbon ionization la not sharply wavelength dependent, the hydrocarbon interference la easily quantified with the laser tuned off-resonance from the clamant of Interest.

Ml A ••eond problem that: we are pcesentLy investigating Is the determination of impurities In SIMOK, a silicon-based semiconductor material prepared by oxygon implantation. This problem represents a combination of microanalysis and trace analysis. The unique chemical properties of silicon/silicon oxide films ore exploited to separate the top, active layers of the material. No chemical separations are done in the experiment. Acid dissolution of the layer is done in combination with leotoplc splicing. The residue from the acid dissolution is thermally deaorbed in the RIMS instrument. The laser Is used to selectively ionize the element of Interest, which was vanadium in the first experiments. Vanadium isotonic measurement highlights the elemental selectivity of the technique since the minor Isotope of vanadium can be significantly interfered with by Isobars of both titanium and chromium. The chemical blank from the reagents used in dissolution provided the limit in the measurement.

In a third experiment the technique of laser resonance Ionization вшае spectrometry was applied to the determination of iodine in oyster tissue. The long-

lived radioisotope, lI,I, was used to spike the samples. Samples were equilibrated with the Xi9l\ wet ashed under controlled conditions, and the iodine was separated by eopreelpltatlon with silver chloride. The analyte was dried as silver ammonium iodide upon a tantalum filament from which iodine was thermally deeorbed in the RIHS instrument. A single-color, 2-photon resonant plus 1-photon ionization scheme was used to form positive iodine ions. Long-lived iodine signals were achieved from 100 ng of iodine. The precision of lt7l/lt9l measurement was evaluated by replicate determinations of the splice, the spike calibration samples, and the oyster tissue samples and was 1.0%. Heeeurement precision among samples was 1.9k for the spika calibration and 1,4% for the oyster tissue. The concentration of Iodine determined in SRH 1566a, Oyster Tissue, was 4.44 ppm.

1. Horellec J., Normsnd D., Petite G.// Adv. At. Hoi. Fhys. 1942. V.18. P.97. 2. Anbartsumyen R.V,, Kalinin V.N.. Letokhov V.S.// Zh. Eksp. Teor. Fie. Pit's* Red. 1971. V13. P.305. 3. Hurst G.S., Nayfsh H.H., Young J.F.//Appl. Phys. Lett. 1938. V.30. P.229. 4. Hurst 6.S., Payne И.С., Kramer S.D., Young J.P.// Rev. Mod. Phys. 1989. V.51. P.767. 5. Moore L.J., Paeeett J.D., Travis J.C.// Anal. Chan. 1984. V.5G. P.2770. 6. Fassett J.D., Paulsen P.J.// Anal. Chem. 1989. V.60. Р.64ЭА. 7. Walker R.J., Fassett J.».// Anal. Cbem. 1986. V.5B. F.2923.

tn CHARACTERIZATION OP SfllSSIOH SPECTRA UPOM DV LASER ABLATIOH AIS-5

OP TBa2CUjO_ I.YB.Pugol', Yu.l.Rybalko, v.H.Juravlev Institute of Low Temperature Pbyaiofl and Engineering of the UkrS; Aoademy of Sciences, Kharkov, USSR N.Schwentner, D.Kuzaer Institute of Atom and Solid-state Fhysioe Pree University Berlin 1000 W.Berlin

there has been considerable Interest In utilising pulsed lasers for preparation of high-Tc- aupersonducting tain file, во undereteading of the laser ablation —ntianlira веевв to be quite important [1], In these experiments we used ArP exieer laser (193 nm) with time duration of laser pulse 10 ns and repetition frequen­ cy 10 Hi. Average power Input in sample was at 5 J». Compu­ ter speetral set-up gave the wavelength resolution 0.6 an. Jhe ablation rate was at 30 A/impulse. The genexal view of the aalssion plasms spect­ ra la the early ablation sta­ 300 400 SOD vV?1™ ge of XBa^UjO. _ is shown in The emission plasma spectrum in the Pig,(a). The aost intensive early ablation stage (a) and in the lines was identified wits final ablation stage (b) emission transition free iso­ lated ions and neutral atone x"m>, ХШ«Ш, Ваш(Вв1>, аа*"<Вв1«. Only few weak Ou atonio lines was detected. Also there was't any emi­ ssion from oxygen atoms and ions. Is consider the reason is due to Mgh loniiation potential ot О and etroog bonding Cu-0. The prevalent enount of Cu and 0 is oontslaed in laser plasm» as moleoular(cluster} fragaents responsible for contlauin epeetrum. Pig.Co) Shows the view of spectrum la the final stage of sample ablation, the Bain diatin- qulsh is the appearance of intensive atomic Cu lines. The change In spsotrun say bo connected with oxygen deficiency. These results indi­ cate that the laser ablation of X-Sa-Cu-0 needs in additional oxygen oupply and posterior «mealing to have the homogenio stedlosntric ra"20u307-r eoBposition.

Refevenoe 1. Ting Q.X.,Shaw D.T..Kwok H.S.//Appl.Phys.Lett, 1988.Vol.53.P.1762. Ж PHOTOTHEMUL LI3BB SHCIBOSCOPTi ООВШТ STATUS, ИЮВШВ AHD EEBBIBOTIVBS V.I. Sriahko Institute of Xnorganio Obemiatry, Siberian Branch of «he DBSR Academy of Scienoea, lovosiDirak, Ш8В With the relative transaittenoe of a «ample being measuring as a rule ia regiatrating the aaall abaorbanoe, it is always ooaplioated by aaall signal aeasusiag ooapered with the large baoicgrounu. She measurement of sample absorbed energy with aero background signal la the ass* preferable. These methods named throughout celorlaetris are baaed ев the dissipation of absorbed lrradiatlve energy intra the aaaple followed by various pnysloal phenomena. Fhotothermal methods uslag the thermally induced alteration of refractive index have the lota of variant a, e.g. thermal lens, thermal prima, photodefleotion and во on, Theae mathoda have been derelopad only from 80-th yeara. Solid» and gases abaorbanoe down to КГ^ and that of liiiulda down to 10"* may be measured, among pnotothermal methoda thermal lens apeotroaoopy based on thermal lena •ffeot deaoribed by fhlnnery and ao markers la 1964 ti) ia the moat well-developed and thus moat eommonly used. Badial distribution of refraotive index inside the aaaple induead by laser beam bains of Qauaaian in any transverse plane eorreapond» to diatributloo of laser beam Intensity, denerated thermal leaalike optloal aliment bring* about «be alteration of beam divergenoe reglavreted as beam oenter latenalty ohenge. additional pros* lamer beam alaa need. Intenalty at the beam oeater is deteoted by deteotor with limited aperture. Thermal lane signal la proportional to power of laser and aample abaorbanoe. She nonlinear onaraoter of the photothermal methods namely the presenae of the feedbaok of the sample with laser irradiation! ia Its grand advantage la oeapexlaon to routine apeotrophotometry. la this «as* the laser ia utilised net only as the powerful mesne of the introduction of light energy into «ha sample, but also as «he delloateet inatromant to regietrete «he generated ebange of the aaaple under irradlaftlsa mhioh Is proportional «be absorbemt ooneantration as a nils. Thermal effeeta, aenaltlvity, sad lastly repraduoibility depend on tharmal-optleal propartlea of «ha asmple («he molar absorptivity, «ha temperature gradient of «ha refraetive index, «ha thermal oomduotlvity sad so on) by ehanglaa theae duiing «he aaaple «raataant it la poaeible to laprove assstttUUy «bo metrologioal oharaoterieties of proeedure obtained.

2M The evolution of the methods as the analytical nay be devided into three conventional period*. The first period has Ъееп devoted to improvement of the Instrument'" 1 equipment of the methods. As concerns our studies the problems had been raised to receive the reproductible analytical signal Cor lntraoavity, single-laser, and dual-laser systems and to oonstruot the Instrumental seta based on this manner of the measurements. It la notable, that in every formerly mentioned ease laser photothermal method was utilised only to determine the aupexsmall absorbanoas (doan to 7*10""). Routine procedures alone were used. Ibis approach is believed to be perspective for the procedures defined with lnstrumentsl part. The second period was devoted the investigation of the possibilities, end the optimisation of the various modification of the photothermal apeotroecopy with the synchronous elaboration of specialised spectrophotometries! prooedures to yield the ••«<— analytical signal. The numerous examples of first and aeoond periods are observed In С23 • Second period is essentially differs from the first one. It is characterised by the purposeful mutual improvement of the ohemloal past and the Instrumental that based on their mutual requirements, but not the meohanioal combination of already knows procedure with the photothermal measurement. However a laser has bean as before remained the passive detector of the themal-optioal properties of a aample. The third period ham begun In 1987. Ctae day we found that the orgenio solutions of the molybdophosphate and molybdosilioate were photosensitive enough. After thorough study the irradiation of Dutanol and isobutanol extracts of these heteropolyaoide (SPA) by laser light over the wide wavelengths range turned out to lead to blue ВРД formation taking plaos due to the photoindused reduction reaction at ЯРА with the aloohol. Dual-beam photothermal spectrometer with oo-axlal contrary direction of aha two beeaa permits to deteot the indues laser signal and/or probe one. It are the bis-funotionality of the laser beam (which induosd the reduction and probes its produots) and that of who aolvent (whioh is the extrageot and whs redacting agent simultaneously) that makes it simplified the prooedures of the determination of these elements. It will be noted that the approasn proposed la realised only for local nonllneer methods and has the great possibilities.

References 1. Leite E.C.C., Moor* Мц thlnnery ЗЛ.// Appl.Pbye.lett. 196*. Vol„5. F. 141. 2. Qrlshko T.I., Tudelevioh I.e.// Zh.lnal.Xhis. 1969

2M MECHAHIS1IS OP AHALXTICAL SIGMAL FOHMATIOH Df FLAME ( — LASER ATOIUC-IOBIZATIOH SPECTROMETRY 1 AI&^ A.A.Gorbatenko, N.B.Zorov, Yu.Ya.Kuzyakov, V.I.Ohaplygin Department of Chemistry, Uoasow State University.Moscow, USSR

One of the most important problems of modern analytical che­ mistry is determination of traces of chemical elements in dif­ ferent samples. Laser atomic ionization (LAI) technique due to its high sensitivity and selectivity is rather promising for solving this problem. Detection limits in LAX method are set by excitation and ionization schemes of analyte atoms. That's why it is Important to study the mechanisms of atomic ionization in flames for achievement high sensitivity of this technique. The results of dependence of Li, К and Pe LAI signals in a flame on the laser power density are given. Two-step excitation eoheme was used for lithium and one-step schemes - for potassium and iron.

The dependences studied have shown that for all these ele­ ments the contribution of photoionization to LAI signal forma­ tion la significant. The question of advantages of multistep excitation for various ionization sohemes of atoms is dicusaed. Detection limits for lithium, potassium and iron have been cal­ culated according to the 33 criterium and were equal at the level of much less than 1ng/ml in liquid samples.

2M MSI ЕШ1 MOTIVATION AMD SOME RECEHT DEVELOPMENTS ,,„ _ ALa~8 G. Samuel Hurst Atom Sciences, Inc. 114 Ridgeway Center Oak Ridge, Tennessee 37830 USA The early work at Oak Ridge National Laboratory (ORNL) on Resonance Ionization Spectroscopy (RIS) was motivated by the old subject of radioactivity. Thus, it was a strong desire to understand the interactions of alpha-particles with-helium gas which lead to Uie new method. Specifically, the creating of He(2's) metastable states had been postulated as a key step in the energy pathways involved after charged particles interact with helium. Д two-step resonance ionization process was used to ionize all of the Ke(2'S) so that absolute populations were measured to verify a pathways model. Following this success, the detection of single atoms by combining lasers and proportional counters was proven. Other atom-counting experiments involved the detection of single atoms of cesium from the spontaneous fission decay of "'Cf. N. Thonnard, will present the analytical capabilities of Atom Sciences. These include the use of ion sputtering to release atoms from solids, followed with RIS, then a mass spectrometer. Also, the ORNL work on noble gas detection has been greatly advanced at Atom Sciences. This talk will be completed by describing the counting of Kr atoms with isotopic selectivity. For instance, a new type of solar neutrino experiment that would be sensitive to the 'Be source is now possible. To improve estimates of the core temperature, many tons of bromine solution could be exposed to the sun to produce a few hundred atoms of "Kr, which would be a primary indication of the 'Be source. The noble-gas atom counter could also be used to measure double beta-decay rates from selenium-B2 which produces krypton-82. The use of krypton-81 (with a half-life of 200,000 years) to study very old groundwater is in process. The RISTRON concept was perceived as a new method for counting noble gas atoms and was reviewed at the 1988 RIS Symposium (G.s. Hurst, и. BialKowski and O.K. Lowndes, "Progress on the RISTRON," in Proceedings of 4th Intl. Symp. on Resonance Ionization Spectroscopy '88, Inst, of Physics Conf. Scries 21, 229, Gaithersburg, HD, 1988, Adam Hilger). This method involves the implantation and release of atoms in semiconductors by laser annealing. Recent studies were therefore made to study charge release during the annealing process, since excessive charge could perturb the ion optics in the RISTRON. An interesting affect was observed with KrF eximer annealing of si and Ge; namely, ions from Si last for Э microseconds after the laser pulse. This may be due to the formation of Knudson layer because of the high concentration of neutral Si atoms in the plume.

a*7 ANALYTICAL APPLICATION OF LASER-INDUCED FLUORESCENCE ! ALS-9 IN JET-COOLED SA№LES Y.HAAS The Hebrew University of Jerusalem. Jerusalem 91904, Israel

Fluorescence excitation is one of the most sensitive analytical methods for the detection and the quantitative determination of atoms and molecules in the gas phase. Routine analytical procedures using this technique in the case of mixtures consisting of many different molecules are often limited by strong spectral overlap of lines belonging to different molecules.

This limitation may be removed to a large extent by using the method of seeded molecular beams: the mixture to be analyzed is diluted by a suitable carrier gas (usually helium is used} and expended through a small nozzle into high vacuum. The resulting jet is crossed by a laser beam, and the ensuing fluorescence is analyzed by routine methods. The advantage of the method is in the extensive cooling that takes place upon expanding the gas - temperatures close to IK can easily be achieved. Due to this cooling, the absorption and emission spectra become highly structured and simple, and the spectroscopic congestion is greatly reduced compared to room temperature conditions. Th6 use of the method in analyzing mixtures of organic molecules will be described. The main limitation is due to cluster formation, and ways to overcome this difficulty will be presented.

ZM use OF COUPLE: STAJJDARDS FOR LASER MICROANALYSIS .- — ALS-101 OF UIHERALS ' ' S.Sh.Madina, H.I.Hadin Institute of Geological Science», Academy of Scienoes of the Kazakh SSR, Alma-Ata, USSR Ketnod of approximate quantitat1те determination of Ag, Aa, Ba, Be, Cu, Cr, Un, Hi, Pb, II, Zn la minerals using synthetic comparison aampleo (CS) has bean developed. The work was carried out on the laser mioroanalyzer LHA-10 with photographic recording of spectra on the prism spectrograph ЙСП-28. CS «ere prepared by pressing standard powders on the basic of oxide into briquettes at increasing pressure 900, 1800, 3300 Ufa and time lag 3 min. Keen measured value of volume density of CS is 2.38 g/cnr. цо-пичш brightness was the criterion of ehoioe of optimum mode of spectra excitement, taken under condition that laser orater diameter should not be less than its doublet depth [1]. Analytical lines of determined elements were situated In the interval 255.0 - 494.0 nm. Deteotlon limits changed from 3'10~** for Be up to 0.1SC for As (pho­ tographic materials of СП-2, авро-22). Discrepancy of physioal and ohemloal parameters of compared ob­ jects taken into acoount at calculation of real concentration of de­ termined element in the analyzed mineral by introduction of correc­ tion factor, whioh was equal to real mass ratio of CS and mineral substance, evaporated from laser orators [2]:

K,0 V / V >>0 «W tenf^Os os /m a tent t where Ct#nt is the tentative value of concentration of determined element, recieved from calibration chart, constructed by "three stan­ dards" method;pCBt fim are CS and mineral volume densities; Vce, Vm are CS and mineral volumes of laser craters, calculated from measure­ ments of diameters on the surface and depth and summed up over all bursts. Quantitative determinations of all mentioned elements in sulphld and femlo minerals, which have been made by this method, were in good agreement with the results of emission analysis of corresponding mo- nof ractlons. References 1. Batanov V.A., Bunkln P.V., Frokhorov A.M. et al.//Journal of The­ oretical and Experimental Physio» [JSP]. 1972.Vol.63. P.586. 2. Hadlna S.Sh., Kadln M.I., Hetalieva T.D.//Zavodskaya laboratoria (USSR). 19в9.Го1.55. F.40.

2» ELEMENT MMLYSIS BY USER ABLATION OF SOLID SAMPLES A1S-11 K. Nlemax Institut fiir Spektrocheiie und Angewandte Spektroskopie (ISAS), P.O.Box 101352, 4600 Dortmund 1, Federal Republic of Germany The application of pulsed lasers for ablation of solid samples has already a long tradition (see e.g. [1,2]). In particular, the applicability of optical emission spec­ trometry (OES) of laser-produced plasmas was investigated by many groups. We started our experiments with the investigation of the ablation and atomizatlon process of solid samples by pulsed laser radiation using a Nd:VAG laser 0=1.06 urn) of excellent mode profile and power stability. The samples were placed in a vacuum-tight cell which could be filled with buffer gas (argon). In order to excite analytes selectively in the plasma plume produced by the Nd:YAG laser, the beam of a pulsed dye laser was sent into the microplasma with a preselected delay. Radiation from the plasma as well as the laser induced fluorescence (LIF) was detected with a sensitized, gatable optical multichannel analyser adapted to a medium resolution spectrograph. The noble gas in the sample cell has two functions. Firstly, it buffers the sample material and keeps it longer in the observation area. Secondly, the noble gas plasma, into which the sample material is penetrating, serves as an energy reservoir for com­ plete atomization. The optimum pressure of the argon buffer gas was found to be about 140 hPa. Analytical results of excellent reproducibility were obtained in OES as well as in LIF, The dynamic ranges of the calibration curves for elements covered typically three to four orders of magnitude in OES and LIF. respectively. Depending on the element, the matrix, the analyts line and the power of the lasers, absolute detection limits of as low as 2 pg and 5 fg were obtained for some elements in OES and LIF, respecti­ vely, with one laser shot only. Relative detection limits down to 1-10 (ig/g and 45 ng/g were found with ten laser shots in OES and LIF, respectively. First succcessful results on internal standadization in OES and LIF will be shown, where samples of different matrices were measured. Recent publications of our group on the subject of element analysis by laser abla­ tion and laser-produced plasmas can be found In Ref. [3-8].

•Emmets 1. Hoenke-BUnkenburg// Prog.Anal.Atom.Spectrosc. 1986. 9. p. 327. 2. Piepmeier E.H.// in: Analytical Applications of Lasers (Ed. E.H. Piepmeier, John Hi ley « Sons, New York 1986) p. 627. 3. Leis F., Sdorra H., Ко J.B., Niemax 1С.// Mki-ochlm.Acta. 1989. in press. 4. Sdorra W., Quentmeier A.. Niemax K.// Mlkrochim.Acta. 1989. in press. 5. Sdorr* N.. Quentmeier A., Niemax К J/ Z.Phys. D. 1989. 13. p. 95. 6. Ко J.B., Sdorra N.. Nieaax K.// Fresenius Z.Anal .Chen. 19B9. in press. 7. Quentmeier A., Sdorra N.. Niemax K.// Spectrochin.Acta в, submitted. 8. Sdorra U., Nlemax K.// Spectrochlm.Acta B, submitted. MO

Ф А ЬАЗЛЯ PLUORE3CEHG3 METHOD TO IHVS3TI0ATE Пм_ p" EVAPORATION OP HETAL3 IN AH INERT ATKOSPHISHB I _ A.H.Nemeta, G.I.Niekolaev, N.V.Bodrov The Central Research Institute for Structural Materials "Prometheus", Leningrad, USSR A high spectral brilliancy of lasers allows to considerably re­ duce the limits of element detection (as compared to the atomic ab­ sorb t ion method). It makes it possible to investigate the evaporation processes in metals and alloys in the range of comparatively unele- vated temperatures and under the lowest vapour pressure. A unique la­ ser-based unit using dye penetrants has been designed and manufactured to determine low concentrations of metal atoms in a graphite cuvette.

A lazer-fluorecence technique has been developed to determine lead and ohromium. The deflected wave length fluorescence recording permits to remove a non-selective laser radiation effect and to reduce the lead detection limit to 10* at/cm'. Besides, a unique technique has been adopted for chromium wich involves the transformation of the two-level fluoresoence diagram into the three-level one through a collision energy transfer from the laser-filled level to another radiation le­ vel, which resulted in an additional two-order reduction of the detec­ tion level. The chromium detection limit achieved amounts to 10 at/enr.

A temperature dependence of lead and chromium vapour density in the graphite cuvette has been studied (temperature range of 230°C-775°C for lead and 725oC-1300°C for ohromium). The possibility to study the evaporation of nickel, manganese and chromium from steels and alloys is demonstrated.

Ml DOUBLE-PULSE EXCITATION OF LASER SPECTRA AIS-13

V.V. Panteleyev, V.A* Rozantaev, A.D. Shirokanov, A. A. Yankovsky Institute of Physics, BSSR Academy of Sciences, Minsk, USSR

It is common knowledge that when exposing solid targets to laser 10 2 radiation with power density of over 10 W/cm under normal condi­ tions in air» there appears a laser spsrk admitting to the target only a nail portion of this flux» This lowers the efficiency of laser sources in atomic emission spectral analysis.

One of the reserves of improving the conditions of ingress of the substance into the laser plume and its excitation can be double-pulse irradiation of the target. We have developed a setup that allows ob­ taining the double-pulse mode with a frequency of up to 50 Hz, the target being exposed to two pulses of energy of up to 0.05 •? shifted in time relative to each other by 0.1 jxm and over. The duration of either of two pulses was about 15 »•» the power density of the laser radiation, with the use of the lense with a focal distance of 75 am, reached 1010 W/c*2.

Using the Laser setup with two shifted laser pulses, we have ob­ tained spectrograms of plasma of solid metal and nonmetal samples with different time of shift between the pulses. The spectral lines intensities and signal-to-noise ratio have been established to in­ crease in the spectra of the plasma obtained on exposure of the targets to laser pulse radiation, under the conditions when the plas­ ma produced by the preceding pulse interacts with the plasma pro» duced by the subsequent pulse. The optimal time intervals between the pulses are, in our conditions, 10 to 15 Ji**

302 LASER SPECTRAL лильтаз or ШЛШАЬ SAMPLES

V.V.Panteleyev, O.I.Putrenko Institute of Physios, BSSR academy of Seieneea, Minsk, USSR

Local laser irradiation of target* provide» a aoat flexible and productive авале for obtaining data on chemical elementary compo- •ition of rarioua natural adnerala, among then inclusions in geolo­ gic samples, individual grains,etc. This is important, for in­ stance, when determining aineralogic signs of regional ore content as wall as in solving other geologio problems.

We used a laser setup with an active eleaant generating single 0.03-0.05 pulse» with a duration of about 10 na, pulse frequenoy being 25 Bz. The focusing system of the setup allowed power density of the laser radiation at a target surface of about 1010f/ca2,which permitted evaporating and exoiting atoms of transparent minerals. We have not used electric discharge» for additional excitation of the laaer plasma.

The laser setup waa successfully applied for qualitative and quantitative analysis of the geologic samples for a wide variety of elements. Since natural minerals are nonuniform in their struc­ ture and chemloal compositions, the standard samples for quantita­ tive analysis were eoapaot tablets made of powdered natural minerals or of a mixture of powder* of different cheaioal compounds whose composition was identical to that of the minerals.

In particular, using such tablets we have constructed calibration obarts and performed quantitative analysis determining impurity elements In silicate minerals, pyrites (pyrrhotites) and ilmenitea, as wall as sodium, potassium and calcium in alkaline feldspars and plagioeleses. The success of the analysis In the latter case was due to the lower power density of the laaer radiation. Minimal concentrations of impurity elements determined from the spectra of the intrinsic plasma glow depend on the apeolfle element and are within 10"3 par cent - 10 per cent. Relative standard deviation was no greater than 0.15.

Sea SEPARATB EVAPORATION AND SAMPLE ATOKIZATION IH VACUUM 1IB-15

V.A.Prlbytkov, O.I.Katveev NFO»Khln>volokno", Mytiehchy, USSR The influence of sample composition on accuracy of atomic analysis results in vacuum oan be removed by using nonisothermal atomization fl!> The structure of atomizer with two temperature zones heated in va- ouum by electron stream with the help of ring cathodes has been des­ cribed. The atomiser allows to provide the optimum by atomization ef­ ficiency rate of substance evaporation from the low-temperature zone and rather high degree of vapor dissociation in high-temperature zone.

The atomizer is employed in atomic ionization analysis of indium for samples containing Indium trifluoride and indium trichloride. The program of atomizer heating provided acceptable for quantitative ana­ lysis time resolution between signals caused by evaporation of indium trichloride and indium trifluoride.

It is shown that the atomization efficiency, close to 1 ( one ), is provided only by nonisothermal method of atomizer heating. The possi­ bility of theoretical description of time dependences of analytical signal on the basis of known thermodynamic properties of sample sub­ stance [2] and the possibility of using nonlsothermal atomization in vacuum with rezonance-ionization detection of atoms for thermal analy­ sis of sample composition is analysed.

The principles for a choice of optimum atomizer heating method to reach the highest values of atomization efficiency and time resolution between signals, caused by evaporation of various oompounds of the analysed element are discussed.

References

1. Pribytlcov V.A., Matveev 0.1. // Zh. analyt. khimii ( Russ. ). 1988. Vol.43.P.2132. 2. Termodyaaaioheskle svolstva lndividualnyh veshchestv ( Ruse. )/ Pod red. Olushko V.P. M.: Nauka. 1979-Vol.3.Book 2. 395 p.

m SPECTROSCOPIC ELBMEHT AlfALYSIS BY LASBR-IHMJCBD I—

L.T.Sukhov Institute of Physics, Siberian Branch of the USSR Academy of Sciences, Krasnoyarsk, USSR

Advantages of using laser radiation in atomic spectral analysis have become evident with the very advent of laeers. However consi­ derable effort to realize direct spectral analysis has been expen­ ded over the last two decades with no appreciable success. Up to now there is no comprehensive understanding of the factors impos­ ing limitation on sensitivity of the method. This is due to the great variety of physical processes involved in laser light inter­ action with solid target. This paper considers successively processes of sample vaporiza­ tion, plasma formation, heating of plasma, dynamics of plasma ex­ pansion from the target into the gaseouB environment, recombination of laser-induced plasma, condensation of vapor of target sample. Behaviour of these processes is considered depending on both the parameters of laser light (wavelength, pulse duration, power den­ sity) and the specific properties of target substance and the ex­ ternal conditions (composition and density of atmosphere, focusing conditions). Optimum laser light parameters and external conditions are re­ commended providing maximum of the atomic phase portion in the vaporized products and high efficiency of vapor heating by laser light. An attempt is made to find out the major factors limiting sensitivity of direct laser spectral analysis. Spatial-temporal characteristics of discrete and continuous-wave spectra of laser-induced plasmas have been studied experimentally. Physical processes that may be responsible for various radiation components of laeer-indiced plasma are suggested. It is recommen­ ded that recombinlng plasma spectrum should be used for analysis. On the basis of the theoretical and experimental results obtained optimum conditions for direct laser spectral analysis have been formulated» radiation wavelength ^.«0.7-1.0 urn, laser pulse dura­ tion t »(l-3) 10~ss, power density on the target q*>10" W/cm , diameter of focusing spot d«0.6-1.0 mm, atmospheric environment pressure P»(1-3) mm mercury. It is shown experimentally that the described above technique allows for most elements to be detected at a single laser pulse with the detection limit tV10-5S and П- 10"1* g.

20.0ак.413 305 THE USE OP THE ATOMIC SPECTROSCOPY ALS-17 IN AGROCHEMICAL SERVICE S.G.Samohvalov, A.v.Puehovsky, I.N.Sibaeva, Y.M.Tjoginov, A.V.Kuznetcov, Y.R.Kolomlsky, N.A.Chebotareva Central Institute of Agrochemlcal Service», Moscow, USSR The primary objective of agrochemlcal service is the control of flrtillty and environmental pollution In agrobiocenoaes. The atonic spectroecopy methodai flame photometry (Ha and K), atomic absorbtton spectroscopy AAS (Ca, Mg, Cu, Zn, Mn, Pe) are widely used to solve these problems. However, the sensitivity of the most widely used flame AAS method Is unsuffleient for direct determination of Pb, Cd, Cr, Hi, Co, Mo and other trace elements In soil and plant analysis. The possibility of application of laser atomlo flurescence spectro­ scopy LAS (experimental device, USSR), atomic emission spectroscopy with Inductively coupled argon plasma ICP (ICAF 9000, Jarrell Ash) and X-ray fluoresoenoe spectrometry (SRM-25, USSR) have been studied. The LAS method with eleotrothermal atomlzatlon used for Fb and Co determination in soil extraots and plant ashes solutions has been developed. It was found that LAS could determine Fb In agrochemlcal samples of complex composition down to 1 ppb. The results of deter­ mination Fb in NBS end National standard reference plant materials are given. The determination of Mg, F, K, Ca, Al, Mn, Pe, Cu, 2n, 171, Cr, В In plant samples by ICP method has been developed. It has been shown that background correction Is necessary for determination of these microelements. It was found that detection limits of the trace ele­ ments In plant are 0.02-0.09 ppm. The results of the National stan- dart Reference plant sample analysis by ICP method are presented. The procedure of X-ray fluorescence method of determination of Щ, ?, S, CI, K, Ca, Mn, Fa, Cu, Zn In plant materials was developed. The results of analysis of NBS Oehard Leaves and National standard refe­ rence materials were given. The possibility of SRM-25 for analysis of trace pollutant elements was discussed.

JO» APPUCATIOH OF BIS TO BOLVIHO MttLYTICkb PROBLEMS I I |AIS-18| N. Thonnard Atom Sciences, Inc., 114 Ridgevay Center Oak Ridge, Tennessee 37830 USA Resonance ionization spectroscopy (RIS), using tunable lasers to stepwise excite neutral atoms of a selected element through one or more energy levels to photoionization, is becoming recognized as an emerging technique with uniquely outstanding sensitivity, selectivity and generality in element analyses. High sensitivity (down to single atoms) arises from saturated ionization in a reasonable volume, selectivity is due to the uniqueness of energy levels for each element, and generality, allowing ionization of all elements in the periodic table except He and Ne, comes from the wide tunability of modern lasers. RIS is being applied in many laboratories world-wide to solving new analytical problems. We discuss here technique and applications development at our facilities.

RIS, combined with mass spectrometry, ie showing promise in allowing measurements that were heretofore not feasible. At Atom Sciences, we have applied RIS to the general areas of direct analysis of solid surfaces down to the parts per trillion level, micro-liter biological or environmental samples containing as little as femtograms of the analyte, and noble gas analyses in which the isotopes of interest are at the part in 10" level [1).

Direct analysis of solids is possible by combining ion sputtering with RIS in a process we have named sputter-initiated RIS (SIRIS). This is a logical extension of secondary ion mass spectrometry (SIMS) in which the few ions produced by the sputtering process are rejected while the preponderant neutral atom cloud produced is probed by RIS lasers for the analyte element. While retaining the deaireable characteristics of SIMS analyses, i.e., monolayer surface analysis, excellent lateral and depth resolution, and versatility, SIRIS provides better quantitation by separating ionization from the sputtering process, better sensitivity and sample utilization due to the high ionization efficiency, and near- uniform sensitivity to all elements. With the proper choice of operating parameters, sample utilization efficiencies greater than 10% can be routinely achieved, while 30 to 50% efficiencies have been achieved occasionally. Data will be presented illustrating the salient features of the SIRIS process over a wide range of applications.

307 Another solids analysis technique utilizes laser atomization combined with RIS (LaRIS). Due to the very high atomization rates possible with LARIS, very fast analyses to detection limits at least three orders of magnitude below SIRIS should be possible. Preliminary data supports this, but quantitation seems to be difficult.

Biomedical and environmental samples are another important application area for RIS. Quantitation to date has been with the isotope dilution technique. Typically, a measured amount of sample (10 to 20 microliters) is combined with a known quantity of isotopic spike. After wet-ashing, the inorganic residue is deposited on a pure substrate, such as gold foil, and introduced for analysis in the SIRIS system. The high sample utilization of SIRIS has allowed sub-parts per billion analyses from few microliter samples, thereby, for example, making trace element analyses of blood from premature infants feasible.

Noble gas analyses (to be discussed by G.S. Hurst) have been possible at the few thousand atom level. As the concentration of analyte atoms is often leas than one atom per cc in a typical mass spectrometer, RIS analyses in a reasonable time have become possible with ал "atom buncher," which atoms are frozen on a few mm' surface and released with a heating laser pulse just before the RIS lasers fire. More details on these applications, and an overview on work from many other laboratories can be found in the proceedings of the last two RIS conferences [2,3 3.

References

1. Thonnard H., Parks J.E., Willis R.D., Moore L.J., Arlinghaus H.P.// Surf. Interf. Sci. 1989 V.14 P. 751. 2. Proceedings of 3rd Intl. Symp. on Resonance Ionization Spectroscopy •86, ed. Hurst G.S., Morgan C.G.//In«t. Phys. Conf. Ser. 1987. V. 84. 3. Proceedings of 4th Intl. synp. on Resonance Ionization Spectroscopy '88, ed. Lucatorto T.B., Parks J.E.//Inst. Phys. Conf. Sar. 1989. V. 94.

3W LASER-INDUCED IONIZATION IN A POWER-MODULATED INDUCTIVELY COUPLED PLASMA Gregory C. Turk. LiJian Yu, Robert L. Matters, Jr., and John C. Travis, National Institute of Standards and Technology, Center for Analytical Chemistry, Galthersburg, MD 20899, USA j ~|

Laser-enhanced ionization

LEI has been detected very high in the tail flame of an extended torch ICP (1). At this location, however, considerable cooling and entralnment of air had taken place. Atom densities were very low, and sensitivity was poor. Laser induced Ionic fluorescence has been utilized as a means of optical detection of laser-induced ionization in the ICP (2). This measurement yielded interesting results regarding the race of Ion-electron recombination in the IOP, but was not sufficiently sensitive or practical for analytical measurements.

We have now taken the approach of performing laser-induced ionization measurements in a power modulated ICP. The rf power to the ICP Is shut off approximately 1 ms before the pulsed dye laser fires. Power is then restored and the cycle repeated with the next laser pulse. During the plasma-off period» 3ie ion-electron density is low enough to allow the detection of laser-induced ionization with water-cooled probe electrodes. Enough free analyte atoms are present to allow sensitive detection. Problems associated with rf interference with the ionization detection circuit are avoided since the rf source Is off. Resonance ionization spectroscopy (RIS) is the dominant mods of laser-induced ionization, since colllsional ionization rates are low at the time of laser-excitation. Voltage-current characteristics in the plasma during the power-off period will be presented as well as detection limits.

REFERBICBS

1. G.C. Turk and R.L. Hatters, Jr.. Anal. Cham.. 57. 1979 (1965).

2. G.C. Turk, 0. Axner, and N. Qmenetto, Specerochlm. Acta &2B, 873 (1987).

309 USEE ETOITED ATOMIC ЯЛОЕЕЭСЕН0В SPECTROUETEY- I ~J_ I ПШНЕНСЕ О? ТНВ IUTBIX OK THE AHALITICAL EBSUKDS |*И-ео|

J. Tllch, f. Sliptltz Academic der Wissenschaften der DDE, Zentralinstitut fur Optilt und Spektroskopie, Berlin, GDB The application of lasers to atomic excitation provides a ratio of excited to nonexcited atoms near unity (saturation). In compari­ son to the temperature of the atomizer the achieved radiation tem­ perature of the excited atoms is ouch higher - nan thermal excita­ tion. This non thermal excitation is the reason for the extreme low limit of detection for elements in aqueous solutions with laser excited atomic fluorescence spectrometry (LSAIS). If the ssmples contain a high amount of matrix atoms in the vapour cloud quenching processes take place and the detection limits drop drastically. № have studied this phenomen for a sample of waste water with a salt content of 350 g/1. Separation of anslvt and matrix atoms by an specially temperaturragiae was not able. When the fluorescence sig­ nal was measured the evaporation of the matrix was visible. Table gives the results for the detection limits. Table 2 gives the combination of spectral lines used.

Limits of Detection (LOD) for wests wster and aqueous solutions Element lOD/og/al aaueoua sol,,. waste water Cf 1.8 Ю6 la 0.04 - Pd 0.04 25 Bh 0.2 100 11 0.0001 1

Table 2. feed combination of spectral lines element Xexoltat./,ul *ob«rr/"» Os 455.536 852.111 In 410.476 451.131 fa 276.309 351.694 Eh 339.685 358.310 Tl 276.787 352.943

3I0 ХНЕ NEW COLLECTOR JOSH FOB THE KICBOSFECIRAL ANALYSIS OF ALS-21 METALS AND ALLOTS USING LASER SAMPLING A.N. Tunanova, N.K. Budnevsky, E.V. Maximova, H.V. Yerykalina, Te.I. Filatov» Research Chaaloal Institute, Gorky Stat* University, Gorky,

Л new form of collector of laser erosion products has been sugges­ ted to increase the locality and to decrease the detection limits of elements in the microspectral analysis with preliminary laser sampl­ ing. She collector is in the form of two graphite semidisks with thick­ ness 50-150fa. On sampling the semidiske are positioned on the sample surface with a specific clearance for a laser beam to pass. For the metals and alloys studied the optimal value of the clearance is 2 - 2.5 times that of a crater diameter formed by the laser. The main portion of the substance ejected concentrates around the crater on the lower disk surface. Separate particles and drops which pass with­ out difficulty through the clearance, while contacting with air, got cold and deposited on the upper side of the semidisks. She new form has advantages in comparison with that described by us earlier 11] in the analysis of inclusions and transition regions bounded in width (less 100(Urn), it allows us to orient easily over the surface on studying narrow-bounded sections of the sample. After sampling the collector with the laser erosion products is introduced into a light source. To improve the detection limits of the microspectral analysis in the excitation stage the influence of superposition of uniform and non-uniform magnetic fields upon a d.c. arc discharge has been studied. It has been established that the superposition of a non-uniform magnetic field upon the are discharge under optimal conditions makes it possible to decrease the microspectral detection limits of a large number of elements (Hi, Or, Fe, Co, Si and others) by a factor of 3-8 those of a destabilized are discharge. This method of the mierospectral analysis with preliminary laser sampling on to the collector in the form of two semidiske was used to study the chemical mierolnhomogeneity with the locality of 15-50/Im and the detection limits within 0.1-0.01 wt.$.

Referenoe

1. Buduevsky H.I., Sumanova A.R., Haxiaova E.V»//Speetroehia. Acta B. 198». Vol.39. P.5.

SI I USING THE ROD-FLAHE SYSTEM IN THE DIRECT ANALYSIS Of ,._ „ SEMICONDUCTOR MATERIALS 8» THE LASER ENHANCED AIS-ZZ IONIZATION METHOD ' ' I.l.Vlasov, v.I.Pavlutskaya, N.v.Chekalin V.l.Vernadsky Institute of Geochemistry and Analytical Chemistry. Moscow, USSR The laser-enhanced ionization in flames is used for the ultratrace element detection in various objects and it assures, compared to the atonic absorption in flames, the detection Halts by 3 to 4 orders lower. The use of flanes as atomizers makes It possible to lower considerably or even ex­ clude the matrix effects, to carry out the direct analysis of complex ob­ jects. But this technique iSdConvenient only for solutions, the detection limit goes no lower than 10 41 and is not free of sow other disadvantages. The analytical spectroscopy also uses at a large extent the nonflame elec­ trothermal atomization which assures lower absolute and relative detection limits compared with the flames. The laser ionization analog of the nonflane atomic absorption system seems prospective, but the possibilities of this approach are not yet realized because of the specific ionization noises conditioned by the hot graphite surface.

The present article proposes and realizes the hybrid "rod-flaae" system combining the advantages of both approaches. This system only vapor­ izes the «licrosample into the flame from a heated graphite surface, where the sample is atomized with the further excitation and ionization of the atoms to be determined. The use of "milder" thermic conditions in a signi­ ficant extent carries away the problems of the nonselective ionization background. The "rod-flame* spectrometer allows to: 1) analyse the micro- quantities of 1-20 «g sample both in liquid and solid state, 2Jseparate the vaporization and atomization processes in time, 3) increase the sample consumption ratio and assure the absolute detection limits at the sub- femtograan level.

The analytical possibilities of the spectrometer were examined on the examples of the detection of indium In CdngTe alloys and of copper in the high purity germanium, floth the solutions and the solid samples di­ rectly were analysed. In the CdHgTe and germanium aqueous solutions the additive nonselective ionization background from matrices determined the detection limits at the 10 » and 10 t respectively. At the direct evapor­ ation of solid samples, besides the signal increase due to higher concen­ tration of the element to be determined in the sample, a significant decre­ ase of the ionization background from the matrix was observed. As a result, at the optimal evaporation conditions, the detection limits were signific­ antly lowered: tor indium in CdHgTe down to 10" i and for copper in german­ ium down to 10 I.

The problem was investigated of the analysis accuracy by comparing the analytical signals of the solutions with the standard additives from the ones of the aqueous standards and solid samples. The possibility is shown of the calibration by aqueous standards. The prospects are being discussed of the method in the analysis of solid and liquid samples of high purity substances.

312 INVESTIGATHJG THE WAYS OP OPTIMIZATION ТтяЗгГ OF TJIii ATOMIC-IONIZATIOM ANALYSIS I L I.I.Vlasov, A.S.KocbetKoir, H.V.Chekalin Vernadaky Institute of Geochemistry and Analytical Chemistry of the USSR Academy of Scienoes, Moscow, U3SH

One of the min objectives of the development of any analytical Method is to achieve the maximum sensitivity and the minium detection limit for the element being determined. These parameters are determined by the ratio between the analytical signal values and the detected noises level. The article «nalyses the main factors influencing these values and the conditions under Khich the maximal signal/noise ratio is realized. In particular: 1) The mechanisms of the formation of the ionization signal at the stage of the electron-ion pairs separation in the external electric field are investigated. The equations describing qualitatively the temporal shape of the ionization current pulses are received. 2) The dependencies of the ionization signal values and shapes on the de­ tection circuit parameters are experimentally investigated. The conditions «Honing the detection of either the current pulse value or the values of the charge generated during the laser pulse are selected. The detecting circuit parameters are determined at which the maximum signal/noise ratio Is obtained. 3) The new method of determining the collislonal ionization rates from the excited levels of the atoms being determined was proposed and real­ ized. The method only requires the knowledge of the ionization signals relative amplitudes at various temporal delays of the second step of ex­ citation relative to the first one; and the method provides with the high precision. 4) The spectra) dependencies of noises from the flame current, the matrix concentration, etc. were investigated. It was shown tnat when working with the aqueous- solutions, the thermal noises of the detection system In­ put resistance are determinant. The experiments carried out make the base for the determination of the conditions allowing to obtain the detection limits of 10"'* g/al and lower.

313 THE SPEOTIUL AHAIiYSIS OH THE BASIS OP THE COHTIWOUS | LASER-ЛНС PLASMA JALS-2» Zh.Zh.Zheenbaev, E.S.Chokoev, S.A.Tootogonov Kirghiz State University, Frunze, USSR The spectral analysis with the use of pulsed lasers radiation finds the wide application in practice» In this work the possibilities of the application of the continuous laser radiation, combined with the elec­ trical arc, are estimated as the Bourse for the emission analysis [1). The erosed torch, formed during the irradiation of a material by the focused radiation of the continuous CO.-laser with the power up to 1 kW, are influence by the plasma of the direct current arc burning between the carbon electrode located horizontally.The standard samples on the basis, imitating the bauxitis, served as the turgets. The low detection limits of Mo, Ge • Zn. were found from the obtained gradua­ ted diagrams. It is seen from the table that the lowest detection li­ mit is observered for the most difficulty-volatilized Ah and, on con­ trary, the highest one is observed for the most light-volatilised Ъг, Shis effect can be explained by the fractional receiving of the inves­ tigated elements in to the discharge. The light-volatilised Zn erodes at the very beginning of the influence of laser radiation on the sample. Therefore it quieklyvolatizes or precipitates on the electrode. .Abie less intensively and more longly received. Apparently, the realized condition is the moat optimum for the diffioulty-volatlle elements. However, in principle, the decrease of the detection limit for other elements can be waited. The presented date show the possibility of ap­ plication of the continuous laser radiation at the analytic purpose of that it was earlier considered to be inexpedient because of the high intensity of brackground of the stationary erosion laser torch. For this it is only nessesary to heat the torch by the additional souroe of energy. Shis permits to atomize the small-dispersed particles pre­ senting in the torch in a large number and being the main Bourse of breckground.

Elements Analytic lines, am Detection limit, % «o 313.259 ' 1.7.10"4 Ко 317.035 2.3.Ю"* (to 303.906 2.4-10"3 Zn 334.502 4.BOO"3 Reference 1. Zheenbuev Zh.Zh., Tootogonov S.A., Chokoev E,S.//Abstracts of XX Congress on the Spectroscopy. Kiev, 1988. Pt 2. P.320.

SI4 ATMOSPHERIC PRESSURE ATOMISERS IS LASER ATOMIC IONIZATION АЬЗ-25 ADVANTAGES AHS DRAWBACKS •J.3.Zorov, S.Yu.Earpove, Yu.Ya.Kuzyakov Department of Chemistry, Moscow State University, Hoscow, иазп

About 10 years has gone since the first publication in the field of laser enhanced atomic ionization technique in flames for trace analysis. Over these years laser atomic ionization spectroscopy has proved its advantages among any others analytical atomic spectros­ copy methods and demonstrated its ability to obtain the detection limits at the level of some parts of picogram in 1 ml of sample. The most publications is USSR and abroad are devoted to application of the atmospheric pressure flames in this technique.

The review of application of various atomizers in laser atomic ionization spectroscopy is given. Specific characteristic proper­ ties of such atomizers are noted. The results of application of va­ rious typee of atomisers such as atmospheric pressure flames, elec­ trothermal atomizers (ETA), combination of ETA and flames or laser vaporization of sample into flames. The processes of analytical signal formation and the role of different faotors Influencing ana­ lytical signal and signal to noise ratio are considered. After the laser action onto solid sample the distribution of vaporized spe­ cies in flames is studied for determination of different analytes. It is shown that the use of such combined atomizers is rather pro­ mising, because it is possible to carry out analysis ot microsamp- les with high accuracy.

318 SPECTRAL ANALYSIS OF OOLOGICAL SAMPLES WTH THEIR I EVAPORATION BY SCANNING «-LASER IRRADIATION I—— E.O.Artamonova, B.R.Kano, S.V.Oshamkov, A.A.Petrov VITR; Institute of PhysicsjLeningrad State University, Leningrad,USSR University of Oriente, Santiago-de-Cuba, Cuba The sajority of aodern sethods of geological objects analysis needs long-term preparation of samples for analysis, including crushing, grat­ ing, dissolving, etc. This makes the analytical procedure significantly longer. Besides, information about distribution of the elenent of inte­ rest is lost. Here we propose a method allowing to conduct direct scanning analysis of geological objects. This is the method of geological samples spectral analysis with their atomizing by scanning irradiation of continuous wave laser. The method's main idea is as follows: under the continuous laser irra­ diation the sample substance is evaporated and is introduced into flame or some inert gas jet, which transfers the substance into the analytical zone. Analysis is performed in accordance with an atomic absorption or atomic-emission scheme. In the former case non-selective absorption is accounted by comparing the analytical (resonance) line and the neighbour­ ing non-resonance line absorption for the element studied at scanning of the chosen spectral region. In the latter case the emission spectrua say be exoited in a flame, arc, spark or IGP. № have realized the exci­ tation in the arc. System of registration and signal processing was crea­ ted on the basis of microcomputer with digital and graphical data output. A method for correction of matrix effect connected with difference in thermophysical sample properties has been developed, wich allowed to de­ crease the analysis error by a factor of 2 - 2.5. The experiments have been performed with the silicate magnetite samples. Si08 content is the samples varied from IS to 60 %. Speed of laser beam sample scanning was 2 mm/s. An error of 2n concentration determination prior to the correc­ tion was 45% and after the correction - I8)i. Similar result was achieved in using correction for Cu determination. Relative detection limits for Cu, -Zn, Ag, Fb, Au, Bi «re comparable with RDL for analysis of powder samples in the arc, but our technique completely excludes any procedure of sample preparation and besides, the total content distribution of element in the sample is determined.

»• LASER ATOMIC PHOTOtONIZATION SPECTROMETER FOR ELEMENTAL ANALYSIS OF HIGH PURITY SUBSTANCES

A. S. Antipenko. UI.Bekov, a A. Meksimov, V.N.Radayev. S.M.Shapln Institute of Chemistry of High Purity Substances, USSR Academy of Sciences. Gorky, USSR

The most pure substances, widely used in semiconductor electronics, are Ge and SI. The impurity content in these semiconductors must be controlled at the level of 10"7- 10"11 Z. Laser atomic photoionlzation spectroscopy is one of the few methods, which are able to solve such analytical problems. Laser atomic photoionlzation spectrometer has been constructed for analysis of high purity solids. Electrothermal atomizer with carbon crucible was used for evaporation of the sample in vacuum. Stepwise excitation of determined atoms was produced by tunable pulsed dye lasers, pumped by exirer laser. Excited to high levels atoms were ionized by pulsed electrical field. This field pushed the ions into the field-free drift tube, served as tlme-of-flight mass-filter with 90Z transmlttlon and relative mass distribution of 16. The produced ions were detected by electron multiplier.

Analytical characteristics of the spectrometer were investigated while working out the nethods of dlreot determination of gallium and aluminium contents in huh purity germanium and of aluminium in high purity silicon. Absolute detection limits of Ga (8*lD"14e) and Al (3*10~i2e) were determined by blank fluctuations, caused by surface contaminations during sample preparation. Maximum probe of 6e was 100 ng and this of Si - 10 ng. «hen the mass of Si sample was more than 10 ng the carbon crucible was destroyed due to interaction with Si. Relative standard deviation of single determination was 0.4 for impurity contents exceeding detection limit by an order of magnitude.

317 THE USE OP FLUORESCEHIIC, ATOMIC-EMISSION AIJD IR-SPECTHOSCOPIC METHODS IH DETERMINATION OP ИШ COMPOSITION OP NATURAL WATERS M.V.Akhmanova, H.S.Saphronova, V.S.Karpov, A.I.Kholodnikh AIS-28 Veraadsky Institute of Geoohemlatry and Analytical Chemistry, USSR Academy of Sciences, Moscow, USSR Chen lidara are used to detect dissolved organic compounds (DOC) In water, there arises the problem of establishing the correspondence of the analytical signal value to the contaminant true concentration. When laser induced fluorescence (LIP) is used as the analytical sig­ nal, the contribution of different classes of natural and anthropoge­ nic organic compounds to the intensity of LIP, as well as tKe quonch- ing of LIP by different inorganic contaminants appears to be very es­ sential. In this work a complex of spectroscopic methods is applied: the IIP method (water's Raman line in comparative signal), UV, visible and IR-spectroscopy, the atomic-emission spectroscopy with (ACS ICP) the aim of the research is to obtain quantitative data on the composi­ tion of natural waters. The experiment was carried out both with model solutions and with real objects (meaning natural waters and sewage). As a result of the work the correlation of the LIP analytical signal was accomplished and the true concentration of natural DOC was established. The values of the contribution to LIP of every component of the object studied were de­ termined. The systematic error of the results obtained by LIP con be reduoed if they are corrected with the help of UV-, IR-spectroscopy and AES ICP. The functional group analysis of contaminants was accom­ plished with the help of UV and IR-spectras of dry residues. AES ICP made it possible to take into account the processes of extinguishing and to obtain quick information on the composition and the content of inorganic macro- and microcontaminants. Тле application of the complex of optical methods suggested allows not only to characterize the sample composition (the summary content of natural DOC with the detection limit of 6.10"° g/l and sr"0.1-0.15; the content of more than 20 inorganic microcomponents with the detec­ tion limit of 1.10-7 _ 1>10-4 вд та 3г-0.02_о.о9) and to identify •. functional organic and anionic Inorganic groups, but also to improve I considerably the correctness of the results obtained by the distance f probing of reservoirs. i

SIS LASER XSOTOIONXZUIOH агжзшяаявх OF a0 TRACES IN I OBOLOOIOAL OBJECTS |АИ-а9 O.I.Bekov, R.S.Belicin, H.H.Konyshev, V.B.Radaev Institute of Spectroscopy, Academy of Sciences of to* USSR, Moaeo* region, Troitsk, DSSR

Co solve modern problem* of prospecting geology of Se one needs to detect lta concentration In orea alth aenaitivity no laaa than О.On Jtf/8 /V« *• ooat sensitive traditional analytical methods axe un­ able to overcome tola limit and therefore thla problem demanda novel analytical approaehee. One of the moat proaiaing analytical method actirely developed of lata la laeer analytical photoionisation spectroscopy {LAPIS), fhia technique la baaed on the thermal atomiaation of a aubatanee in vacuum and aubaaquont reaonanoe atap photoionlsatlon of atoma through Bydbarg or autolonlsing statea. The main advantagea of thla method in oomparl- aon with traditional onee ia lta extremely high aeleotivity and aenal- tivity of atoaa deteotiou, a poaaibility to diraotly analyse the sub- atanoe without eaaential matrix effeeta. Co analyae geological eaaplea LAPIS apectrometar with Eg-laaqr waa uaad Л7« laaer radiation aavalangtha at three atagea of exoitation werei /^«630.57 am, A 2" 506.89 па, Я , • 601.53 am. Che atandard aoid dissolution waa uaed aa the aaaple treatment. Atomisation of the ali- quore part of aolutlon aaa realised in tantalum cruoible to avoid for­ mation of oartidea. The calibration curve obtained with comparlaon of water aolutiona waa found to be linear in the concentration range Ю'-'-Ю"7*. Che de­ teotion limit of So waa 2*10 <• Additional method and usage of atan­ dard aaaplaa ebowed the independence of Se analytical signal of matrix compound. References 1» Korahunov B.O., Resnik А.Ы., Semenov Г.Л. // Scandium. Ы.1.

Metallurgis, 1987,ч1вЗ р. 2. laser Analytical Spaotroaeopy / Ed. by V.S.Letokhov. H.! lauka, 1986^.77-119.

a» DETECTION OF TRACE ELEMENT COHCBNIRATIONS BY USEE I... „ AU3—PU ATOMIC FLUORESCENCE SPECTROMETRY METHOD I 1

M.A.Bolehov, A.V.Zybin, V.O.Koloshiiikov, S.H.Rudnev, I.I.Smirenklna Institute of Spectroscopy) Academy of Sciences of the USSR, Troitzk,Moscow region,USSH

The report presents the results of trace element concentration measurements for a number of metals, obtained during two last years with automated laser atomic fluorescence spectrometer LAPAS-I. Laser part of the spectrometer oases on a dye laser pumped by ZeCl excimer laser. Atomizatlon of samples is realized in the graphite electro­ thermal atomizer operating either in an inert gas atmosphere, or un­ der low pressure. All parts of the spectrometer along with accumula­ tion and processing of analytical information are controlled by com­ puter complex. By means of the spectrometer there has been made a series of analyses without preconcentration of ice and snow samples from Antaroties to deteot lead trace concentrations. She measured ones vary from 40 pg/ml to 0.3 pg/ml.

A serious problem during the analysis of the elements in terms of resonance fluorescence is nonselective scattering of the exciting radiation. While probing Cd traoe concentrations there was studied a variant of the method when a' weak resonance line of Cd with radia­ tive lifetime $t 1 4s was excited. In this case the fluoresoenee signal is registrated only within the duration limit of the gate de­ layed by 50 ns with regard to the exciting laser pulse. In the above indicated scheme of excitation and registration there has been reach­ ed the deteotion limit for Od at 0.1 Kg/ml level. The technique to deteot without preconeentration Pb,?e elements in ultrapure nitric acid was developed. Method variants with atomi- mizatlon process under atmospheric pressure of the inert gas (in ca­ se of lead) and under low pressure (in oase of iron)have been investi­ gated.

ж TIME-RESOLVED USER INDUCED FLUORESCENCE DETECTION |AIS-31 or NITROOW, ITS OXIDES AND НЕОН IH FIRE GASES I 1 A.A.Bol'shakov, H.V.Golovenkov, S.V.Oshemkov Institute of Physics, Leningrad State University, Leningrad, USSR Gas analysis by laser-induced fluorescence method, perspective for de­ termination of trace concentrations is developed to a small extent while successful applications of this method are just connected with evaporati­ on of condensed samples. Poor development is caused by the fact that re­

sonance transitions for gases (excluding HOg, HO, S0a) lie in inaccessib­ le for laser ultraviolet. He consider two possibilities of laser-induced fluorescence analysis of gases: fluorescence excitation from ground state (e.g.for NOg [1]) and that from metastable state (e.g.for He [8]). Time resolution used in both cases leads to increase of signal/noice ratio. Temporal background selection was successfully used [1] in determina­

tion of NOg in He, Ar, Hs and air for decrease of nonselective scattering laser radiation that is an inevitable source of noise. Decreasing fluore­ scence was registrated in -0.1 ms after the laser pulse off, when the si­ gnal/noise ratio was increased by the order of magnitude over its value at the moment of laser pulse cut off. The detection limit was 0.5 ppb. Temporal background selection in connection with spectral selection gives hope that a detection limit of 0.01 ppb may be aohieved.

Using plasmochemical reactions for oxidation, NO and Na may be detec­

ted by registration of N02 fluorescence. Detection limits of NO and N8 in inert gases can be correspondingly estimated as 0.1 and 1 ppb. For analyzing hardly excited gases in common case double-step (plasma* laser) fluorescence excitation proves to be the most efficient. Effective

formation of metastable molecules of N2 was held in pulse discharge fol­

lowed by registration fluorescence (380.5 nm) induced by N2-laser. Alter­ natively, fluorescence (427.8 nm) may be induced by dye laser (391.4 nm) from the ground state of Nj ion. Using temporal plasma background selec­

tion the detection limit of Ha in helium may be reduced lower than lOppb. Shifted He fluorescence (816.4 nm) was recorded in the afterglow [2] for determination of He in He. The population of He metastable state was caused by HeNe* recombination. Temporal selection of plasma recombination emission background allowed to reach the detection limit of 0.3 ppb. For determination of He in Ar the neon fluorescence was registered at the beginning of the discharge pulse. At this moment the electron tempera­ ture was maximum that led to increase of He metastable population. The detection limit of He in argon may be lower than 100 ppm.

Use of time-resolved laser induced fluorescence detection of S0a and HO in pure gases is supposed. 1. Colovenkov N.V. et ml //Zh.Prikl.Spektrosk. 1987Уо1.47. P.7S3. 2. Bol'shakov k.k. et al //Zh.Prikl.Spektrosk. 188ВУо1.4в. Р.896.

2I.3aK.4I3 321 ON THE USE OF LASER RADIATION FOR THE SPECTRAL ANALYSIS | IALB-J2 OP POLYCRYSTAIilBB AND AMORPHOUS AliOYS ' Yu.Buravlyov, N.Cbemyavskagra Donetsk State University, Donetsk, USSR Despite the relatively numerous vrorks on the speotral analysis of different materials with the use of the laser radiation, sons its aspeots are not studied sufficiently perfeotly. We ooneider in the present work the features of the influenoe of the "thirds" elements, of the struoture and of the dimensions of the specimen on the results of the analysis of alloys with ferrous base. The objects of investigation were the simple, stainless, high-speed and refractive steels as well as the alloys of Ре.цЩ.дР^Вп type, in the font of amorphous bands with 30-100 jMa thiokness, up to 1 m width and corresponding specimens in the polyorystalline condition. The investigation was performed with the use of the "LHA-1" laser oioroanalysator with the "PGS-2" speotrograf, laser pulses were in the free generation mode. The generalisation of the obtained data permitted the estimation of the "thirds" elements, specimen dimensions and struoture on the results of the laser analysis. It is established,for instanoe, that the aystematio shifts of the corresponding calibration ourves, de­ pendents from the grade of alloys difference by the composition and structure, nay achieve 10-30 rel.St. It is found that the variations in the gas medium in the zone of action of laser pulses results in the difference in the laser erosion of alloys and in the fractional evaporation of the particular elements. In the performing the laser struoture analysis, one suet take into aooount the influenoe of struoture on the intensity of the ele­ ments spectral lines due to the difference in the laser erosion of the amorphous and polyorystalline alloys as well as the variations of the alloys struoture and composition under the aotion of laser radiation (the data of the X-rays speotral microanalysis). The aasa-epectroaetrio investigation have shown that the defeot oonoentratlon on the contact speolmen surface is higher than on the free one. The influenoe of this factor may oause a corresponding systematic error in the results of analysis. The depth of the orator in the laser pulses aotion on the speci­ mens in the form of a band beoomes oompatlblo with its thiokness. Therefore, It is appropriate to introduse the notion of its "orl;i- oal" thiokness.

1» INIRACAVITY LASER SPECTROSCOPY ANALYSIS OP I mCROIKPURITIES IN THE SURFACE LAYERS I

V.S. Burakov, P.Ya. Misakov, P.A. Naumenkov, S.N. Raikov Institute of Physics, BS5R Academy of Sciences, Minsk, USSR The intracavity laser spectroscopy (ICLS) method «hen used in com­ bination with laser evaporation and atomization significantly extends the scope of practical application of the atomic absorption analysis of materials' surface purity [1,21- On analysing microimpuritles in surface layers this method permits lowering the detection limits (DL) by one or two orders of magnitude as against DL of impurities speci­ fied for high-purity commercial materials, which are currently on the level of 10"6-10"7 per cent [3]. The radiation of a Q-switched ruby laser-atomizer was focused on the surface of targets of Al alloys and Si plates with a maximal light flux power density of up to 1 GW/cm . The laser erosion plume being formed appeared in a nonselective cavity of a nanosecond dye la­ ser-spectrometer generating a smooth broad-band spectrum within the range of 370-1200 nm. The ICLS diagnostics of laser plasma has enabled us to establish the kinetics of the target material ingress into the erosion plume and to construct the dynamic fields of densities of atoms and ions of both the basic material (Al, Si) and impurity (Ca, Iln, K, J?e, Ti, etc.). Axial speeds («1 km/s) and angle of escape («110°) of the absorbing centers have been measured. The decay of the vapor-gas cloud at the afterglow stage is of an exponential character, duration being up to 100 jus. The regularities obtained have permitted us to optimize the laser- atomizer operating condition as well as to select the analytical zone and erosion plume probing time by the ICLS method. As a result, we have elucidated the character of distribution of Al and Ca mioroimpu- —7 —8 ritiea on the surface of SI plates, DL being as low as 10 '-10 per cent.

References

1. Vulfson B.K., Dvorkin V.I., Karyakin A.V., Khomyak A.S.// Zh. Pri- kladnoi 3pektroskopii. 1983.Vol.38. P. 537. 2. Burakov V.S., Hisakov P.Ya., Naumenkov P.A.et al.// Applica­ tion of Spectral Analysis in National Eoonomy and Scientific Re­ search. Minsk, 1984. P. 4. 3. Karpov Yu.A., Allmarln I.P.// Methods of High-Purity Materials Analysis. U. i№uka,1987. P. 23.

323 OIRECT ANALYSIS OF ORGANIC SOLVENTS BV THE USER ENHANCED IONIZATION ALS-54 E.V.Glukhan, v.S.Dorofeyev, I.I.VIasov, A.G.Marunkov, N.V.Chekattn Scientific-Production Trust IREA. Moscow, USSR

The analysis of chemical agents in order to control their purificat­ ion degree at the level of the impurities contents of 10~7I and loner is one of the prospective directions of the use of the laser enhanced ioniz­ ation in flames. The present work shows the possibilities of determination of Li, Na, K, So, Cu in acetone, isopropanol. and phosphoric acid. Two designs of the laser spectrometer were used: 1) with the flame atomizer- ionizer and pneumatic nebulization of a sample into flames for the solut­ ion analysis, and 2) with the rod-flame atomizer-ionizer for the substance microquantities analysis with the sample (1*'50 mg) evaporation into flames from an electrically heated surface.

The high sensitivity two-steps laser excitation schemes of atoms were carried out with the limits of detection (LoO) in the aqueous solutions at the level of M"11»!!)"14 g/nl. The effects were investigated appearing in the flames while intro­ ducing the organic solvents into them. When vaporizing the microsamples from the rods no differences were detected compared to the aqueous solut­ ions. At the pneumatic nebulisation of the pure acetone and isopropanol into flames significant variations of combustion were observed; to restore the initial combustion the ratio fuel/oxydant had to be lowered. There were observed various oehaviors of the analytical signal for every one of tne elements.

The various concentration matrices interferences on the analytical signal were investigated by comparing the signals of the elements being determined in the aqueous solution and in the matrix while introducing the standard additive. The optimal conditions were determined at which the minimal ionization oackground from the matrix is observed, rue LoOs estim­ ations in the specimens were carried out. The lowest LoOs were received for the lithium in an acetone and isopropanol, - 10 i. For the other elements they stay within the range of n'(10 «10 %). The measured con­ tents of the elements in the samples of high purity solvents and acids are by 1»2 orders higher than the LoOs.

3M DIRECT ВЕТНМШАТЮТ OP SILICON IN INDIUM AND Г~ 1 ALS-35 GALLIUM BY METHOD OP LASER ATOMIC FLUORESCENCE I SPECTROMETRY S.A.Deehln, I.A.Hayorov State Scientific-Research and Design Institute of Rare Hetal Industry, Moscow, USSR

A method of laser atomic fluorescence spectrometry «as applied for direct determination of silicon In high purity Indium and gal­ lium. The experimental works were carried out on laser atomic spectro­ meter. The experimental setup and construction of the spectrometer are presented In £\J. As atomizer was used a planar magnetron that permitted Immediate sputtering of solid samples of analysed materials. Such a technique lowers blank experiment correction. Silicon atoms were exited on 251.432 nm and fluorescence was observed on 252.85 nm. Calibration was made using model reference samples of indium and gallium with known amounts of sllloon. Por both cases lower limits of concentration range were about 5 ng/g.

Reference 1. Apatin V.H., Arkhangelsk!! B.V., Belabor H.A. et al. // Spactro- chim. Acta. 1989. Vol. 44B, N 3. P. 253.

S26 USER-EXCITED FLUORESCENCE ANALYSIS OP LEAD IN GEOLOGICAL l, I ALS-36 SAMPLES AT THEIR EVAPORATION BY PULSED LASER IRRADIATION ' ' O.N.Ezhov, B.R.Kano*, S.V.Oshemkov, A.A.Petrov Institute of Physics, Leningrad State University, Leningrad, USSR "University of Oriente, Santiago-de-Cuba, Cuba Laser-excited atonic fluorescence spectrometry in combination with sample laser evaporation allows to perfon direct element determination with relatively low detection limits [1-3]. In the paper possibilities of this method application for analysis of granite geological samples are considered.The experiments were held on the laser-fluorescent spectrometer, including vacuumized chamber, evaporating Q-switched IAG:Nd3+ laser, synchronised with pulsed dye laser and electronic registration system based on ISKRA-1251 computer. In comparison with [3] some modifications are made in the spectrometer. Instead of the multinode laser for evaporation singlemode laser was used. That helped to improve reproducibility of measurements and loca­ lity of analysis. Two strobe-voltmeters were used in the registration system, one of them measured plasma background and the other one-total signal of fluorescence and the background. Further background subtract­ ion was performed by microcomputer which provided decrease of backgro­ und fluctuations influence upon the analytical signal. Pressed tablets made of granite powder with known lead concentration were used as stan­ dards. On the basis of fluorescence signal kinetics and laser plume emi­ ssion background investigations at different conditions optimal parame­ ters of laser analysis procedure were chosen: delay time of the zonding laser pulse relative to the evaporating one, height of the zonding la­ ser beam over the sample, power of evaporating laser irradiation. Calibrative curve, plotted in accordance with granite samples with lead concentration of 10"' - 10"* % mass, appeared to be linear. Rela­ tive detection limit, calculated from the curve with account of back­ ground fluctuation values made 10~e# mass, at area and depth of sample laser action - 10"scms and iOji, correspondingly. References 1. Tilch J, Falk H., Paetzold H.- J.,et al.//Colloq.Spectr.Int.XXIV. Garmich-Partenkirchen,1965. Bookabstr.V2. Dortmund S.A. P.324. 2. Cnernobrodov E.G., Sherozia G.A.//Zh.Anal.Chin.1987.V.42.N1.P.48. 3. Ezhov O.N., Oshemkov S.V., Petrov A.A.//Zh.Pricl.Spectrosc. 1988. V.49, N2. P.309.

3M АРГЫСАИОВ (9 TBI PHOTOCHEMICAL ТНЕВШ, ШВ ГСВ ЯШ |д АНАИ313 ОТ iLOOBOL SOLuTICHS OF THE НВЯВ0РОШС11В I T.P. GziSbkO, T.Z. OrlSbkO Institute of Inorgenlo Chemistry, Siberian Branch of the TBSB Aoadeay at aolenoes, Revoslblrsk, TJBSR nolybdophoaphorlo and aolybdosilleie heteropolyaolda (HFA) «ere found to be easily photeredueed la the butanol, iaobutanol, and pantanol solutions under the irradiation by helium-oadaiua, arson, nitrogen, and exlmer laaara. So monitor the photoroduetien dual-beam tbaraal lana spectrometer with on-arlal contrary dlraetlon of the laaar Ъаааа waa used. Yellow and blue HP* monitoring waa fulfilled due to the altaration of tba tndnoa and probe laaara Intensities, ecrxospondantly. She calibration curves tana piotured In the c ooordlnataa p sl - K^ ( where Krf - the slope of tba graph given 8 (8 s) In those t - log (8,- o" e" • S0, S, and S, are the photodlode signal at the Tttfflnrilne, during the Irradiation, and at the and of the flrat stage of the photoreduotlon. for he11\ra-oads1us Indues laser with poser of 12 m» the effective eonatant of aotion of molybdoslllele aold photoreduetion In iaobutanol turned out to be 1.J tinea that of molybdophosphorlo ana ranging froa 1,29*10"* to 6.47*10 M. In such a ease the calibration curve is linear orer the phosphorus eooeantration range of 1.29*10"' to 1.29*10"^ H. Comparison of the tbeoratioal and experimental data obtained for pboaphoras/ailleen НИ mixture in tern of Initial rate oonflrma the oeenrenoe of the essential autual klnetio effeots In thin mixture oauaed perhaps by the Intaraotlon between the aloohol and HP». Ine error of the experimental 1^ is -29* for the mixture with Cp »CS1 = 6.47-10"* H. In further study this autual offset sill be investigated and controlled thoroughly to increase the accuracy of the resolution of P/8i mixtures. As ooneema the asreury lamp irradiation, the photoreduotlon not turned to occur la pentanol with the optical glasa filters 18-1 or UP3-6. Under complete irradiation the reaction is •lowly proceeding. If previous with argon is absent, blue HP* will be oxidised la Initial yellow form la see» time. The reversible character of these photoreaotions combined with the automonltorlng and monitoring of the Initial and resultant forms based on the refractive Index change alio* to reoelre both the analytical Information end to estimate the values of the main parameters of the prooeesea under inveatlgation and these of the system st all. She analysis of the real samples revealed the great role of the water concentration in the autual klnetle effects.

S27 WO-WAVBbEHGTH TUMBLE Al 0 sMJ bASHl 2 3 ALS-38 A.Glsbrecht, A.Deleva, M.Menchev, T.Fatrikov, Z.Fechev Institute of Electronics, Sofia, Bulgaria

Applications of tunable lasers in tbe analytical spectroscopy are known. Among one of the moat promising are TitAlgO, lasers. The Proposed eohena of the selective cavity L1J makes possible the generation of two independently tunable wavelengths in practically in all visible and near IR spectral region with eontrolable time delay between the two pulses. A combinated cavity with two active media (TltAlgO, orystal and the set of dyes), conneoted by a wavelength selector (Fizeau wedge - PW) Is used. The tuning of a particular wavelength In the range ^ (660-950 nm) is done by translating PW, and in the range Jtj (550- 700 nm) - by aligning the grating. The time delay between the two pulses X^< Xg Is determinated by the nature of the generation of two active media. While the dye laser pulae resembles the pumping pulse (YAGiKd laser), the generation of the T1:A1.0, laser appears with time delay 10-50 ns determinated by pumping intensity. By regulating the pumping power level it Is pos­ sible to obtain coupled pulses with controllable delay and indepen­ dently tunable wavelength. That is of Interest for spectroscopic app­ lications, especially for kinetic fluorescence studies. Increasing the signal/noise ratio, etc.

Reference

1. Nenchev X. // A. C. IT 77133. 1986. Bulg.

SM T30 CHANNEL SPECTROMETER РОВ LASBR IHDUC13D FUJORESCEHCiS I ALS-39 I.B.Gornushkin I 1 Institute of Silicate Chemistry of the USSR Academy of

Sciences, Leiiingredt USSR Laser induced atonic fluorescence (LIT) is considered to be e single elenent technique, nevertheless, one can use a laser (Nd- YAG, excimer) to pump simultaneously two or «ore dye lasers. We elaborated LIF spectrometer with electrothermal atomizer and two dye lasers pumped by Bd-Хаб laser. The registration system has two independent channels. If dye lasers are tuned at appropriate absorption transitions of two different elements we can detect atomic fluorescence (AF) of them both at once using the same sample. The method is mostly effective when we need to detect elements with different physieo-chemicsl properties such as volatility, binding energy. We determined Fb and Co traces in running water and the Heva river water by using the same water aliquotes (20^il). At first it of volatile element (Fb) is induced by one of dye lasers at s low temperature of atomiser cell enough for atomiss- tion of this very element, but not for the other one. Then the temperature is quickly increased to atomise the other element - Co, which is excited by the second dye laser. The simulteneoua detec­ ting of two elements in the same cycle of atomiiatioB ia possible too. Vs carried out the simultaneous determination of two similar elements - alkaline metals Id and as impurities in high purity quarts glasses. The samples were decomposed, the matrix excluded and impurities concentrated beforehand. The mass of the sample was 20 - 70 mg ВД. So, two channel LIP spectrometer provides optimum conditions for high sensitive detecting of two different elements simulte- neously or step-by-etep in the seme atomizetion cycle using the ssme sample. Absolute detection limits in this case are similar to those for single element LIP determination end lie within the range I0"12 - IO"1* g [2].

References

1. Bolshov H.A., Gornushkin I.B., Zylbershtein Oh.I. et al.// Zbum.Jnalit.Chim. 1987. Vol.43. P.312. 2. Qormishkin I.B.//Proc.XIVI CSI. Sofia (Bulgaria), 1989.Vol.1. P.15.

m LABER-FLUORESCENT DETERMINATION OF COBALT TRACES WITH I SAMPLE ATOMIZATION IN THE STROBED HOT HOLLOW CATHODE Ius ~i|0 O.S.Lunyov, D.E.Maximov* S.V.Oshemkov, A.N.Rudnevsky* Institute of Physics,Leningrad State University, Leningrad, "Institute of Chemistry, Gorky State University, Gorky, USSR The paper analyses the possibilities of the use of laser-fluorescent method for determination of superlow cobalt concentrations in dry resi­ dues of aqueous solutions at their atoaization in hot hollow cathode. Experiaental set up includes quartz discharge tube with graphite hollow cathode ( HC ), tunable pulsed dye laser, system of collection and spectral filtration of fluorescence irradiation and strobed electro­ nic circuit of signal registration.

Cathode with dry residue of C0SO4 aqueous solution was placed into discharge tube and discharge in neon at a pressure of 2 KPa was initia­ ted. After prefiring for a minute at 1000'C the atoaization of the samp­ le was carried out at the cathode temperature of 1600°C ( discharge cur­ rent 0,6 A ). Excitation and registration of fluorescence had been per­ formed at wavelengths 304<4 nm and 340.5 nm, consequently. Significant ( app. by 100 times ) decrease of plasma background им provided by cutting off discharge current and excitation of fluorescence in the afterglow. It is shown that plasma quickly ( app. for 1 j» ) relaxes after the discharge extinction and the value of fluorescence is constant for 300 ye, for the atomizer temperature practically doesn't ohange at the used on-off time ratio of out pulses ("ISO ).

The processes or sample burning out at different hollow cathode te­ mperatures, dependence of signal amplitude on the sample quantity, pres­ sure and sort of gas-disoharge oarrier were investigated in the paper. Extrapolation of calibration curve to the triple level of background RMS fluctuation, determined by non-selective scattered .laser irradiation gives detection limit of 16 ppt. The possibilities of direct Co determination in AlgO» in powders are shown in the paper. DIR30T METALS DETSHMIHATIOII IH BOCKS BY LASER | ИГНАНСМ) IONIZATION IN FLAH33 I ""' A.G.JJarunkov, V.I.Pavlutskuya, B.V.Chekalin Vernadaky Institute of Geochemistry and Analytical Chemistry of the USSR Academy of Sciences, Moscow, USSR

The creation of direct, high sensitivity methods of the trace elements determination in the environment objects, free of the matrix interferences, is very Important for the solut­ ion of geochemical, technological and ecological problems. Very prospective for this purpose is the use of the laser en­ hanced Ionization in flames. The high sensitivity and spectral selectivity of the method, conditioned by the stepwise inter­ action of the laser radiation with an atom, make it possible to obtain at the analysis of various objects the detection limits of 10"'* and loner.

The present article Investigates the possibilities of the direct analysis of rocks - the standard magnesial basalt, the alaskite granite, the trapp, the meiсhemIt and others, for the contents of lithium, rubidium, caesium. The investigation of the matrix Interferences on the analytical signal has shown that they are reduced to the additive ionization background. The emergence of the background is due, principally, to the •ultlphoton ionization of the CaOH molecule and is highly dependent on the excitation conditions. The optimization of these conditions made it possible to obtain the detection limits in the rocks as Ion as 10"'*.

The lithium, rubidium and caesium contents in the samples »rt determined by the calibration characteristics for the standard aqueous solutions and by the standard additives meth­ od. The coincidence of the results received between them and with the certified values has shown that the direct deter­ minations of elements can be done without using the standard composition samples and confirmed the accuracy of the measure­ ments with the calibration by the aqueous solutions. The fur­ ther prospects of the method шг* being discussed.

331 LASS» IIICBOPHOBE ANALYSIS OF HATUHAL ALS-tS SOLD PARTICLE AND CASSITEBITES 3 L.lt.Saunova, S.Q.Shchelchkova, V.S.Suknev Institute of Geological Soienoes, Yakutsk, USSR Methods have been developed for quantitative detexnination of the minor elements AB,Bi,Oo,Hi,te, Pb, Pt, Sb, Sn, Те, Za is gold partiolee and Fe, In, Kb, Sc, la, Ti, W in eassiterites (SnOg). The analyses «ere made on a laser mieroanalyzer LHA-10 con- bined with a diffraction-grating spectrograph (Carl Zeiss, Jena). The Q-awitch regime was used. Spectra excitation conditions «ere chosen experimentally. Microplasma radiation was recorded on SF-2 photographic plates which were developed in a phenidone develo­ per. The lower detection limit for various elements varies from 1 to 100 ppm.

Commercially manufactured gold-silver alloys were used as re­ ference standards. To allow for the gold fineness, the following analytical parameter was used : lg (p/100) *Sansl/SAu, where p is fineness of the sample,S is density of line.

In cassiterite analyses, pellets of artificial maxtures pre­ pared on the basis of a chemically pure tin oxide were used as reference standards. The mixture was thoroughly ground, then gradually pressed. Maximum pressure was ?*105 icPa. Relative standard deviation varies within 0.1 - O.J.

332 шшшшхпш о; CHHECAL СОМРОЗШОН «ID содома THICKNESS К 1ASKR 1CCE01HALY3IS AIS-43 V.V.Fentelsyev, T.A.Bozanteev, A.A.Xankovsky Institute of Physio», BSSR academy of Science», Шлак, USSR

Selaotion of the proper laser operation sa «ell aa of the war of beam focusing penaite obtaining tbe required material damage loca­ lity in area and depth. In this conneotion it is expedient to иве laaer radiation fox analysing various coating», films and surfaoe layer*. The present work baa been done on a laaer microssalyser.where the source of excitation of atomic spectra was plasma produced on irradiating the targets by laser radiation with 0.03-0.04 J pulse energy, 10 ns pulse duration and 25 Ha pulse frequency. Single pulses were also used. Tbe focal distance of the lenae focusing laser radiation was 50 an. Beeording of the spectra was nade pho­ tographically, using only the intrlnsio laser plasma glow without additional electric discharges.

With tbe aid of the laser nUroanalyser qualitative analysis of oomposite films and surface layers bee been performed and three- end four-component ooatings hare been quantitatively analysed. It is shown that the use of the above laser operation for quantitative analysis of films and coatings allows to use the conventional mono­ lithic standard samples. The method developed permits determination of the film and coating thickness within 10 nm - 200 urn. i Analysis of different objects has been carried out. Including metal filme deposited on quarts fibers; fiber surfaces after Droaohldg through spenneretsi oxidlc films and oxidation depth. §';'• Qualitative analysis of various ooatings and deposits has been Ы- performed and thickness of elusdnlsed layers,etc. nee been deter- Ы- mined, the type of coatings and substrata, their physical proper- .;-.' ф; ties, conductivity, tranaparenee,ete. being of no significance. Jf i 5*- LASER ATOMIC ABSORPTION SPECTROMETRY DETERMINATION! 1 АХЯ-4Д OF CONCENTRATION PROFILES IN THICKFILM-MULTILAYER- I**" STRUCTURES

F. Steglich, G. Reppa VEB Robotron-Elektronik, Radeberg, GOR Laser atomic absorption spectroscopy (LAAS) has been increasely used for the trace analysis of metals in solid samples Л, l]. This method was applied far the half- quantitative distribution analysis of thickfilm-multilayer- systems which include resistors under the dielectric layers. We investigated diffusion processes of the resistor ink elements Pb, Bi, Ru, Ti and 5n into the "analyte free" dielectrics after the firing process. Additional the copper diffusion from the conductor-termination into buried and not covered resistors was enlightened.

By means of statistical experimental design the optimal conditions for the transport and atomization of the laser ablated material were ascertained. ThB influence of the deposition-and injectian-LAAS-technique /27 on sensitivity was investigated.

The analytical results explain the shift of resistance values and temperature coefficients of resistance. Me found that the Pb- and Си-diffusion was the most important process during manufacturing of multilayer circuits.

Refarenoas

1. Dittrich K., Nennrich R.// Spectrochim. acta. 1780. V.J5B.P.731 2. Vennrich R., Dittrich K.// Ibid. 1»B7. V.42B.P.995

334 USER MICROSPECTRAL ANALYSIS OF CARBON-CONTAINING REFRACTORY MASSES

T. Taolov, C. Fravtehava Iron and Steel Research Institute, 1870 Sofia, Bulgaria A method has been developed for laaar aicroepectral analyaia of carbon-containing vibrating maases. applied in linings of blast furnaea trough» and ataal ladle». Tha content of carbon, silicon, aluminium, iron, calcium, magnesium and manganese baa baan deter­ mined in aactiona with a aire of 100 urn. The analyaia baa been performed by using a laser mieroapeetral analyzer LMA-1 with a Md- glaaa resonator (ODR), The standard samples have been prepared in the form of briquet­ tes of silicon carbide end the oxides of aluminium, calcium, mag­ nesium, iron and manganese. The sintering of briquettes has been carried out in inert medium, in conditions similar to those of refractory production. The applicability of the prepared standard aaeplea haa been tested according to the criteria of [ll« Analytical parameters have been chosen, as wall as a way of recording reaults [ 2] and optimum condition» of operation of the spectrograph and laser analyser. Since carbon determination is alao required, the auxiliary electrodea for additional excitation are made of copper. The correctness of the newly-developed method has bean checked by comparison of the results, obtained by using UtA, to the reault obtained by chemical methods and mlcroprebe area scanning. The good coincidence of the results confirms the good prospects of tha method. The obtained analysis data elucidate the materiela wear mecha­ nism in the operation process.

References 1. Tsolov T. et nW/toeaenius Z.Anal.Chem. 1986.7ol.323.P.228. 2. Taolov т., PrevtoheTa С.//1Юк1.В«.19в6.Уо1.Э6, Яо.б.Р.61.

3» THE APPLICATION OF LASER UASS-SPECTROHBTRY METHOD FOR ALS-46 ABALYMOAL CONTROL OF FURS ALUIUHIUH ADS ALLOYS ON IIS BASS

R.U.VaJchobovs, B.H.Subkhankulov Tadjik State [falrerslty, Dushanbe, USSR

The methods of admixtures determination in pure aluminium on laser mass-spectrometer nAHAL»2n have been worked out* The chosen conditions of analysis allowed to determine a serine of traces (Kg, Si, Ca, Sc, Ti, 7, Or, Mn, Fe, Co, Hi, Ou, Zn and others) in detection limit of 0.1 - 0.01 P.P.m. The method has heen also used for macrocomponents determination in alloys Al-Ti, Al-Sl-Ti on the base of pure A:. Mass spectrometry application allowed to obtain data about macrocomponents distribution on sample's surfaoe as well as the data about average content of traces in the sample and by suoh way to control technology* Under standard samples' analysis have been established metro- logioal characteristics of the method: correctness was 30%, convergency - 209. The coefficient of relative sensitivity for majority elements was close to unit. X-RAY SPECTROSCOPY

22.3ак.413 DETEBJIINAIION OF BIPUBITIBS III ZIHOOHIUM, XHS-1 ПШШ AND BOSON OXIDES BY X-RAY ЕШОНЕВСЕНСЕ

F.H.Ali, q.A.A.Jasslm, H.H.Alrazak Iraqi Atomic Energy Comission, B.O.Box 765, Xuwaitha, Baghdad, Iraq

A method is described for the determination of trace concent­ ration (ppm) of J?e, Zn, Bi, Cr, lin, Fb, V, Ho, Cd, li, Co, Cu, D and Th in zirconium,titanium and boron oxides by X-ray fluorescence. Two procedures were used for sample preparation.First, by pollet formation of the sample after adding a starch as binding agent and a fusion procedure as glass disk bead. The lower detection limits of the elements obtained from the X- ray determination (ppm) are Fe(I<0, Zn(15), Bi(30), Cr(25), Hn(I7), Pb(35), V(30), Jlo(25), Cd(27), E.(28), Co(23), Cu(25), U(I8) and Th(I5i№e advantage of this method is fast and requires no chemical treatment, the method has a good precision for the impurity ele­ ment.

ЗИ USE OP X-RAY RADIATION FOR DIAGNOSTICS OP SPECTROMETER XRS-2 ADD DSTERHINATION OP MATERIAL COMPONENT COMPOSITION

V.R.Alperovieh Giprotsement, Leningrad, USSR Impulses registered by the apparatus bear Information about the state not only of the sample,but also of the spectrometer. Separa­ tion of these components and their farther use alio* for the analy­ sis precision to be increased substantially. It is possible to ex­ tract this information with the help of an information processing algoritm based on the use of two control samples and on a program of comparison of values of analytical line intensities and some their functions with the set digital limits.

It is not traditional to use spectrometers for determination of component composition of mixtures. DiffTactometers are more often used for these purposes. But the possibility of the multielement analysis of sample enables the component composition to be determi­ ned quantitatively with reasonable acouracy» A method of determina­ tion of slag, gypsum and clinker content In cements has been develo­ ped at the Institute of Ciprotsement. The model for determination of the components is built in the form of a system of multiple regres- . slon equations which as a rule Include from 4 to 8 significant fac­ tors (intensities and their products). The coefficients of equations are determined on pressed emitters by the method of least squares.

In view of component characteristics variation with time the principal difficulty when developing the techniques is the choice of stable models. In spite of use of statistical tests in choosing the optimum form of the equations we failed to formalize completely the process.

33» CALCULATION OF ELECTRON DISTRIBUTION IN SOLID TARGbT |~XRS^T| EXPOSED TO ELECTRON BEAM L.A.Bbkaleinikov, E.A.Tropp A.F.Ioffe Phyeico-Technico.1 Institute, Academy of Science of the USSR, Leningrad, USSR To define the generation function of primary X-ray caused by elec­ tron beam with energy of some tens kiloelectronvolte in a solid tar­ get the information about electron distribution is necessary. The in­ formation can be obtained by solving linear kinetic equation which describes the electron relaxation process in the target. It h&a been shown in fl] tfcat for targets with large atomic пшЪег the electron relaxation process on all depths exept thin layer near the surface is the diffusion in coordinate space accompanied by ener­ gy loss. In the layer near the surface with the depth of transport Bean free path A„ the electron distribution becomes isotropic and the redistribution on energy on a small scale takes place. There is a peculiarity in the solution of the equation in diffusion area in

the vicinity of г * 0, £ » £c • In particular this leads to divergence of backaeattering electron energy spectrum near the value £ * £„ . To eliminate this peculiarity of electron distribution function the kinetic equation in the layer near the surface with the scale of

depth A0 and the scale of energy £eA„/i0 ( &, is the path length travelled by an electron) is considered. The analytical soluti­ on of the equation is found by using (1) continuous energy lose ap­ proximation and (2) the Landau model for inelastic part of collision integral. To obtain the solution the method of expansion on spherical harmonics in halfspheres is enployed.lt is shown that the solution eliminates the peculiarity in the point г• 0, £ • £j and agrees with the diffusion solution for large values of г and c„ £ . The distribution of x-ray production in depth and energy spectrum of back scattered electrons are calculated by the solution.

Reference 1. Balcaleinlkov L.A., Tropp E.A.//J.Techn.Fhys. 1986. Vol.56. P.16.

340 THE X-RAY FLUQRSSCHIS AHAUSIS WITH «Ш USB OP THB ГгвмГ1 UBIVSHSAL EQUATION FOE THE STAHDARO-SCATTERSD RADIATION ' ..... i METHOD A.V.Bakbtiarov, L,P.Korobeynlkova, D.H. Strogano v, H.A.Verman Leningrad State University, MHTK "Uekhenobr", Leningrad, USSR The method of standard - incoherent scattered characteristic ra­

diation from an X-ray tube anode (nin„) which is usually used for determination of low concentrations of heavy elements in samples with light matrix was used for complex products having different contents of measured and hindering elements. The concentration of the measured element was calculated according to the universal equation Z~1 /» t „ о I

where fl$ is the intensity (count rate) of an analytical line of the

measured element; П№ is the intensity of line of the hindering ele­ ment whose absorption edge is situated between the analytical line \

and the comparable lineH^; Пе, ft^, Л , Ьц are the constants whose values do not depend on matrix composition and concentrations of neither measured nor hindering elements (these constants are de­ termined in samples with known Сд values).

In order to determine Ho we measure Пд and И,„с in samples having low C. values (less than 0.1 jt) and various matrixes and after that draw the correlation graph of specific intensity of the analytical line 1Л=1(|/Сд versus nine intensity. R° value can be calculated _ according tp5 the following expression Rj =п5УСС"СпЙ ИоО «*•?•

Ид and Пгяс values are measured in a standard sample with Ct not more than O.K. The ft coefficient is determined as the angular coef­ ficient of a linear correlation graph for the additional parameter R l *= IIАЛСдСИик-По)versus the flA intensity in samples without hindering elements. Analogous to this the 0« value can he calculated for each hindering element according to correlation graphs for Rj. versus Им intensity (for the latter we use samples with small 0. values and wide variations in the content of a given hindering element). The universal equation was used for ores and their processing products in different netal deposits; iron, tantalum, tungsten, po- lymetals, ots. It ensures high aceurasy of the analysis and simpli­ fies its procedure. Reference 1. Bakhtiarov A.V.// The apparatus and methods of the X-ray analysis. Issue 21. Leningrad, 1S78. P. 3-15.

Ml DETERMINATION OP DEPTH-PROFILES Ш SUHPAOK LAYERS XRS-5 OJ? 30LID.3 BY ANOULAR RKS0LV3D X-RAY PH0TOJ3LECTRON SPECTROSCOPY O.A.Baschenko, V.I.Hefedov Institute of General and Inorganic Chemistry of the Academy of Sciences of the USSR, Moscow, USSR in the present work the nmerlcal method which we proposed in (1-3) for restoration of depth-concentration profiles of elements in the surface layers of solids with thickness up to 10 nm based on the data of angular resolved XPS, is extended to embrace the case of four-component samples. It was shown for a number of model systems that the suggested procedure of accounting the a priory Information (i.e. thet етегу depth-concentration profile Is a non-negative and bounded function and may have no more than one extremum) enables us to obtain sulutlow which are resistant to the really attainable at the present day «10% error level in experimental data. It was found that determination of the ratios of elemental concentrations by the slmllfled method, that is from the the XPS line intensities at the same take-off angles в (usually 8=45°), may lead to considerable errors (up to and over 200X) for the uppermost layer due to neglect of real concentration gradients in the sample. Hon destructive restoration of depth-concentration profiles was conducted on the basis of experimental angular XPS intensity distributions for several samples with 3-4 components. For a TiOg sample ( with a hydrocarbon contamination layer) It was established that the ratio of Ti 2p and 0 is line intensities at e=4S° gives the 1:3 proportion of atoms, while the obtained profiles point at the presence of stoichiometric oxide

Ti02, but only from the depths more than *2 nm. Above this oxide layer lies a film containing adsorbed oxygen and hydrocarbons. Depth-concenratlon profiles have been also obtained for SiOj and I1H. References 1. Bascbenko O.A., Hefedov V.I.//Poverhnost'.19B7. H.T. P.T5 (in Russian). 2. Baschenko O.A., Hefedov V.I./VPovertnoef .19вТ. в. 10. P.99 (in Russian). 3. Hefedov V.I., Baschenko O.A.// J.Blectron Spectrosc. 1968. Vol. 47. P.l-25.

342 THE EMHRICAL CRITERIOH OF SELBCTISO BEHCH MARK SPECIMEHS I IH X-RAY ЗРЕ0ШШМ AlfAECSIS OP SILICATES BY CM I XBa"6 QUAKTOMETER TI3IHO MELTED SPECIMENS S.A.Batzuev, V.O.Kraaavobllcov, A.D.Kiraev Inatitute of Geology sad Geophyalca, Hovoaibirak. USSR The selection of benoh mark specimens la hindered by tha influence of aeveral factors; 1. The problem of maintaining teaperature stability in HF-melting. 2. Statiatieal divergence of the reaulta due to the low intenaitiea of the light olemanta (Ha, Kg, Al). 3. Necessity for considering variation! of tha coacentratione in bench marks from the apeclfied values in view of faotors 1. 2. The propoaad procedure of aaleoting bench mark apecimena ia a» follow»: 1. Analysla of tha atandarda on each bench mark apecimen. 2. The following value ia calculated for each bench nark and each standard epeeimeni n Л4*'_#**\*

where» n^ - number of channels: C?j - specified content of i - element in i - atandard apecimen; CjJ' - experimentally de­ termined content of i - element in 1 - atandard epeolmen ualng к • benoh mark» 3. For each bench mark apeoimen the quality coefficient la calculat­ ed by i

0^ - mln qlt Where к - tha number of the benoh nark specimen. 4. Bench mark specimen with a maximum quality coefficient ia optimum. This method baa bean realised on OHSI-PASKAL for microcomputer 15-ВИС0 used in CBI quantomater. Application of thla method to a great number of analyses during two years showed hign reliability and low sensitivity to tha Instability of the equipment. The eame orlterlon waa applied in Г0. Referenoe 1. Kuahnlrenko Ye.A., Katjukhin V.A. // Climate and health of people. Intern. Syap. VHO/VOZ/YUHBF. Leningrad, 1986. 7. 115.

343 DEOONVOLUTION OF COMPLEX X-RAY *UIORE3CE2K SPECTfiA XHS-7 Yu.P.Betin A.P.Nikolskiy, V.H.2avgorodniy Industrial Scientific and Technical Complex "Soyuztsvetmetavtomatika", Iloscow, UuSH She practical application of X-ray fluorescent analysis me­ thod is sometimes hindered by inadequate energy resolution of registered spectra. Assuming that separate lines have Caussian form resolution can be improved by means of digital filtering.

In the report the possibility of spectra deconvolution with linear and nonlinear digital filters is investigated. She resolution gain through linear nonrecursive filter is attained by means of Fourier spectrum transform in the frequency range with a specially selected function and subsequent trans­ formation into the energy range. The methods for suppression of noises that have frequencies within the sampling interval are examined.

The intensity of initial spectrum analytic lines are defined by the method of comparing experimental and theoretical ampli­ tude values of low frequency harmonicc. the results of mathema­ tical modeling show that intensity is assessed with toe accuracy of 1 and 2 percent at similar values of signal and noise dispersion.

The nonlinear local filter that is dependent on one parameter and retains all the characteristic lines, their positions and intensity in the spectrum transformed is offered. Dispersion of each spectrum line is reduced by a value that is dependent on the filter parameter selected. She filter examined is tested on model and actual instrumental spectra. The spectra restored are compared with the results re­ ceived by the method of 3ayesian deconvolution.

344 ИИИИАТИИ OP И XBS-8 or шиждив л soioia В лво СГ Х-ШХ ижтпт вон» вт гае S.M.Blokhln, A.A.Ylasov Physics Research Institute,Rostov State University, RoBtoT-oib-the Dan, USSR O.A.Baschenko Institute of General and Inorganic Cbeaistry of the Academy of Sciences of the USSR, Moscow, USSR The method previously proposed by the authors [1) for obtaining the depth profiles of the concentration of impurities through the angular dependence of the yield (I) of X-ray radiation excited by accelerated Ions is now used for determining the distinctive features of the depth distribution of the concentrations of various Impurities in a silicon sample. The procedure of determining concentration profiles from experimentally aeasured values of Kcpj) (where

Referenees 1. Blokhln S.H.tTlasov A.A.//Proc. the Ш Ail-Union Conference on the Physics of Interaction between Charged Particles and Crystals. 1.: Moscow State University, 19B2. Р.Э7 ( in Russian). 2. Mefedov V.I., aaschenko 0.A./7 '/.Electron Spectr. 1966701.17. I 1.1. P.1-25 ШХ OF SXSIEMAIIC ERROR ШАОИОЗТЮЗ РОН IHSTRUMEMAL Г~ 1 XRS-9 METHODS I lJ B.Yu.Bondarenko Horil'sk Mining Metallurgioel Complex Horil'sk, USSR lb* way of systematic error (SE) diagnostics which is used to-day i» based on 3tudent_t^test checking of statistical significance of other than serodt'C-^galue for average deviation resulting from method «bile studying or method for reference (for example chemioal method). In such • case however only constant component of systema­ tic error (CSE) is diagnosed and possible error crept which varies linearly together with concentration increase is Ignored (LSE). Some factor of poor cheek effected on procedure of analysis can lead to overestimation of low concentration or underestimation of high con­ centration or vloe versa;» value will tend to zero; t-test will in­ dicate systematic error absence while it is available; that is to say the distortion of results can not be determined statistically. '.therefore the way of Independent dlagnoatioe for CSE (constant sys­ tematic error) and for LSE (linear systematic error) was developed to eliminate mutual effect. It is based on analysing of ellipse posi­ tion aa a coanon confident region for O. and & parameters within equa- tionC-O+f^^with respect to straight lines e»0 and *T*i which correspond to CSE and LSE absence followed by tests according to statistical criteria. Algorithm is synthesized so that availability of linear systematic erjjor is cheeked firstly and only after its ef­ fect la eliminated eonetant systematic error is diagnosed. There are common analytical expressions for coefficients of the equations for instrumental aetbuds which appllcate constraint equati­ ons with linear parameters. They have been corrected to eliminate sys­ tematic deviation from results of method for reference. Computer-aided results being compared have in particular demonst­ rated that CSS to LSE proportion for analysis by X-ray spectrometry (more than 100 diagnostics) tvma about three-seven, rhe same propor­ tion for ohemioal proximate methods-runs about aix-four. The latest findings have illustrated high linear systematio error rate and pro­ ved the necessity of it to be diagnosed and to be taken into account side by side with constant systematic error. The way of analysing is practised in analytical services at two of metal-making complexes in the USSR.

34» QUANTITY OP 1НЮ1ШАТ10И III X-RAY SPSCTfflJH AHALY3I3 V.V.Druz XRS-10 Research Institute of Mechanics and Applied Mathematics, Rostov-on-Don, USSR Quality of the result K»i«i} obtained in determininj components I is usually characterized by mean-square error (KSL) 4a{4(} with res­ pect to true concentration Cm{Ci} .The latter is always known with cer­ tain MEL B»{0<} since multivariate range A=»C is bounded (.particularly in stable technological products).Jherefore Э by itself doesn't give insight into necessity and usefulness of analysis,to hft a source of in­ formation about substance composition,and general or component-to-сош- poncnt uncertainties in a priory and a posteriory (before and after the analysis) knowlege should be compared. Measure of the first and the second general uncertainty is entrony H—JcUf-4»f and mean entropy A ' respectively where t*f(*) ie the compound probability density (,TO) of value CtA occurrence in sample; pmp(KIC) is the conditional PD to obtain concentration КеЯ as the result of teat whereas really it ieС ;all PD are normalized to 1; ttCm-ljlelCt, «tff«IJlrfAV .The quantity Г-ff-ff of information is the greater,the more various С and lower noise level corrupting С to К . The research ie useful whenffO. As an example consider the scope for complete analysis of (Л+1)- conponent system to obtain mass concentrations 0*^*1-3^3^ under fol­ lowing conditions,which are quite natural for X-ray spectrum method. 1.A11 С are equiprobable.lt giveB: fmn!; ti-n(i-d.)nrl (expectation Cj" 1/(л+1) ie prior concentration with ИЗЕ C{(»)»5-Vi*Cn+4".e.g.tf£t4)-29)'.

2.Ev«nts Kt,Cf. U>>>«+1) are independent: p(Klt)~gjiPi(Kilet).£atlor>i- вв him-jl4CfPfi*t Pi ere equal,hence ifmltldCffchi .USE »j=S-4j. In this case (in bits) I— Ufcrft!f»$/e^3-(ftW-ftlf^M- where B«V2«7/2/5jV5e%.for normal/uniforn/trigonal/.. P3 ft respectively.

E.g.taking В-УЗи,»--1/6/15, whenS-«»,»--0(ai«const(eymS) /-2.6/Й.1 (.max)/-1.5i misinformation)) when e»-l;«,«t.1№/ft"S) Г-6/39/101 bit. Any other continuous PD i gives lesser quantity / of information. The number Л of channels and BJE ii(*iS) rauat be mutually optimized for acceptable / in quantometers engineeri^s and analysis techniques.

347 A ИИ» СОНСВИКЖ OV THB X-RAX FLUORBSCBTCB BQUATIOHS ) ] AID Х-ВАУ МДОВЛЗСНИ AHAMSIS [188-11 j V.V.Drus ВимпЬ Institute of Mechanics and Applied Mathematics, Rostov-on-Don, USSR The gap between becoming more complicated theory of X-ray fluores­ cence (IP) and corresponding widespread analysis practice is increa- sing.A way to eliminate it is suggested for hoaogeneous and thick spe­ cimen admitting substitution of typical XF expression еяр(-?г) at p—•» by the impulse Dirac function £t.(?i)»8»£a)/£, «here < *0 is variable. In attenuation coefficient /u-,(X)fav the X-radiation of wave length

Ae 1Лс,Я/1 the oofactor v(!0 for considering (J) and all aecompaning elements can be separated rather precisely (A, and Я, is the boundary of primary spectrum and detecting XF respectively).The total coeffici­ ent M(X)ot the specimen can be reduced to Л(Л) in view of attenuati­ on edges Я for wave length Л«СЛ»»Д»1 fixed at will.Then XF intensity J^-Vj-4,Cv) d) W*<*M. V,-^(A)-C^/H(A), ЛЧ.2, ...,J,„ .,Q, depends on mass combined arguments 0*V,*1 of intsrfereing elements R only, but not on mas* concentration {

, (J»+i,lIi)-Y,*ib.dn-V*-*i, (d„,-tn}m

with accuracy to »1jf, which is in acoordanoe with the premisses of the XF theory. The elements interaction constant coefficients at reaulrlne the calculation of awkward integral XF exitation-attenuation functions

i,(V,) and §rCyf/)Vf) must bs onoe tabulated beforehand from conditions

In *t(W,.Wn\**l) for Sherman function у»-*»*"-(*•*/*») ^-ap­ proximation (**-»•«) givesjj,»4ht»1.rhe experimental calibrating fac­ tor it corrects (1)-(*) to frame and negleoted considerations. She XF give* only ratios of concentrations or C,lM -To find the ab­ solute С one needs in addition prior or experimental compositional re­ lation ti(c)-1, j*(M$ml ОГЛ(МО -1,necessarily inkomegensoum.lt deter­ mines possibility, method and in the main aoeurae? of the analysis.

Mt possiBiLin op wsuama THEORETICAL COKRJSCTIOH METHOD УОН X-ЯАУ FLUORESCENCE ANALYSIS OF HETKR0CEN30US POV/DSR SA11M.ES S.I.Buir.ialiaev, L!.G.farnopol3ky, T.G.Duimakaeva.A.Ya.Shpolyansky tiesearch Institute of Physics, Rostov State University, Hostov-on-Don, USSR XHS-12

Conventional variants of theoretical correction method (TCM) used in X-ray fluorescence analysis are justified for the homogeneous specimens. In analysing tile heterogeneous powder samples it becomes necessary to apply a "heterogeneous" theory of fluorescence inten­ sity and to take into consideration density p of a real (i.e. ta­ king into account degree of packing) sample. de have shown that it is possible to apply TCM for analysing heterogeneous powder samples of wide element concentration ranges using the following equations:

WW T** . ^>

±i 1 * GtifAp or Г-Г*'Ь ^tt^'J*6* <2) WW "ум" , __,

Here uf and A Й are variations of density and degree of packing of the unknown) respectively, relative to the reference sample. The in- terelement influence coefficients!*;; have been obtained for the idea­ lised assumption of the stability o± the sample density in the pro­ cess of increasing the interfering element concentration Qj. Analysis nith the help of JSq. (1) requires measuring density f of the unknown. In order to use Eq.(2) it is necessary to know in addi­ tion the solid phase density of the unknown whion is determined by iteration using density values O, of the solid phase of the cons­ tituents. Testing has been made by means of the experiment with a mathemati­ cal model (Jiosev and Smagunova's theory for the fluorescence inten­ sity of the heterogeneous sample). Relative standard deviation (jS) of the analysis of four-component systems Cu - Hi - Fe - Ti (the ele­ ment concentration varied from 15 to 35*) was 0.65, 0.7Э, 0.32, 1.2 and 0.70, 0.83, 0.55, 0.7? for (1) and (2) respectively. Results for the conventional variant of TCU are $.0, 5.6, 5.2, 7.2. MAYS OF TAKItfH INTO CONSIDERATION HETEROGENEITY OP Л POfflHi SAMPLE III X-RAY PLUORESCEHCE ANALYSIS lxBS-13 S.I.Duimakaev, A. Ye.Shpolyanaky Physics Research Institute, Rostov State University, Rostov-on- Don, USSR Sample heterogeneity is one of the most difficult problems in XRP analysis. Experimental results indicate fairly large and in general non-unique dependence of fluorescence intensity on particle size of a powder sample. In the present communication possibilities of taking into consi­ deration the influence of heterogeneity within various theoretical models are discussed. Particular attention is paid to the models £l ,2] that are simple and physically meaningful for the interpreta­ tion of the effect. It has been shown that for polydisperse powders it is advisable to use two essentially important sizes within the explicit basic theory \2~[ - the average 'fluorescent' particle size and the average particle size of the sample as a whole. It is also expedient to give up the rude assumption Г 2] that the size of in- terparticle emptiness is equal to the partisle size. One of the main advantages of the model £l] is that its struc­ ture enables making theoretical approximations for a heterogeneous sample on the basis of a homogeneous sample element fluoresoenoe in­ tensity theory which is in a very good agreement with the experiment. Within this theory when the preparation conditions are maintained invariable, knowledge of particle size is no longer a requirement. The paper presents some peculiarities (the neceauity to specially take into account sample density, etc.) of the theoretical correction for interelement influence in XRP analysis of powder samples. Possi­ bilities given by XRP analysis of powder sample composition when the exact knowledge of the sample particle size is not required and when the analyte present in the heterogeneous powder sample is in various compounds have been discussed. Ways of taking into account 'variable1 particle size, in particular the uncontrolled variation with the help of Км - and Ka- intensity ratio, in XRP analysis have been justified.

Reference»

1. Losev H.P. quantitative X-ray fluorescence analysis. U.\ Hauka, 1969. 2. Berry P.P., Puruta Т., Rhodes J.R.//Adv. X-Ray Anal. 1969. Vol.12. P.412-432.

360 ШРЫПШСВ OP HALOQSBIDB ABDITIVBS Ш ИШ ИГВМАВХЫЯС Г~— 1 XRS—14 07 РЫГПгаи 0ТОС1ВИЗ ЙШЯ0 ТОЗГОВ IH Х-ВаГ I ЯИОЯВЗСВНСВ ШЩШ19 a. Shrhardt, P. Dittrloh VBB Hanafold Kombinat, Poreohunge

4#—. BXPEBIIIESTAL X-RAY K« AHD KJJ I3CBS-15I SPECTRA OF SCAHMOT I _£J V.I.Fertikov, L.I.Konissexova, I.V.Orlgoxovich, G.¥a.Pushkina, Yu.A.Erahov ПРО "Stekloplastlk", Moscow State University, Moskow, USSR

At present investigators give much attention to accumulation of data bank of chemical X-ray line shift of Internal electronic transi­ tions Д7. This can be explained by the fact that this characteristic is highly informative. Magnitude of chemical X-ray line shifts allows to estimate the degxea ot atomic oxidation and coordlnational state of the atom and to determine amorphous state structure and molecular bond energy /2, \l.

The report presents Investigation results of ohemlcal KA and Kp X-ray line shifts of sixteen scandium compounds. It has been found that the shifts of X-ray lines depend on ligand. Direction and magnitude of chemical shifts in studied compounds are

determined. Begative shift of Кл line at increasing ligand electric negativity has been discovered. Obtained results concerning energy state of sulphur atoms in sul­ fide and sulfate are in good agreement with literary data /47 • The new characteristic - "relation of Intensities" has been introduced which allows to Interpret bond type In a unigue manner.

References 1. Hefedov V.I., Urusov V.S., Kohana H.M. // Geokhimya. 1973, H 1. P. 11-15. 2. Aalanova U.S., DorzMev D.B , Saposhkova L. A. et al. // Phisika 1 Khimiya stekla. 1982. HI, P. 34-37. 3. Tyshkovskii G.b., Sapozhkova L.A., Fertlkov V I et al. // Phi­ sika i Khimiya steklcu 1988. Vol. 14, 13. P. 463-467. 4. Harbut K.I. // Isvestya AH SSSR. Ser. Phislka. 1974. Vol. 38, Я 3, ?. 546-561.

к: ABOUT CALCULATIOK OP X-HAY FLUORESCHNCiS INTENSITY POH [ THiS РСШИВ SUIRRY-ЫКВ MATERIALS I MS~16 A.L.Plnkelstein, V.P.Afontn, T.K.Gutiicheve, A.G.Kalugin Institute of Geochemistry, Siberian Branch of the USSR Academy or Sciences, Irkutsk, USSR

The slurry model, In which the spaolal distribution of non-homoge- nlties Is desorlbed aa the " Polsson's ensemble" flj of the solid phase partloles dispersed in the homogeneous enclosing matrix , is used to derive the analytioal equations for x-ray fluoresoenoe and the scattered primary radiation Intensities of the powder slurry-like sub­ stances. In a suoh model the probability density funotion of the par­ tloles Interdlstance distribution Is given In terns of:

f

•here 00 , Cj - the volume contents of the enclosing matrix and the solid phase, respectively; d - the effective mean else of the solid phase particles. When the solid phase partiolea have just the same else, the equa­ tion of x-ray fluoresosnee intensity will be: i- e'^'d

where ; If - x-ray fluoresoenoe Intensity of the solid phase, If It Is pure and homogeneous j V, , Uj, - the linear absorption ooeffioients of the enclosing matrix and the solid phase, respectively. The oalottlatlon results of x-ray fluoresoenoe and seattered prima­ ry radiation Intensities are given in comparison with the own experi­ ments and data, published In the literature ft,J7- The oomparison with the experiment shows that the equation (1) better daserlbes the x-ray fluoreseenoe Intensity dependence on the particle else than the equations of the authors CU proposed before. The generalisation of the equation (1) for the ease of dispersion of partloles with a given size distribution Is proposed.

References

1. Feller V. Introduction in the probability theory and ita applica­ tion. K.i Kir, 1984. 2. Berry P.В., furuta Т., Rhodes J.B.// Adv.X-ray Anal.1969.Vol.12J.612 3. Volodln S.A., Revenko A.G., Afonln V.p.// Zavod.LaW987.Vol.53.P.24.

23.3eK.4i3 Ш I-RAI FbOORHSCBHCB (IE») A5ALISIS О» ROOKS SI JOIHI USB OF p- AHD ot-COHRBCIXOX I LI H.S.Pogeleon, H.A.Korovkliia, A.T.Savitchev, I.A.Roetchina Institute of Lithosphers, Veraadsky Institute of Geochemistry and Analytical Chemistry, USSR Academy of Seienoas, Moscow, USSR Satisfactory results of XKF-analyais on multlohannal spectrometer of rocks with widely varying composition were obtained by applying d-correction regression method to the samples prepared by fusion in relation rook/flux 1s12 [1] .Shis approach to the matrix influence problem is not effective in the case of simultaneous determination of major, minor and trace elements since highly diluted sample is not re­ presentative for elements present in loir concentrations. For XRF analysis of 10 rock forming and A minor and trace elements (with atomic numbers 2(30 ) in rooks of widely varying composition (mafic, acid and alkaline magnetic rocks, cherts, clastic sediments, clays, carbonates and bauxites) we used linear system of equation in the form: °1 " h < 4 - V (^ +2°Vil +гг^11кС1°к >* <1 > where 1^- measured intensity of characteristic emission line of i-th element, J*. - mass absorption coefficient of the i-th element radia­ tion by the sample.Background intensity 1^ is defined ass \ • \ + VA- i (2» _ that permits to take into account the background dependence on matrix composition. In (1) to the/"-correction formula ^-correction is added in the form of Olaisse-Quintin, that assures better approximation abi­ lities of equation,Coefficients of (1) and (2) were determined empiri­ cally on the set of standard samples with known compositions.Content of main rock forming elements in the samples varied from parts per cent to tenths per cent.By calculation of coefficients for every element in the low and high concentration range the value was minimised. She measurements were fulfilled by XRF-aimulteneous spectrometer РВГ- LIP3 РИ-16О0 (anod -Ah, 40 ml, 50 klO.The element were homogenised by fusion in relation rock/flux (Ы-В.О-) 1i(3 • 5).Obtained accuracy and reproducibility of results are mainly within the requirements of labo­ ratory mass scale analysis.

References 1. Rostshlne I.A., Shevaleevsky I.D., Korovklna I.A., Kajorov A.P.// J.Anal. Спев. 1982. Vol.37. F.1611. 2. Afonln T.P., Ganltobeva I.I., Plskunova L.».//I-Ray Fluorescence Silicate Analysis. N.t lauka, 1984. P.95.

U* THE MAIN TENDENCIES OF DEYELOPKENT IN THE CHEMICAL-X-RAY ГГ 1 XRS-18 SPECTRUM ANALYSIS ' F. A.Ginerfarb, F. I. Lobanov* I. A. Roshina** Moscow Institute of Flne-Chemlcal Technology «Institute of system Analysis **vernadsky Institute of Geochemistry and Analytical Chemistry, Academy of Sciences Of the USSR, Hosoow, USSR

X-ray spectrum analysis (XRA) is widely used for determination of chemical composition m different substances and materials. X-ray fluorescense analysis (XRF), X-ray radiometric analysis (XRR), electron probe X-ray microanalysis (EPMA) are most development amongst XRA methods. The advantage of all above-mentioned methods in their high accuracy allowing to ensure Sp -0.01 are direot measurements. However this parameter can essentially deteriorate on sample preparation stage because of lnhomogenelty of chemical, phase or granulometric composition. Great systematic errors can appear because of difference between characteristics of analysed and standard samples. Therefore great attention is payed to stages of sample preparation and graduation that are main reasons of accidental and systematic errors. Two main techniques are nost often used for sample preparation: waterless chemical-thermal treatment (СП) and chemical treatment of samples by aqueous solutions (CTAS).The new hybrid method appeared as a result of investigations in these directions. This is the method of chemical-X-ray spectrum analysis (CXRA). The Most important directions of CTT are: 1)selection of universal fluxes with low mean value of atomic number (for example, lithium tetraborate) for chemical homogenizatlon of ores and minerals in melts and for decrease of systematic errors connected with X-ray absorption; 2)select!on of universal fluxes with high mean value of atomic number (for example, bismuth oxide) for chemical homogenization of complicated high-temperature substances (for example, complicated oxides crystals) in melts and for stabilisation of matrix effects in case of sample composition change; 3)oxidation melting of inhomogenious metal samples with formation of glasses;

Ш 4)solution of high-temperature alloys and noble metals containing materials in universal metallic melt (for example, melts of nickel or plumbum; 5)chemical treatment of sample for necessary components extraction into vapour phase and their condensation in thin layer on substrate. The main directions of CTAS are: l)chemical solution of all sample or its individual components and its keeping in next to neutral solution using complex forming reagents, followed by XRA of aqueous solutions; 2)liquid extraction of determined components from aqueous solutions in organic phase and XRA of organic phase; 3)extraction of determined components from solutions into bulk or thin layer sorbent and XRA of solid sorbent. The techniques of CTAS in CXRA are often more simple.They allow easily to add inside standard into analysed sample.But these analysed and standard samples aren't stable in time.The techniques of CTT in CXRA allow to make analysed and standard samples suitable for repeated use and long keeping. Along with 2 above mentioned directions of CXRA suitable for bulk analysis by mean of XRF and XRR methods, the development of chemical EPMA (CEPMA) begins. The different techniques are used in CEPMA; -express chemical display of analysed phases or microsections by means of selected etching or selected painting; -chemical removal of surface pollutions causing errors In EPWA and PIXE methods; -chemical etching under very small angles for lnoreas» of analysed section in multllayered structure "chemical grinding" ). In PIXE method chemical stabilisation of sample surface in situ is perspective. Concrete techniques of performing CXRA and CEPMA are considered on the basic of our own research and literature data of other authors' research. The strategy of CXRA techniques altering for different objects of analysis is being considered.

ЗИ .•BOUT join OSHG IHB пяаимшгш, PAHAMBMRS AKD |твя_— dUCORMOIIOI APJROACHBS MR HALTS IS 07 MATERIALS |*M-19 WISH ORHAI VARIAMOIS ОТ COMP0SITI0« T.I.aunlohava, A.li.Mnkmlantaln, V.Ia.BorkhodoeT Institute of Geoohemletry of Siberian Branch of tha USSR Academy of Solanoaa, Irkutsk, USSR

Relationship equations, correcting matrix effects, with the In­ fluence coefficients, calculated with the help of theoretloal expres­ sion for x-ray fluorescence intensity, assume that the Influence of element i on the analyte i, estimated once, nay be applied for any system. As it Is known, however, this Influence depends on the total composition of each considered sample. Therefore such relationship equations give an acceptable accuracy of analysis only for materials with snail matrix effects or the limited variations of composition. Unfortunately, under routine analysis such situations are not rare when this condition is violated and, as a consequence, approximation ability of basic equations does not guarantee the absence of signifi­ cant systematic error in the calculated oontents for composition of the Investigated material. In the given Information the results of estimating compositions of rooks and steels are shown for whleh eC -correction algorithm 07 doss not provide the required correctness. For rocks abnormally high contents of minor elements result In the unsatisfactory acouraoy;for steels insufficient approximation ability of used correction rela­ tionship is a cause of it. The possibility of refining composition estimation, obtained by relationship eguatlon, with the help of the fundamental parameters approaoh is Investigated. Version of this ap­ proach with the optimisation of numerical Integration after continu­ ous x-ray spectrum of tube, algorithm of whloh Is executed on mini­ computer /V, was used. The ealoulationa showed, that along with im­ proving aoouraoy of compositions, obtained after refining .by funda­ mental parameters approach, the productivities of both correction ap­ proaches sasmsd to be comparable due to proximity of compositions, to be refined and received after using the fundamental parameters ap­ proach. Joint application of these correction approaches permits to extend a list of materials for whloh x-ray fluoresoenoe epeotrometry provides ths required aoouraoy of analysis, and to piok out the tota­ lity of matrix effects correction algorithms suffieient for analysis of materials, composition of which varies widely. Rsf«геном 1. Jlnkelsnteln A.L., Ounlohova Т.Я., Afocln V.P.// J.Aaal.Chem. 1964. Tol.39. P.397-404. 2. •wtfcodoar V.xW/IMd. 1988. Vol.43. P. 1584. 317 THE ШШВШ OF THE Х-НЫ CHARACTERISTIC RADIATIOHs I 1 XRS-20 CALCULATION ВГ THE APPROXIMATE SOLUTION OF THE ' ' ELECTRON TRANSPORT EQUATION

N.A.Gunko, E.A.Tropp, T.B.Popova A.F.Ioffe Physico-Technical Institute, Academy of Sciences of the USSR, Leningrad, USSR Most of the presently known methods for determining the distri­ bution function of X-ray production and the intensity of the characteristic X-ray radiation from the specimen are based on semi- empirical approaches obtained for homogenious media. These for­ mulae include a number of parameters, the limits of their variation being found experimentally or by Uonte-Carlo simulation models. This situation hinders the use of the electron micro-probe analysis for the studies of more complicated objects. This paper presents an approach of overcoming the above men­ tioned difficulties. The approach is based on the solution of the equation describing the electron transport and X-ray production in solidetl]. Analytical expressions for the distribution function of primary X-ray production as well as for the intensity of the primary (electron) and secondary (fluorescent) characteristic X- ray radiation have been obtained. The results for various cases such as homogenious one-component specimen, bulk targets and targets of the type "layer on the sub­ strate" are compared with numerical and experimental data available in literature.

Reference 1. Gunko H.A., Tropp E.A. Methods of X-Ray spectral analysis. Novosibirsk: Hauka, 1986.

3S8 STRUCTURAL CHARACTERIZATION OF CU-ZN-AL-OXIDE- XHS-21 CATALYSTS PRECURSORS'BY MEANS OF XPS/XAES, XRD

AND SEM/EDX

K. Rlchter, B. Peplinski, w. linger and E. Schierhorn Acad. Sci. GDR / Analytical Center, Berlin-Adlershof, GDR Calcined Cu-Zn-Al-oxide catalysts and their precipitated precursors are non-homogeneous samples. Generally, they consist of several-hydroxycarbonate phases; the technically roast important ones are (Cu,Zn)-malachite, (Cu.Zn^COjCOtOj,

and (Cu.Zn.AD-hydrotalcite,

The XPS/XAES data are presented -s "chemical maps" as introduced by Wagner et al./l/. Investigating the Zn related emission ot real catalysts, it was found that the Zn-photo- and Auger-emission differ from those observed with well defined ZnO. The kinetics of dehydration and amorphisation of hydro- talcite was investigated with a novel XRD-in-situ-eell. It was found, that hydrotalcite may exist in two different forms: as a well-crystallized, hydrated and as a partially crystalli­ zed, X-ray amorphous, dehydrated form. The phase transition between these two forms is reversible, and its temperature markedly depends on the Cu/Zn ratio in the sample. The morphology and the chemical composition of the catalysts were .characterized by means of SEM/EOX.

Reference

1. Wagner, CO., Gale, L.H. and Raymond, R.H. Anal. Слеш. 51 (1979) i66

at» A PRIORI ESTIMATION OF ERROR IN X-RAY | 1 XBS-22 SPECTRAL ANALYSIS > •

B.D.Kalinin, R.I.Plotnikov LNPO "BOUREVESTNIK", Leningrad, USSR The standard instrumental error of analysis expressed in concent­ rations is written as: , 6ci = бктГТс ' where <£„- is the standard instrumental error for a set of counts. Assuming that: _

and approximatin(TKi - "V4g thre dependence N = f(C) by the fractional-linear function:

м-Г P + cu ^ - p) *ТГ/ No' where N is a set of counts from pure element* p is the ratio of ab­ sorption properties of matrix to absorption properties of unknown ele­ ment (taking into account additional excitation), К is the contrast (ratio of counting rate for pure element to background counting rate),

AQ is the main instrumental error (relative standard error of counting rate without statistical constituent)/ we obtain:

Values N and К for the given instruments and chemical elements can be determined from counting rates and contrasts of specimens of known composition, values p are calculated according to the expression: f/.-jPi-l. where /j is the relative intensity of line of unknown element in о the specimen (relative to intensity of the same line for pure eleme­ nt) calculated by means of a program for calculation of theoretical intensities. Methodological constituent of analysis error due to nonaccountab- le factors can be determined by the equation: б"сн -N /4cV£Kb °5 U -ГЬ»'» where K.. is the coefficient of influence of factor j on line inten­ sity of element i, D- is the variance of factor j, and r.. is the co­ efficient of correlation between content of element i and influency factor j . The obtained expressions permit to estimate the expected analysis error having a knowledge of metrological characteristics of the instrument.

ЗвО X-RAY SPECTRAL ANALYSIS WITH SEPARATE ACCOUNT OF XHS-23 INTERELEMENT INFLUENCES

B.D.Kalinin, R.I.Plotnikov LNPO "BOUREVESTNIK", Leningrad, USSR

Direct excitation of unknown element i by bremsstrahlung and characteristic X-ray tube radiation

IL = Fi/"u(C)/'t(C)]> (1> We suggest solution of equation (1) in the following form:

a T = aQ + Za-jlj + IjZajjIj * Ip2 pj

i+^BfcyE-.a^c.-cftj w ^r i -I*ijr «j - cp

R are where Lr, k^., Jr»^4Kr theoretical influence coefficients allowing for absorption of primary and fluorescence radiation by the sample (k.• ), additional excitation (B^ ) and absorption of ijr . jr additionally exciting radiation iCJ^t,-) for ranges of primary spec- st ^ trum L j C. are contents of chemical elements j in a standard spe­ cimen for which there were calculated the influence coefficients,

a a are a-, a,, i-j» DT empirical coefficients of superposition of spe­ ctral lines allowing for background and higher effects determined by the method of least squares using specimens of known composition. The expression obtained provides separate account of primary beam polychromaticity, absorption and additional excitation which results in considerable increase of analysis accuracy. Thus, for example, in comparison with widespread method of theo­ retical corrections «/-coefficients) the account of additional exci­ tation according to equation (2) permits to reduce by 2-3 times the inaccuracy in determination of chromium in steels within the con­ tents range 0.1-30%. Similar reduction of inaccuracy due to account of primary beam polychromaticity takes place in determination of Fe in iron ores.

Ml MONTE-CARLO CALCULATION OF X-RAY FLUORESCENCE INTENSITY IN HETEROGENEOUS MEDIA

Kaluzhin A.G. XRS-24 Norilsk Mining a Metallurgical Works, Norilsk, USSR *— —

The model of Monte-Carlo calculation of X-ray fluorescence intensity for multiphase heterogeneous medium has been developed. The intensity calculation is carried out by modified Monte-Carlo method, and the fol­ lowing sinple interaction events are simulated: 1. The direct characteristic radiation excitation with the primary photon, when interacting with the analyzed element. The secondary photon is considered "survived" weighing U, exp(-£"mx), inhere W - the probabili­ ty of atom transition with photon emission; 1 = the lines of characte­ ristic spectrum; Xmx = the gross optical length towards surface. 2. The excitation with the secondary photon, emitted by k-th element, which is part of the sample with assigned weight Ы.. 5. The excitation with the scattered primary photon, having the cor­ responding statistic weight» including scattering sross-section. Only single collisions are considered in this version. The free path length generation waa performed by "maximum cross-sec­ tion" method. The model experiment was carried out for two-phase pulp and powder systems*- In case of pulpa, Polsson'a diatribution of partic­ les assembly in homogeneous accomodating medium was used, as inhomoge- neitiea space diatribution approximation. In this esse the generation of

distance between particles ia performed by the formulas t=-ln(g)/at where a=C_/(C,d); g = random number (0-l)| cn»ci * content (by volume) of accomodating and analyzed phases respectively; d s spherical partic­ les' diameter. Evaluation (for pulps) of contribution to the intensity of scattering radiation excitation effect has shown growth of the latter with particle size increase, and the essential increase of contribution with respect to homogeneous media of analogous composition. The contri­ bution of secondary excitation decreases with particle si2e increase and does not exceed the corresponding contribution value for homogeneous media. The results are presented of X-ray fluorescence intensity calculation in comparison with the reference and experimental data. The program is written in PASCAL and realized in MS DOS >.Э operating system.

312 MTHOD OP июоюбпю свииспмвтю X-HABIATIOB SPBCTIU

I.I. Xondratiev Par Baatern Regional Bydromoteorologlcal Research Institute, Vladivostok, USSR algorithms of programmes processing spectra are being elaborate! by mathematical method». Is a rule, there «re several methods, every- «И of which is used to automate one or more proceaeing stages, usual­ ly, universal programmes bare «tout ten processing atagea (calibra­ tion, localisation of peaka, background aubtraetione, peak area cal­ culation and ao on), mathematical methods wed In programmes determine their complication. She author has worked out mathematical method for automation of several proteasing atagea. The method is fitting parameterea of func­ tion approximating spectrum peak. Junction is being fitted lteratively. Correlation coefficient Is used as optimisation criteria. Correlation coefficients are calculated between spectrum peak accounts and the function approximating it. function fitting is finished when correla­ tion coefficient reach to maximum. The central channel of peak and its full width at half maximum (fwha) are optimised by fitting, ac­ counts in the backgroundleaa peak are calculated by regression equa­ tion, is a function optimising the peak, Sanaa's distribution is used. But any other function can be used as sell. Sue to fitting algorithm we can use a SUB of two Gauss's functions for solving doublets at spectrum. Correlation coefficient used in fitting is a good criteria for evaluating of peak approximation error in spectrum. She suggested method helps to solve several problems of processing! to eaeulate central channel of peak, Mm, accounts In backgroundless peak sad to solve doublets. On base of the suggested method there was worked out an algorithm and a programme "АРОвв". Che programme algorithm includes, besides the described method, a series of other methods which helped to auto­ mate all spectra processing stages. The programme сед be realised on very simple computers with memory volume 24 kB . the first variant of the programme Is created for apparatus spect­ ra processing during X-ray spectrum analysis of ecologioal objects. She second variant Is used for spectra processing during ^-ray spectrum analyses of sample radionuclide composition.

Ф— X-RAY ANALYSIS OP ЯОЯ-НОМООШВОиэ SOLIDS I " XHS—2o N.H.Kraanopolekaya, V.y.Volkov Institute of Physios, Rostov State University, Rostov-on-Don, USSR

Certainly the methods of X-ray analysis (XRA) accomplished for homogeneous samples may be applied as sell for investigation of he­ terogeneous solids, for instanoe, in ecology and microelectronics» Hence the effects of chemical composition heterogeneity and configu­ ration heterogeneity in various points of assay on the resulting ana­ lytical X-ray yield are to be ascertained, Xhe following objects have been examined: - monolayer of solid particlesi - atomic monolayer on massive substrate; - structure formed by alternating homogeneous thin layers. Analytical formulas for X-ray intensity, induced by ions and mono- energetic fluorescenoe are derived. Errors' evaluations are fulfilled for convenient approximations simplifying complicated calculations. Xhe possibilities and applying boundaries of X-ray method for element analysis and determination of some configuration sample parameters are studied. Experimental results that prove the correctness of ob­ tained formulas are given.

ж

Ш- .чг"»:-; ;г::;с: :•::•:;: X-RAY sm-:wsx?\ FOR IUTOHITY Т0ЯЗ IN CkY'/TAL'J XRS-27 ';...,Ku'Wjir:, !5.::.Tro,jaij-So]ov,1an

..и;ч;г. iliy..' ijtntc tfnlverp' tyf ,3aporozhyof U3I3R

Гл.? 1 etter devotes aoriniderati en of results ••f eluctronic etatea :-f Joi'tM 1опв Investigation bacod fiti X-ray spectroaoopy flnta in •.arlons oryatn'.n before and after irradiation and termul effects. :!nder .'.;rftdiation if-, '-ray, t", ots ) of dielectrics we hivo changed electrons distribution in varionp defects of doped crystals. And in majority case? electronic state of this ions chan­ ge and we registatj the valency shift of X-roy lines of ions ( V::;:KL ).

'.'.'e created method for determination cf ViSXIH. [1] • The theoretical value of VoXKi. far Or K^ -line under Cr3+ - Cr transition equal i .96 e>/. Then the experimental one changes from 0.2 to 0,95 eV ;• variant crystals. In this cas= wc may determine the eonoentrat.-.i at change valency iona [21.

Tiie similar Investigation implemented for oxide crystals doped by 3rd- and4-th-ionsp 'He put out the data about stability of varions electronic states of regular ion3 in alkali-haloid crystals arid ones with pcroVBjjite structure i3>. For these results we have the best agreement with optical and ЮН-data und the main principles of defects creation in wide zone crystals were proposed.

Keferences

1 Kulagin N.A»,3viridov o.T. The Methods of Bleotronic Structure Calculation For Free and Impurity Iona. M.: Uauka, 1986. 2 Kulagin H.A..Sviridov b,iy/j.phy8.C.1984. Vol.17. P.4539. 3 Kulagin N.A.,Sandulenko V.A.,TroJan-Golovjan G.NV/Ooll.Abst. X11 SCK. K.,1989. Vol.1. P.373.

MS X-RAY FLUORESCENCE ANALYSIS WITHOUT STANDARDS XRS-281 A.Marchut Institute of Petroleum Processing,Krakow, Poland The fundamental parameter method has been a powerful technique for spectrochemical analysis. In most cases this technique with use of standard is applied. The alternative way is the method without stan­ dards. In this method the measured itegrated intensity of radiation (E) of analysed element has to be correoted due to counter effeclency

(w1), integrated reflection of crystal (w^), transmission of radiat­ ion (Wj) by gan in measuring chamber and transmission of radiation by filters. So, the corrected intensity of radiation (I) oan be expres­ sed by equation,

T Б сд *1 • wk ' w1 • V where to Is the angular rate of crystal. On the other hand the corrected intensity given by the above equat­ ion can be at the same time expressed by equation given by Shiraiws and Fujino. The set of such equations for the analysed elements in the sample can be solved in numerical way. The fundamental parameter method without standards has been app­ lied to analysis of alloys» The brasses containing six elements in one case and three elements in the other were analysed. The chromium tube, flow proportional counter, LIP 200 and L1F 220 were used. The analyses were carried out with use of vacuum in measuring chamber. The obtained concentrations of metals in the analysed alloys have baen compared with the concentrations evaluated with the help of fun­ damental parameters method with use of standards.

Ш INFLUENCE OF DBPENDEKCE OF oC -COF.FFICIERTS FROI! CHEIIICAL I XRS-29 COf'POSITIOM OF SAMPLES OH RESULTS OF X-RAY FLUORESCENCE I —Li AHALYSIS OF STEELS E.I.tfolchanova, A.K.Smacunova, T.K.Gunicheva State University, Irkutsk, USSR In routine analysis U.K.de Jongh method A/(DEJ) is widely used In which the л -coefficients are accepted constant. However in x-ray flu orescence analysis of materials with great variations of chemioal com position in general«(-coefficients are not constant values.The simple algorithm (LAC), approximating the change of oc-ooefflclents with in­ crease ofinterferringelements concentration from 0 to 100 t, is pro­ posed in the paper [Zl. The fundamental parameters method 1в rarely used for x-ray fluoresoence analysis of steels beoause of its low pro ductlvity. Version of this method /"3/(R0U) decreases essentially the analysis time on account of that the influence coefficients are deber mined only once at the first iteration step of the contents calcula­ tion. Ve compared the efficiency of the mentioned algorithms under x-ray fluorescence determination of Cr In steels, elements concentrations in which are changed within ("): Cr from 0 to 30, Ml from 0 to 3*, W from 0 to 24, Kn from 0 to i7, "o from 0 to 6, Co from 0 to 10, V from 0 to 7, Pe from 50 to 99 et.eet.The shown range of compositionc, to be determined, covered chemical composition of 456 different marks of high-speed, high-alloy and low-alloy steels.Under realizing LAC al gorlthm oc-coefficients were calculated for case of the change of the interfetirrlngelements concentration from 0 to 100$, and also inside the real ranges. It is obtained, that the required accuracy of results of x-ray fluorescence analysis of steels is ensured by LAC algorithm on account of inoludlng oC-coefficients. In в real analysis conditions the errors, arising because of the difference of the samples micro- structure and the inexactness of the chemioal analysis data exist al­ ways, therefore may consider that aocurranoiaa of all three algorithm* ere like. It should be noted, the good results given by the DEJ-algo- rlthn were obtained only after the optimization of construction condi tlon of the calibration function C,/(1+ Z«L.eO>f(I.). References

1.d» Jongb W.K.// X-Rajr Spectrin. 1973. Vol.2. P.151. 2, laohanoe G.R.// Paper presented at the International Conference on Industrial Inorganic Elemental Analysis, Nets, France, June 3. 1961 S.Rousseau R.M.//X-Ray Spectrom.198*1.Vol.13. P.115.

M7 CALCULATIOH О* SECOHDAffif ЕЛИТАТЮИ EPHS01S IK Л-HAY | j XHS-30 M.UOifjiBCiiNCK ANALYSIS OP SURFACE SOLIDS ' ' I'.S.Uaumtaev, V.P.Volkov Institute or Physics, Rostov State University, Hostov-on-Uon, USSR

The accuracy of X-ray fluorescence analysis ( Jffli'A ) depends upon the correct calculation of secondary excitation effects of various nature. This exploration is devoted to examination of X-ray analy­ tical intensity secondary excitation by photons, photoelectrons and scattered radiation. Influence of the distribution function form and parameters on the intensity in admixture analysis of solids' surface layers is also studied. Formulas for calculation of various secondary excitation effects are offered as well as the experimental results confirming the cor­ rectness of proposed formulas.

m X-RUf SPBCTROHBIRI IB ИОН-FBRRODS HBTALIOTKf Г~~ A.P.Hickolsky, B.I.Verhovsky I "31 ОПТ Complex SOXUZISVKTMBTAVTOIUTICA lloeoow, USSR

X-ray spectrometry method - one of the main methods of in­ dustrial analytical control In non-ferrous metallurgy. All in all more than 200 X-ray spectrometry complexes equipped with computers and systems of sampling) samples transportation and preparation are used at the enterprises of non-ferrous metallurgy. In non-ferrous metallurgy it is necessary to perform analysis within a rather wide range of elements to be determined (practi­ cally all the periodic table) and their contents - from trace ele­ ments to those close to 100£. It is necessary to define traoe ele­ ments contents in super pure substances, including noble metals, high contents - in alloys of non-ferrous metals, including noble ones. When determining high contents in alloys a high accuracy of analysis is required, for example, in brass containing 90% Ou accuracy should be no less than t 0,1$. It is necessary to make pulp analysis in stream with low limits of detection, for example, for copper - within the range 0.01% with the content of solid 20;'i, that is in fact within the range 0i002£. Analysis of noble metals and noble metals containing substances is a special chapter. Objects of this class analysis vary in con­ tents, aggregate state, properties. Beside the objeets of analysis listed above there are many others, less specific objects (ores, concentrates, slags, pulps and others). Howdays X-ray spectrometry is used in the enterprises of non- ferrous metallurgy for analysis of alloys on the basis of Cu, Hi, Al, noble and other metals, ares, and products of their processing, pulps, materials of alumina production as well as other materials within the range of chemical elements oontents of 0-01 - 100% and within the range of atomic numbers Z « IIHa - 92V. "

24.3aic.4I3 ЗИ A PROGRAMME SYSTEM FOR AUTOMATIZATION OF METHODICAL AND STATISTICAL INVESTIGATIONS IN X-RAY AND AES QUANTITATIVE ANALYSIS XRS-32 N.v.Pershin, A.A.Golubev. V.l.Mosichev, V.V.Vasal*ev Central Research Inatitute for Structural Materials "Prometheus", Leningrad. USSR

A programme system for EC and IBM computers is designed. The system includes four main subsystems: regression, optimi­ sation, statistical and theoretical modes. The regression subsystem allows to estimate linear and various nonlinear modeIs by different methods i.e. stepwise regression (for multidimentional polynomials). gradient methods, simplex method, adaptive Monte-Carlo methods etc. The optimisation subsystem allows to construct D-optimal and quasioptimal de­ signs of calibration standards. The statistical subsystem provides various statistical investigations. The theoretical subsystem is designed specially for X-ray analysis. The ori­ ginal fundamental parameters program with theoretical appro­ ximation of primary spectrum is used. It allows to take into account different second and third order effects, thus provi­ ding relative accuracy of theoretical calculations within 1 - 3 *. The original semitheoretical approach (1,2) is inc­ luded, based on the use of optimal designs of hypothetical standards, fundamental parameters method and calibration equa­ tions with separate account both of instrumental and of matrix absorption and secondary fluorescence effects. All subsystems are interconnected. Due to special dialogue software outworked the system is easy to use by nontrained analysts. References 1. Kosloher T.I, i Parihin Ж.Т// Abatr. of XX Coll. Spectr. Int. Prague. 1977 P. 196. 2. Koslehar V.I», Pershln H.Y., Vloolwr G.IvfCan. j. spectr. Tol.29, I 2. P.39-62.

170 REGRESSION EVALUATION OF EFFECTIVE PARAMETERS IN I FUNDAMENTAL EQUATION FOR X-RAY ANALYSIS |Д8-33

N.V.Pershin, A.A.Golubev, V.I.Mosichev, S.I.Nicolaev Central Research Institute for Structural Materials "Prometheus", Leningrad. USSR

It is known, that fundamental parameters method is based on the use of equation

C* - cf ( I* / if , ( Ftf".?- ,g )/F(S*.P* .J , 1 a a a a where £ . t . I . I - concentrations and intensities of elements for analysed sample ( x ) and reference standard ( st ). F( С P. a ) - fundamental physical equation, p - inst­ rumental and 9 - fundamental parameters.

The accuracy of the method is directly dependent on accuracy of reference standard and parameters P and g used. In order to minimise errors, caused by these factors, a new method is pro­ posed. The method is based on regression estimation of correc­ ted "effective" values for С and some instrumental parameters P (incident and take-off angles of spectrometer, parameters of X-ray tube and primary spectrum etc.). For this purpose limited set of calibration standards is used, the composition of which is preferably close to that of samples analysed. A special non­ linear method is elaborated, which gives the effective values of parameters, providing the minimisation of differences between chemical and calculated values of concentrations.

The experimental verification on Fe - Cr - Ni samples showed that the method proposed provides 1.4 -2.4 gain in accuracy and 3-5 gain in precision. Effective parameters are calculated only once on preliminary stage of methodic developments. For routine calculations the initial computer program with corrected "effec­ tive" parameters is used. Thus, the analysis time does not change.

171 SEPARATE ACCOUNT OF MATRIX AND INSTRUMENTAL EFFECTS IN QUANTITATIVE X-RAY ANALYSIS OF XHS-J4 ELEMENTS NOT PROVIDED WITH STANDARD SAMPLES

N.V.Pershin. V.I.Mosichev Central Research Institute for Structural Materials "Prometheus". Leningrad. USSR

А пен method for calibration of X-Ray fluorescence spectrome­ ters using scanning spectrometry channel is proposed. The me­ thod is based on a separate account of matrix and instrumental effects and needs no calibration standards for the element anal­ ysed. The matrix effects are accounted theoretically, using fun­ damental parameters, the radiation losses in spectrometry chan­ nel are accounted with the help of the spectral function of ra­ diation losses (SFRL). The latter is found by comparing the ex­ perimental and corresponding theoretical relative intensities. obtained on a limited set of pure element emitters. For calibra­ tion in the whole spectral range of XRS (0.3 - 10.0 X) it is sufficient to have 10 to 15 pure element emitters made of most wide spread elements. The method provides a promt development of quantitative analysis for the elements which are not provided with standard samples, and the preparation of pure element emit­ ters for which is impossible or problematic. The practical verification of the method was made using scanning spectrometer Philips PW 1200 "C" by analysing a set of 146 standard samples. covering a wide group of Pe-, Ni-, Co-. Sn-, Zn-, and Al- base alloys. The mean relative error of the method was 3 - 5 Я in ana­ lytical range 0.1 - 3.0 wt *. In addition it was found that SFRL. which is a pure instrumental characteristic, can be also used for correcting some fundamental parameters, in particular those, characterising the comparative effectiveness of sxitation of lines, relating to different atomic series. The method pro­ posed, can be used in X-Ray microanalysis as well.

S»

^ MICB0GE0METRICA1 EFFECTS OP THE SAMPLE SURFACE HI THE И'А, PQLYCHROKATIC APPROXIMATION I ХНв-зТ! K.A.Portnov, B.I.Kitov, A.V.Smagounov, V.V. Seleznev I —I Irkutsk State University, Irkutsk, USSR The quality of the sample surface is one of tbe reasons tbat creates a strong dependence of tbe accuracy on tbe analysed signal. Ibis process bas not yet been studied thoroughly. We created a ma­ thematical model allowing to calculate the fluorescence intensity of a sample with rough surface radiated with a polychromatic primary fluorescence. Tbe spectral distribution of the tube is given with re gard to tbe backword dispersion of electrons in anode and tbe abeor ption of fluorescence by tbe anode material and by the tube window. This model was checked on a wide range of powder and moulded mate rials of various element consistency: sphalerite, caesiterite, bueb nerite,qalenite, bronze, brass, high carbon steel, high manganese steel, For tbe measurements on the roughness parameters of moulded Bamples a roughness indicator was used.

She calculating experiment proved tbe influence of sample surface quality on tbe analysed signal being affected by many causes among which the main are the shadow and the screen effects. The force of these effects is determined by tbe surface raierogeometry, tbe spec trometer geometry and the sample chemical contents.

As it was found out, tbe use of tbe monochromatic approximation in analysing rough surfaces may in some oases considerably distort the results. In tbis paper it is shown that alongside with the well known instrumental method of compensation for tbe surface quality effect, there exists the possibility of an analytical approach to this phenomenon and this approach lets to minimize the influence of the sample surface roughness in tbe KPA while using serial apparatus.

373 COMPARISON OP DIEFiSRiaJTIAL AND INTEGRAL APPROACHES TO METROLOGICAL ATTESTATION OP AUTOMATIC SXSTSNS FOR ANALYTICAL CONTROL A.N.Sm&gur.ova, V.A.Kozlov, O.H.Karpukova, D.P.Nalobin, v.G.Ivanov Irkutsk State University, Irkutsk, USSR A differential and two types of integral approaches are proposed for metrologies! attestation of automatic systems for analytical control (ASAC), baaed on x-ray fluorescence analysis [ij . As to the first method, any ASAC subsystem is characterized separately. For this purpose descriptions of the experiment plans and methods of sta­ tistic treatment of its results are given in order to estimate random and systematic errors of each individual subsystem. Gene - rally metrologies! characteristics of system on the whole are es­ tablished by summation of all estimates obtained for subsystems. Two experiment plans are given, which allow to estimate metrologi- cal characteristics of the whole system ( the integral approach ). As to the first plan two knives must be established in the sample pi­ cker. The knives pick out two samples independently, nearly at the same time. This method allows to take account of the work qualities of all subsystems besides the sample transportation subsystem into the analyser. The second experiment plan is based on the preparation of synthetic slurries from the known composition samples and on their establishment into transportation block. In this oase the sample picking subsystem attestation is excluded. It is shown that the integral approach advantages in comparison with the differential one are shortening of attestation experiment duration and decreasing of labour expenditures. Its disadvantage is absence of information about the qualities of ASAC individual subsys­ tems. The integral approach is recommended to use under ASAC perio­ dic metrological verification. When ASAC attestation is for the first time the integral approach may be applied only to ASAC working properly.

Reference 1. Kozlov V.A., Smagunova A.N., Karpukova O.M. et al // Abstracts of the 2nd Heating of X-Bay Spectrom. Anal. Irkutsk (Soviet Union), 1989. P. 135.

374 Tvo Nev approecbu to Saai-Onantitattve Kontgen n

Ё.8.А. Salt tod J. da Croot, 1*1 ГЬШра, Lalyvof 1, 7602 EA Alaelo, Ям katnTrlanaa

Tiro Saat-Ooantltatlva eototiooe are presented- Seei-Quantltative analyals can ba aufflclant for preanalyala, check on contamination», and ad hoc problaae. •oth taai-Ouaatitetlva epproechee five rough indication» of too total coaaoiitiea of uoknovn aaaole» In the case liallar atandard» nor ragreaaian line» an present. Solid», llquida, aaall odd ahapad eaaple», loo** pandora can bt anelyeed aa auch. sealQeantt Starting froa a aean «corded by MO SaalQeant perfomea the follwing atopa by typing ona «ingle cniinii flrat It parforaa an autoaatlc qualitative analyals I.e. the background la flttod, tho peeka a» found and thay an identified. Secondly tba prograa aalacta neceeaary and optlaal ataadarda froa a ua« «applied databeee of «tandarda and eatleate» tba total coaposltlon using Crlaa rwdaaentel 'araaatera, or fklllpa' Fundaaantal Feraaetare. PniOnant»! Intanaitle» ara obtained by an 1*0 analytical Program that aaaauras «p to 60 aoat coaaonly occwiag «liainti and 7 background poaitiou. Iba concentration» of the»» elaaent» ara calculated If their concentration la larger than 0.01 X, and an eitiaated arror li given, standard! covering all eleaanta ara delivered «ith the prograa. * Product of V. J. da Jongb, Onega Data Syataae.

1Я BSTMATIOM or ЩИЮМвХСАЬ CHARACTBRISTIC3 X-RAY spacTROsco?r BI тнв июнов or сжна о» ВГОВТЮШАСТ XBS-39 V.A. Sukhenov, V.H. Belot, Ph.G. Unger foaak Stat» UnlTereity, Toaek, USSR bet ua examine Шит oallbratlve dependence Y • AC + B, (1) where X la analytical elgnal (A.S.), С la unknown concentration, A and В are paranatal*. A rang* of value* of parameter» A and В can b« dataminad by the ayeten of inequalities, ao aa A.S. la maaaured with tha error £ i *e for l f 171. (a) Polygon (2) «a oan oall polygon indeterminacy and mark by tha let- tar Л . It can be put Into eome ellipaie A.,, equal ( 0, P > 0, E>0. bat it be attached to measuring concentration of the pfaaae A.S. equal

У0.Then «a oan find aatiaatlon of concentration Cg free above and from below altb. tbe balp of formulae:

,Ta-B-£. /*«•**£ \ 0. • aln I ° к CI • aax I I . Attached to appro-

xiaation of the plurality Л by elllpala Л 1 we have:

0 (B,A)f Л, I A ' e (B,A)f Л,1 А ' To deteralne nuabera BJ and 5J it la naseesary to eolve two extreme ргоЫеаа:

-fi -* Я" attached to BS2 + 2DXY + FY2 • 1j Y • X x»r *°- * -ft^ -» *>* attached to ВХг + 2ПК + И2 « 1. .Their deoi- Y + J *»T alone oan ba narked through

у £ -fl-x; Y0- e -%-x* 4 " ' „« « » "о " "Гр f I » <*•»* В and X are eetiaationa of paraaetera В and A.

*7» THE IHPbOEHCE OP ATOMIC NUMBER OH THE SEHSITIVITY OF XRS-40 Sir ANALYSIS WITH THE USB OP VARIOUS CRYSTALS B.Svardalova*, T.Belan**, V.Lasarova «• Reeaarch Institute of RHKG, 702 00 Oetrara, CSPR Trinee Iron and Steelworks, 739 70 Trlnoe, CSPS The oomaerolal exploitation of "multilayer" pseudoorystels (Lay- red Synthatio Mloroitruotures) for tha analyala of light and ultra­ light alamanta rapraaanta tha «oat important progress in ZRF spectro­ metry of today. To evaluate tha propartlaa of varioua oryatala «a compared the sensitivities of datarmination of В, О, О, Р, Ha, Hg, Al and Si with the uae of 1Я1а AZ 11 (2d • 11,1 nm), AX 06 (5.7 nm) and AZ 04 (4.46 ив) and natural crystals TUP (2.58 nm), АЭТО.Об na> and PET (0.875 на)* measurements vera performed on tha simultaneous­ ly-sequential apeotroBetera ARL 8680. Aa it oould he aaen on the graph tha AZ 06 crystal oan be used for «Ida range of light elements. We use It for the analysis of me­ tallurgical alags, sinters and oast Iron. The AX 11 is a proper crystal for the determination of С in pig Iron and oast iron,but It is not sensible enough for tha determination of low oontents of С in ateal.

11 12 J3 14 tt.lo m> a* Ai и

377 X-RAY ANALYSIS USIHO SPECTHUM EXCITATION BY MOHOENERBETIC IKS-41 FLUORESCENCE, PBOTOHS AND ALPHA-PARTICLES V.F.Volkov Institute of Physios, Rostov State University, Hostov-on-Don, USSE

X-ray analyuis using spectrum excitation by monoenergetic fluores­ cence, protons and alpha-particles has spread widely in solution of analytical problems for ecology, microelectronics, production of pure and superpure matter. The following problems axe examined in the research! 1. Secondary excitation deposit in analytical peak intensity (secon­ dary exoitation by 8*-electrons, secondary photons and scattered radiation). 2. Excitation conditions, devioe constructive parameters and sample preparation optimization in order to increase the spectrum cont­ rast and to lower the detection limit. 3. The spectrum treating methods for multielement specimens ur ng the semiconductor deteotlon. 4. The metrological characteristics for some particular analytical methodioa In «oology.

178 UTILIZATION 0? ALPHA SOURCE FOR ELEMENT COMPOSITION !.„, „ I XHS-42 DETERMINATION BY X-RAYS AHD GAMMA-RADIATION ' ' V.F.Volkov, V.N.Sinitaln,B.?a.J)unduchenko,Xa.V.Kabirov Institute of Phyalca, Rostov State Unlvereity, Eoatov-on-Don, USSR Ionization croee-eections for atom inner shells by 5 MeV alpha- partloles are comparable «rtth photoionization croaa-aeetiona by X- raya for elementa with 5£Z£30 t13 • *8 the alpha-particles brem- satrahlung intensity la low, the utilization of alpha source (alpha-particles energy is 5 MeV) for X-ray characteristic spectrum excitation and detection of light element concentrations is to be highly auoceaaful. Simultaneously the nuclear (et, v^-reaotiona with energy of gamma-radiation from hundreds of keV up to several MeVa occur. They make it possible to determine concentrations of elements from Li (Z - 3) to Oa (Z - 20) [2] . The following parameters aro determined with the experimental set up including alpha source block for spectral excitation, Ge(Li)- and Si(Li)-apeotrometers and pulse-height analyzer AI-4096> the beat ar­ rangement of source, specimen and detector, when the "aignal/fon" ra­ tio i» the greatest( X-ray spectra deteotion limits for elements with 17*ZO0 (10"4- 10~3SW» nuclear reactions spectra detection limite for elementa with 3*Z*11 (0.1 - 0.5%). The obtained detection limits are sufficient for routine analyaia of product» of metallurgy, raw raaterialao f cement industry and some other nature and biological sample».

References

1. Voldeet E.//Prikladnaya apectrometria rentgaoovakogo ielutchenla. M.. Atonlidat, 1977.166 P- 2. Deoonniok G., Demortier G.. Bodart P.//Atomio Energy Review, Supplement В 2, 1981. P.151-234.

37» ШЕНЗТ DISPERSIVE I-BAY FLUOBESCBHCE AHALISIS XRS-*3 0? GB010GICA1 STANDARD REPBRBHCB MATERIALS USING THE AHFA SOFTWARE PACKAGE M.K.Vuchkov, P.Bavezova*, E.Karaivanova", Z.Halacheva* Institute of Nuclear Research and Nuclear Energy, Sofia * Geologioal Enterprise for Laboratory Research, Sofia, Bulgaria

On the basic of THE AEFA software package multiple international geological standards with significant interelement effects and broad concentration ranges have been studied in order to develop a general analytical program for x-ray fluorescence analysis of geological ma­ terials. The measurements have been carried out using link 860 spectrometer and a user developed excitation system based on an Am annular source. A set of international geological standards and their synthetic compounds has been used for analytical calibration applying the fol­ lowing mathematical models, incorporated in the AEPA package: 1. Linear or additive intensity correction model: N °a • °. • E *Ii'h i 2. Full linear/quadratic/multiplicative intensity correction model H H Ca- "°. Kii-Ji + hi'x'z± i t d 5. Linear md multiplicative intensity correction model:

°." «. • (I i 4. Lucas-Tooth and Pyne intensity correction model:

°. "A o *h- V

381 DEVELOPMENT AKD APPLICATION OF JCHF ANALYSIS POH DETBRKINIHG XRS-45 ELEMENT COtlPOSITIOH AND SURFACE DENSITY 07 UNSATURATED SAMPLES" 3Y USII.'G THEOHETICAL CORRECTION METHOD A.N.Yeritenko, A.L.Tavetyansky KPO "Sojttztavetmetavtomatika11, Northern Caucasus Division, Rostov-on-Don, USSR

ХНЕ determination of composition and surfaoe density of unsatu­ rated specimens is difficult because there are no certified unsatu­ rated standard samples*

Therefore it is important that some XRF procedures aiming at de­ creasing the number of the required graduation samples should be worked out. This can be done with the help of theoretical correction for interelement influences. In the present paper a version of the theoretical correction tech­ nique in which correction influence coefficients are calculated in the 'point' of the reference sample has been developed.

This version is valid when there is great difference in the com­ position and surface densities of the unknown and the reference sam­ ple. It doesn't require knowledge of the surface density which can change up to the value corresponding to a thick sample.

The paper is also ooncerned with the case when X-ray lines not of all elements are measurable. Then correction for the influence of the undeterminable elements on the fluorescence intensity of the de­ terminable ones is introduced by measuring Compton scattering inten­ sity of primary X-rays.

Analytical expression that conneots values of interelement influ­ ence coefficients calculated for various reference samples has been obtained. It simplifies transition from one reference sample to ano­ ther and serves as a base for tabulating influence coefficients. Testing has been made by mathematical simulation methods for a large set of samples Hi - Cu - Ga - As - Se, and by using experiment­ al data for a number of Se » Hi compositions.

3M CLASSIFI3A1I0H OF GHASOATION FIELDS Ш НОКРАИАМЙГШСI RECTOBATIOH OF ИВРЕИШВНСЕВ 1И 2C-HAY SPECTiflJH ANALYSIS [____ V.II. Zavgorodnly, A.P.Nikolskiy Industrial Scientific and Technical Complex "Soyuztevetmatavtomatika", Koscow, USSa

Quality of X-ray spectrum analysis depends on considerable extent on the selection of subset of elements of the graduation field applied for plotting graduation dependencies.

Successive analysis of initial data allows to take maximal advantage of useful information for predicting the contents of components defined.

The initial graduation field is distributed to classes with the help of iterative procedure by dynamic condensation method and distribution quality is defined. The sample analysed is attributed to the relevant class judging by greatest proximity criterion in optimally selected metric.

Nonparametric assession comes to plotting local graduation dependence individual for each sample and every element in the sample analysed. The selection of setting parameters corresponds to the quality of initial field destribution.

In the report the comparison of nonparametric analysis results with content assessment made by regreselonal gradua­ tion dependences for certain materials is performed.

383 DETERIOHATIOH OP THE DEPTH PROFILE OP IHOM I СОИСЕЯТЙАТЮМ IH PE-HX STRUCTUHE BY PIXE AHD ВНР METHODS I XBS^7 V.A.Altynov, R.A.Ilkhamov, A.P.Kobzev Joint Institute for Huelear Research, Dubna, USSR R.Sandrlk Institute or Physics, EPRC SAC, Bratislava, Czechoslovakia The depth distribution of iron in the Ре-Mi structure «as studied by applying the PIXE as well as the MP methods. In the ease of FIXE method the concentration profile was calculated by modelling the de­ pendence of the experimental X-ray yield on proton energy. The ef­ fect of the secondary excitation of iron by K^ radiation of nickel was taken into account. The method allows one to determine the con- . oentratlon profile of iron with a relative error of abouth 10% near the sample surface and of about 30% at a depth of 15 Mm. For comparison the Iron concentration profile has also been deter­ mined with a destructive technique. Por this purpose the transverse section of the sample was scanned using electron mlcroprobe (EUF) and Kgi X-ray yields of Fe and Hi were measured. A good agreement between the profiles determined by PIXE and EUF methods up to a depth of 10 ит was achieved.

1

SM APPLICATION 0? THE X-RAX FLDORESCEKCE AHALXSIS POR I 3T0ICHI0MBTRY COBTROL OF COMPLEX OIIDES |XRS-»B

A.B.Blank, B.I.Shtrtior, Z.M.IartoTa,s.Yu.SumarokoT Institute for Single Oryetala, Kharkov, USSR Single and polyoryatala of ooaplex laorganlo oxldaa art uaed la eleotronlea, eelntillation, laaer and high temperature aupereondue- tlng technique. The X-ray fluoraeoanoe analyaia la on» of th» proaialng method» for material stolehloactry oontrol duo to high rmpldnoa» and aoouxa- oy and alao noaaibillty of alaultaneoue determination of aararal »le- nonta (fro* В to U). Sine» th» praaant day derloe» are characterised Ъу low level of apparatua arrora, the dominating factor for th» ane- lyala arror la th» ргоЪ» preparation stag». When different flux»» (borate» and phoaphatea) are uaed, th» influence of production aetboda of ealttera Is the foxa of glaaaea £л] on the total analyala error waa etudied for a number of ozlda ayatama. It la found that method» of emitter formation from the aelt with free aurfaoe la characterised by the minimum arror «hen the abaper temperature la a» low aa poaalble. It la ahown that fluxea on phoa- phataa aatlafy theae oonditlona beat of all. Iheae fluxea hare eom- paratlTely low fuelon temperature (750-950 °0) and a «Ida temperatu­ re range of glaaa formation. Obtained emitter» don't require annea­ ling for relaxation of theraoelaatlo atraaaea &J,

When th» analyei» of XGd(V0.)2« SrTIO,, La,Qdc8lO1.>0d2Sl0., yB*2Cu30z' 11)Вл2Сл2Сиу0х' B10.7?bO.3C*S2ei.8Ox ** *•*• *хЛ ta* СГУ»- tal dlffraotlon analyeer la uaad ayateaatlo error» aren't higher than 0.3-0.6 rel.H. The tlae needed for the whole analyele of three •amp­ le» Including th» probe preparation «tag» la « 1.5 hr.

Rafereneea

1. Afonln V.P., Gunlohera Т.К., Plakunova L.P. She X-ray fluoraacent alllcate aaalyela. Novosibirsk,: Пайка, 1987. P.114, 123 (Ruaeian). 2. flaalnoahenko V.P., Kbtok L.A., Shlaanekaya I.P. et el// Dokl. Akad, "auk Ukr SSR. ser. A. 1987. - • 11. P.52-84 (Ruaaian).

25.3aK.4I3 see РЕКРлВАМОЯ Of SFSCIHBIS FOE X - BAT ВРИИШМ INAIXSIS HI

T.P.Blanhcuk,J.V.e»vlna,T.P.lhumlava(V.G.Jtoetin Gintsretaet, Moscow,USSB X-ray apeotrum analysis la widely used today to analyse auiti-ooapo- nent powder produots of пов-fenous Mtallnrgy.Bowaver results of euoh analysis are Influenced to • gnat extent by ehenioal compoaitlon,foxm of oompoand and degree of ooamlaution of the Bpeelmens.Application of «intoning for preparations of euoh specimens «How» to exolude those factora.The inreatigatlon carried out resulted la a uniTeroal method of sintering specimens for slaultaneous multi-elemental analysis of di­ fferent produot» of pyronetallurgy and ore-dressing,containing 8,by X-ray epoctrua analysis. aberaal grarimetric and X-ray pbaa* analyaee show that abas sustan- oea containing S,suoh aa Cu sulphides and sulphates,pyrlte and eulphur intaraot with ainter mixture 8 does not volatilise below 122J-1273°K. The meobanlam of the ohaaloal prooeaaaa going on while beating the pro- ducta andar atudy to the given teaperaturea waa investigated and opti­ ons reglaea of heat treatment were ohoaen. A mixture of Ы metaborate, Из or Za oxides and Ha oarboaate taken In apeolflo proportions was ohoaen as test slater mixture. The seltlsg aixture proridea a low-meltlag and low-Tlacosity salt whloh does not reaot with the graphite and forma a highly hoaogeneoua glasar substance with alnlana surfaoa atralna after oooling.Zbe eamp- lea obtained are hoaoganeoua In oomposltion and hare even aaooth sur­ faces free of oraoks. Hoaogenlety of the samples was examined by SBV- 01 electron alorosoope famished with "Мах" adaptor made by "Philllpa". She suggeated method of preparation enablea analyeea of different materlala to be performed with only one tjpa of calibration charts whloh improves the апаЗуаев capacity. Tb» following spectrometers, "»luoroprlat",8ail-20 and ВВП-гон were used for the Investigations with a computeriBpeolaens were melted In graphite crucibles la "Hersog" aeal-autoaatlo furnace. Che determinab­ le oonoentration lnterfala for 8,Cu,ag and Oa arei О.З-ЗДЦ 0.5-2?*) 1,2-12.49Ц 6-12)1, and their root moaneinaro derlations are 0.09-1.28) 0.016-0.52* 0.01-0.05) 0.48-1.15 гевреойтеЗу. the «bore method is proteoted by inrention certificate •о.-идою.гав.

3M CHOOSING OPTIMUM CONDITIONS OP SAMPLE PREPARATION IS XRS-50 X-RAY FbUORESCEHCB ANALYSIS OP CEMENT PRODUCTION MATERIALS

I.V.Bogdanova, V.N.llaximov, ?.R.Alperovich Glproteement, Leningrad, USSR The mineralogies! and granulometric differences in the nonmetal- lio materials matrix are levelled through sample transformation into the eolld eolation by means of fusion with glass-forming fluxes. The studies performed showed that a mixture of the lithium tetra­ borate with one fourth of the lithium carbonate containing 3-5* of an oxidizer should be considered as the best flux for the cement production materials with a wide range of the composition variation (clay! sand, limestone, clinker, cement, iron and sulphate additi­ ves, blast-furnace slag etc.). It is more convenient, slmplb and economical to prepare emitters by fusing a mixture of the sample and the flux on a graphite disk according to the method developed by the Institute of Glprotosment. the temperature-time factors and the sample-to-flux ratio were studied for optimization and unification of the fusion conditions.

It was found out that the stabilization of the Intensities of analytical lines of J^s Si, Ca, Ve, Al, Kg and S sets In by the fifth minute of the fusion at a temperature of 950°C and the sample- -to-flux ratio of 1<5. The matrix lnterelement effect decreases sub- steadially at such a dilution. A further increase in the sample di­ lution- with flux results in a molten viscosity Increase, a reduction of the chemical and mechanical stability of the fused layer, a sub­ stantial decrease in the concentrations! sensitivity and In an in­ crease in the analysis reproducibility errors. The elevation of the fusion temperature above 950*C is accompanied by loss of suoh vola­ tile elements as sulphur, chlorine, alkali metals. The chosen opti­ mum conditions of the sample preparation allowed for use for all the mentioned materials of single system of multiple regression equa­ tions the correlation coefficients of which are determined from a rather limited set of 20-25 standard samples. The X-ray fluorescence analysis procedure developed can be used in laboratories of solenti- fio-researeh Institutes as well as (when somewhat simplified) in la­ boratories of industrial enterprises.

387

4*L X-HAY. SPECTRUM FHJOHBSCEKOE AKAMSXS OF CARBOH-BASED MATERIALS B.G.Cheblakova, V.A.Egorova, V.u.Murashkina, A.J.Kuteinikov XRS-51 HIIGraphit, Moscow, USSR The possibility of using an X-ray spectrum fluorescence method for analysis of carbon-based materials (petroleum coke, coal tar pitch, mixtures, and graphite) has been considered. Results of investigation on the development of methods of X-ray spectrum determination of additives (Si, Mn, Al) and impurity elements (Mg, Al, Si, P, S, V, Be, Oo, Hi, Zr, Hf, V, etc.) in carbon materials using a non-dispersion X-ray analyzer ffAFG-1 (USSB) and X-ray fluores­ cence scan spectrometer VEA-ЗО (GDR) with a control computer "Blectro- nika 60 IF* are presented. Procedures of preparing samples for the analysis and peculiarities of determining individual elements have been considered. In terms of measurements made on model specimens a model for accounting the mutual effect of the elements is selected. Besults of the experimental defining of the limits of detecting 28 impurity elements in graphite are presented. The detection limits ran­ ge from 1. 10-3* to 1,10~^% by mass depending on the element atomic number. Metrological characteristics of the developed X-ray spectrum fluo­ rescence methods are presented which comply with the requirements put to chemical and atomic-spectrum methods of analysis.

зав Z-R1I 1H1LYSIS OF THE TRACB ELEMENTS m iMOSPHERIO 1ER0SOL XRS-52I

1.7. Brmakov, Т.Н. Zakharov, I.I. Kondrat'ev Par laetern nydromoteoroloelcal Research Institute, Vladivostok., UBSH (The atmospheric air quality ii determined to the great extent by the elementary composition and concentration of an atmospheric aerosol. For the elementary composition Investigation the air eamplea are collected on the filters. For this а1ш in the USSR the fibre fil­ ters are used, after sampling the filters are ashed, decomposed che­ mically, analyzed on an atonic absorption spectrometer. The authors have worked out the saaple preparation technique and sample*» analysis by the X-ray method. The technique has been worked out for the elementary analysis of a sample composition of the atmos­ pheric aerosol. The aerosol samples are selected on the filter with diameter 200mm. lo prepare samples for analysis the filter was cut in four segments that were pressed in four tablets with diameter 40 am. Before pressing the filter was put that way it's exposed side was the working (irradiated) side of the sample for analysis. To ex­ clude the filter pollution the pressing process was carried out in a press-form that was made of acrylic plastic. The filter has been pressed under 100 atm pressure that allows to get a hard sample for analysis that Is convenient for working and preservation. The elemen­ tary composition was analysed on the X-ray spectrometers SHI-20 and ВРЛНЕИ. Informational Input from spectrometers are carried out on • personal computer. Toe elements He, 11, 81, K, Ca, Tl, He, Fe were analysed on the SRH-20, the elements Fe, Zn, On, Fb were analysed on the SEISE. The analysis results of the samples, prepared of the same filter, were averaged what allows to exclude the error due to the irregular aerosol distribution on the filter surface. For the proce­ ssing of the analysis results some programmes have seen compiled by the authors. The SPifil processing analysis results programme includes the peek form analysis that allows to resolve the instrumental (appa­ ratus) nonresolved lines. for the spectrometers's calibration .the state standard 8P-J and the sample analysis results of the atomic absorption method have been used.

389 RADIOMETRIC METHODS OF AKAUfSIS OF BOM-FEBBOUS I — METALUJHGT PRODUCTS | XRS-53 B.N.Gil'bert, E.G.Obrazovsky, I.P.Buzlaeva "Hydrotsvetmet", Novosibirsk, USSS The X-ray radiometric analysis hae gained widespread acceptance as multielement, nondestructive and fast technique. In spite of the obvious advantages of method the matrix correction is the main prob­ lem. She fluorescence to scatter ratio method is the most widespread technique for matrix correction however the field of its applicabi­ lity is restricted by low < <: I-5SO or very high ( 5. 70-95?0 concent­ rations of the element of interest. The suggested modification of the methods of the matrix correction is based on the use as analyti­ cal parameter the ratio Hi/Ns (where Ni, Us are the peak areas of the characteristic fluorescence and incoherent scattered radiation) with variable power x^Hi/Ив. Shis modification expands the appli­ cability in using backsc&ttered radiation for matrix correction and lowers the systematic errors in 3-4 times. The method of Hf, Та,' V, Ее, Os, Ir determination based on con­ siderably different attenuation by these elements of K^ and X^fo- lines of X-ray Ft, Au, Hg, SI, Pb, Bi, respectively, is suggested.

She registration of K^j 2-lines is carried out by Ge-detector with energy resolution 0.7 keV for the 60-80 keV X-rays energy.The method is used for determination of these elements with concentration ran­ ging from O.I to I0O)i. The X-ray radiometric method, differing from the being by geomet­ ry of mutual arrangement of radioisotope exiting source-sample-de­ tector is worked out. In this method the exciting source, bringing as a solution on polyethylene film is located between the detector and the sample without screening. Such arrangement gives the high efficiency of excitation and registration, that allows to use the low activity sources ( ~ IO' Bg) and lowers considerably the requi­ rements to radiation safety. Under these conditions the detection limit of about 0.05 mass pereents is achieved for V and exciting source ''Co.

390 X-RAY AHALYSIS OP IHDOSTRIAb TRODUCTS ОТ THE BASIS OP П^ГТГ

ООАЬ Я.ВАНГИ8 WASTE

I.K. Sromozova Giprotsement, Leningrad, USSR In the recent years the fuel-containing waste (coal cleaning waete) found a wider application ав a raw nix component in the ce­ ment industry. A distinguishing feature of these products is pre­ sence of volatile combustible organic matters which complicate both the chemical and the X-ray analysis of the raw mixes.

The substitution of the argillaceous component of the raw mix of the "Sukholozhsktsement" worke by the Xbrklno coal-cleaning plant waste Impaired the accuracy of the X-ray analysis of the raw slurr­ ies, particularly for calcium oxide. In a number of cases the analy­ sis error reached Vf> and above.

The investigation carried out showed that the main difficulties of the X-ray analysis of slurries with coal cleaning waste are cau­ sed by the non-stolchlometric correlation between the calcium oxide content and the value of the Ignition loss of these slurries at a temperature of 9ti0e0.

Improvements in the X-ray analysis technique were necessary as well aa the use of the individual calibration for slurries contain­ ing the cnal cleaning waste. Various models of quantometers, flux compositions, sintering tem­ peratures were tested.

The application of a new model of the 0И1-25 quantooeter and a special flux made it possible to perform the X-ray analysis of slur­ ries with and without coal cleaning waste with the same calibration graph. The root-mean-square error of the main oxides control was as follows (In mass *)i

CaO - 0.10) SiOg - 0.06] AlgOj - 0.02) Pe203 - O.03| HgO - 0.12.

3(1 " щи^ _ ИОЖТСИОЗРЯСЯШ, MBTHOD о» SILICOM соятжг ВВШШХНАХИ» II AUOYS ИШ-55 I.I.KhadjUmukoamedova, l.K.Oelkln, H.-U.Vakhobova Tadjik Stat* University, Dushanbe, USSR

The main limiting factors of direct determination of silicon content in ingots of silicon -aluminium alloys by roentgeno- spectral method are disbalance processes on the interface melt- solid phase resulted In' the redistribution of silicon content in pure aluminium and a small thickness of informatic layer con­ ditioned by intensive absorption of characteristic emission. In connection, that diagram of the binary system state Al-Si is of eutectic type, when silicon content less than 10$ the surface layer should be concentrated of aluminium. Under silicon content more than 10$ the surface layer concentrates of sili­ con. High-temperature annealing seems to result to mechanical tension removal but does not influence on components distribu­ tion. The obtained data allow to judge about macrocomponents dis­ tribution of alloys and watch over technological control of their production Al-Si, Al-Si-Ti, Al-Si-Hb.

Ml SORPIIOR - X-RAY fEDORESOBKOB DBTBRMUfATIOH OP RARE XRS-561 PLAimm HBIAIS B.G.Khomutova, L.P.Zytenko, A.P.Rysev, A.A.Dilektorelcy Louonoeov Moscow Institute of Pine Chemioal Teohnology, Moscow, USSR Determination of large amounts of rax* platinum metals In complex _ natural and industrial products by Tarioua composition by X-ray fluo- гезовпог method needs to tranafer deterained eleaents into unified matrix» Tor tbia purpose seleotlve sorbents are used, lnoluding nitrogen oontalning sorbents "Polyorgs* for platinum,palladium and rodlua determination [1]. In thla work a number of sulphur-, nitrogen-oontalning organio compounds was Inxsstlgated to determine ruthenium, iridium and osmium hy X-ray fluoreaoenoe method. Inrestlgated aorbents are Industrial products unlike "Polyorgs" aorbenta. The sorption from hydroohlorio aold aolutiena of determined eleaents waa lnraatlgated. The aorbenta war* a powder, praotloally unsoluble in water. She extraotlon was 20» or 98* into the aorbenta range, that allowed to choose the most effeotlTe aorbent. Hydroohlorio aoid oonoentratioa, phase oontaot time and Temperature influenoe on ruthenium, Iridium and osmium extraction obtained. Platinum metals extractions statlo oondltiona were ohoaentl M ECI at 90-95°C in the oourse of 40 min. It was determined, that non-ferrous metals and Iron not prarant to sorption and to analyaia. Borbtion oonoentrate was analyaed by x-ray flyoresoense method after drying and pressing into borlo aold tablet. X-ray intensity meaaurements were made In spectrometer FW-1400 (JUUpa) with aoandlum target X-ray tube, operated at .70 кТ.ЭО mi. Exposition lasted 40s. inalytioal lines were Iy, for Ir and Os, and E^ for Ru. external atandard method was used for analysis. Standarc saaplee wexa preparated by sorption of platinum metals from oomplex platinum metals ohlorlde solutions. C„ • 0<1», 3r 1 0ЛВ. She ao- ouraoy of method was oonflrnsd by analysis of USSR standard sample.

Raferenoe 1. Jiyasoedova O.V. et al.//Zh.Analyt.Khim. 19S8.Vol.*3.P.673-676.

MS DETBHH1HATI0H О» BLaiBWTS Ш PLATIHU1J IUSTALS COMPLEX I ___ - 00ИР0ШГОЗ BY X-RAY PLOORBSCHTCB AHALYSIS I _ B.G.Xhomutova, N.H.Sinlzin Lomonosov Moscow Institute of Pine Chemical Technology, Moscow, USSR

Platinum met«la oomplexes analysis Is neoessary, beoause oertain composition oomplexes have most applloatlon in medioine and teohnlos. Determination of elements in platinum metals oomplexes by ohemioal metods Is complicated as separate method use for each elements: gravlmetry - for platinum metals, Shenlger method - for Halogens, flame photometry - for allrall metals, ets. The results of these methods are preoislon, but these metods are long and requiring the expenditure of auoh labour. The use of X-ray flyoresoenoe analysis aooelerated the determinations.exoept high results precision of ohemioal methods*

X-ray intensity measurements were made In speotrometer PW-1400 (Philips) with tungsten target X-ray tube, operated at 30kV, 25 mA,

in helium. Analytical lines: Krf - F, Cl.Na, Pd, Eu, Rh; L^ - Os, K,Rb, Cs, Br, Ix, Ft. Analysis was carried out in solutions. Com­ pounds analysing by other methode were used for standart solutions.

It was ascertained, that UO mm/ml determined element solution analytioal signal lndepend on as analysing oompound oomposltion as on solvent, whloh oonslsted elements with atomio number (Z) < 11. This solvents replaoe by eaoh other, therefore, one can analyse comp­ lexes in organlo solutions (Z «£ 11) with standart aquous solutions.

It was determined that platinum metals compound solutions are stable under the aotion of X-ray emission. Osmium aoid and neutral solutions are an exoeptioa: osmium analytloal signal deoreased in this solutions. The reason of this was dlsoussed. We used aloali solution or ethanol addition to stabilise analytical signal.

Calibration ourved ploted In lvO-ОЛ mg/ml of determination element. Ilemental interactions were absent in ohosen oonsentrate range. Sj.ea0.i02. The aoouraoy of results Is confirmed by analysis of known complexes, analysing other methods. Deterajnedoomplexes

are: MejH Xy].

*M APPLICATION OP snTCHROTROH RADIATION POR X-RAY | PLUORBSCEHCB BLEMBHI AlfALYSIS | XRS-58 V.P.Khvostova, V.A.Trunova GIK3DHBT, Moscow Institute of Inorganio ChemiBtry of Siberian Branch of the Academy of Scienoes of the USSR, Hovoaibirsk, USSR

The highly sensitive non-destructive instrumental analysis of biological and biomedical microsamples, individual seeds of cere­ als, individual grains of single-mineral fractions aa wall aa that of the thin films was performed at a special apparatus designed for the X-ray fluoreacenaf; analysis through toe application of the synchrotron radiation (SB) of the VBPP-3 aooumulator (Institute of Nuclear Physics, Siberian Branch of the Aoademy of Sciences of the DSSR) С 1 J. The apparatus consists of a vacuum monoohromator of primary (exciting) SK-beam, a sample compartment, monoohromator of secon­ dary emission ( X-ray fluorescense ) and ailicium-lithium semicon­ ductor ( SO ). The quantitative analysis is. monitored through the application of transit-avalanche ionization compartment mounted before the sample on the monoonromatizod SK-baam. The Synpor disos ( d»8 mm ) housing reference samples, contai­ ning from 0.1 to 80 ppm of each of 30 elements to be determined as well aa biomeiical samples, films, individual mineral grains and pressure-produced radiators of cereal seeds and milled food items are placed in tsflons dishes between layers of tight Mylar of 6.3 am thickness /"2.7. The quantitative evaluation is done w?th the application of external standard technique. Control funotiona over the analysis and spectrum proeeaaing were performed by 0DRA-1305 computer. With the K-series recorded and 3 minutes exposure time the detection limit is equal to 0.1 ppm ( 1-10"7g/g ) - 0.01 ppm

( 1-10 j/| ), subject to change depending on an element, with Sp. 0.10-0.25 . References 1. Baryshev V.B., Kolmogorov Yu.P., Kulipanov G.M., Skrinsky A.M. //Anal.Chem. Hosoow . 1986 Vol. 41, R 3. P. 389 . 2. Khostova V.P., Trunova V.A//Buol. Instr. methods. 1987 . a 261. p. 295 .

395 С0НВ1ИАТГОЛ OP X-RAT PmORBSOBHOB ЛЗГО BBUTHOT АСТ1УАТЮК xaS-59 HBIBODS in DBTBRHTMATIOT or sotra RARB вьвмвяге АГО HOBLB MBTAIS G.H.Kolesov, C.V.Ballma, A.Z.IUkllehsnelqr, A.L.borens, S.K.Praaad, D.Tu.Sapoeunikov, I.C.Sinyaev

Vernadiky Institute of Gaoehralstxjr and Analytical Chemistry, Aoedeaj of Sciences of tba USSR, Hoeoow, USSR X-ray fluorescence(XRF)and neutron activation methods of analysis (NAA)are worked out and modified with the aim of .attaining complete information about composition and distribution of some rare elements and noble metals which are used in geochemical and cosmoohemical in­ vestigations as indicators. XRF.a)For the determination of Ca,Ti,Y,Cr and Rb,Sr,y,Zr,Nb ele­ ments excitation block with circular source of Fe and two 109Cd sources were used accordingly. Samples were prepared in the form of thin layers on paper filters or on adhesive tape, X-raysd^Jwere mea­ sured with multichannel analyser equippadwith Ge-detecton and spectra

were used for the determination of some heavy elements. Samples were prepared in the form of tablets. Rock samples(KH,SG-lA,SGD-lA,ST-lA), ore samples(SeT-8,RUS-4),shales(TS-2)and others were used as standards XRF-SR.In this method iron meteorite samples in the form of thin sheet and rock samples in the form of powder were taken. The samples were placed on dacron film and cemented with lac. They were assembled at an angle of 45 to primary monochromatic synchrotron radiation(SR) of energy 26-45 KeV and secondary fluorescent radiations were regis­ tered with semiconductor detector. For example, D^^ of Pd,Rh,Ru,Zr,

1 Hb were found as n.10* ** for Sr=0.1. MAA.a)In INAA samples were irradiated with thermal and epithermal neutrons with a neutron flux of 3,6 x 10 to 4.3 x 10 n/cm ,Neutrons preferably screened by Cd- and B-filters were used in the determina­ tion of Rb,Mo,Tb,Hf,Ta(-20 more) elements. T/цп. was found to be

before or after irradiation of samples. Particularly, the microassay fusion is done with nickel sulfide, In this case, the D, ._ of noble -6 я iim. metals found as n.10 °-n.l0"°% for S^O,05-0.20. In analysing different natural objects and Industrial materials one of the methods indicated above and combination of these methods can be used.

Ж THE CONCEPT О? THE X-RAY FLUOBESQBHCB IHPORJUIIVE AND 1 АНЛИИСлЬ SYSTEM (IRPIAS) AID IIS ЛРРЫСЛТИЛЗ IK XHS-60i GEOuHEHICAX AID ИПГПЮяИВЯТАЬ STUDIBS L.P.Korobeynilcova, S.I.Korobeynlkov Leningrad Stat* University, «НТК "Mekhanobr", Leningrad, USSR Gsochemical itudlea at various atagea of prospeetings and exploration» need the existence of а common informative and analytical sjratem providing the moat rational information about substance composition. Recent developments in instrumentation and in software for the X-ray fluorescence analysis permitted to design the XBPIAS concept baaed on a hierarchic series of automated X-ray complexes. The XRFIAS hierarchy' is an adequate representation of links existing in natural ayatemat rocks - minerals - chemical elements. The use of the X-ray radiometric method together with the X-ray apactrometric fluorescence analysis gives the possibility to create a distribut­ ed and branched analytical system and subdivide it into three levels. The first level - portable X-ray radiometric complexes - Is essential for determining (in situ) the major indicator-elements in a geochamleal (environmental) system for the purpose of anomaly registration. The second level - portable X-ray spectrometrlc IOC - concerns the XHSPA of powder lamplea from registered aaomaliea. Element compositions of rocks, ores, soils as well as minerals and solid sediments can ba determined from small amounts of material (200 mg). Certain informative elements are analysed at the dark level. A "personal analyser1' for explorative geochendsts is propossd which performs analysing and data proossaing simul­ taneously. The third, the highest level, is baaed on a precision high-productive stationary complex consisting of a multichannel spectrometer and a special monochromatic analyser connected to a computer. This level forms a controlling Informative and analy­ tical centre where the information from two firat levels ia stored and processed. The XRHA3 has common both hard- and software baaed on the universal equation for the standard technique - non-coherent scattered radiation and the standard data bank. Each level baa a certain number of determinable element*. The example for XRPIAS designed for rare metal deposits is presented.

3*7 X-RAY FLUORESCENCE ANALYSIS OF CHROMITE ORES I «-о-. N.A.Korovkina, I.A.Boatchina, E.V.Kulikovskaja Vernadsky Institute of Geochemistry and Analitycal Chemistry of the USSR Academy of Science, Moscow, USSR XRF method «as used for simultaneous determination of major ele­ ments of ehromite ores with the spectrometer PW-1600 (anode - Rh, 50kV, 40mA). The sample preparation by the fusion «1th LlgB^O- «as used to make a suitable glass disk. The standards and samples «ere fused at 1150°C in a graphite crucible In the sample/flux ratio 1:5; 1:12; 1:16. A typical fusion cycle took 12 minutes. The technique for nine element simultaneous determination (Mg, Al, Si, Ca, Tl, V, Cr, Hn, Pe) from single fused dj.ec has been deve­ loped. 20 standards «ere used for calibrating of program. Hatrix ef­ fects and line overlap «ere taken Into aeoount. A «Ide range of samples of different chromium contents «as ana­ lysed. Accuracy (standard deviation) of the technique la illustrated in the Table.

Components Range of concentration Standard deviation 1:5 f • 12 | 1 tie HgO 6,0 - 0,0 0,49 0,51 0,22 ^Э 1,0 - 25,0 0,44 0,05 0,05 sio2 2,0 - 36,0 0,20 0,23 0,27 CaO 0,1 - 1,0 0,04 0.04 0,04

TIO2 0,01- 0,5 0,13 0,05 0,007

0r203 4,0 - 60,0 4,8 1.3 0,89 HnO 0,1 - 0,3 0,05 0,04 0,04 PeO 6,0 - 40,0 3.3 0,86 0,51

M8 DETSRKIMATIOB OF TRACE HEAVY METALS IM HATURAL WATERS •• * XRS-62 N.A.Korovkina, I.A.Rostohina, A.P.Majorov, V.P.Rone , D.K.Vircava'.M.V.Viroavs** Vernadsky Institute of Geochemistry and Analytical Chemistry of the USSR Academy of Science, Moscow, USSR Institute of Inorganic Chemistry, Riga, USSB Institute of Physics of Aoademy of Science of the Latvian SSR, Riga, USSR The technique of XRF-determination of heavy metals In natural wa­ ters is elaborated. The preconcentrailon is used for the sample pre­ paration, A method of preconcentration Is based on the application of 8-mer- captoquinoline for binding of dissolved form of mlcroamounts of heavy metals into chelate compounds and then obtaining co-preclpitator of the metal chelates by oxidizing the excess of reagent with hydrogen peroxide to bis (8-quinolyl) disulphide. The optimal conditions was selected for co-precipitation with 8-mercaptoquinoline V, Cr, Mn, Fe, Co, Hi, Cu, Zn, Mo and Ss from the natural waters of different sali­ nity to obtain concentrates suited for XRF analysis. 8-Hercaptoquinoline In water solutions form highly stable che­ late compounds (wioh are Insoluble in water) with transition and non- transition d-elements co-precipitated then on bis (6-quinolyl) dlsul- phide when its finely dispersed state is formed over the pH range on 2,5 to 12. The concentration coefficient is 14000. The precipitate (about 70 ag) filtered off on a Huclepore memb­ rane, washed, dried, mixed with the chromatographic cellulose powder and pressed Into pellets. It gives homogeneous targets suitable for XRP-analysis by simultaneous X-ray spectrometer system Hf-1600 (X- ray tube with Rh-anod, 50 Vf, 40 шА, measuring time - 180 *.). The linear relationship between countrates and elements concent­ ration of oontrol samples in the range from 1 to 800 • 10 g/1 was obtained. The coefficient of correlation was up to 0.998. The com­ bined usage of XRF technique and the group co-precipitation provides detection limits n • 10 g/1 for Hn, Fe, Co, Ki, Zn.

ЯИ

Ж THE METHOD OP ПЕТЕИШГАТГОН OP UAJOR ASH ORE ELEMENTS OP Pe-Hn OONORBTIOHS BY X-RAY PbUORBSOBHCE XRS-63 T.G.Kuemlna F.P.ahirehov Institute of Oceanology,USSR Academy of Soiences, Hoscow.USSB The X-ray method is used for the determination of major and ore elements of Pe -iln concretions. Optimum conditions for X-ray fluo - rescent measurements have been chosen. Sample for analysis are prepared by grinding of the powder in the agate mortar and pressing one in the pellet (without any Ms- ding substance). The parabolic equation was used for the calculation of major elements' concentrations!

where 1, — the intensity of the characteristic fluorescent radi — ation;

Ci - the element percentage; mass - absorption of the analytical wavelength by the sample;

'Mfioi_ - mass - absorption of the analytical wavelength by the pure element; ^i» °* oi* /boi — ев"**011*8! which have been determined by using the standards. The method of successive approximations is used. The analysis of ore elements (Co,Hi,Cd,Zn) requires right de­ termination of the ground. The calculation of the percentage of ore elements is made by using of the multiplicative method of /* - correction together with the logarithmical presentation of parameters:

where Aoi — mass - absorption of reference. Concentration of ore metals are determinated just after the calculation of major elements. Result, obtained by using this method, are olose to ones of the chemical method* ВИНАОТЮИ X-RAY SPHCTRIM БВтВНИШАТЮН OP ЮНО HMALS UjB^4 ni ФНВ OBJBCTS OP TUB апгсвояивнт I P.I.Lobaaov, S.A.Logunova, H.H.Andreyeva Kazakh State University, Alma-Ata, USSR A harmonic combination of methods for concentration, separation and subsequent detection of elements which leads to the formation of a stable unbreakable combination is a result of new hybrid methods of analysis. The present paper deals with the utilization of low-melting sub­ stances (1KB) for extraction-concentration detection of toxic metals (bismuth, copper, lead) in various objects of the environment follow­ ed by their determination with the help of roentgenofluorescence or roentgenometry methods.

The low-melting substances used were Individual and technical

fractions of higher carbonic acids (Cj- - C2_) as well as their mix­ tures with di-2-ethylhexilphosphoric acid (D2BHJK), Optimal conditions for quantitative extraction of metals into melt have been found. The effect of the contact time as well as toe de­ pendence between the aqueous and organic phases on the extraction ef­ ficiency and the distribution coefficient of metals have been studied.

The possibility and expediency of combining extraction and sul­ phide precipitation of bismuth with the aim of elaborating a new hyb­ rid sulphlde-extraction-roentgenospectrum method for bismuth detec­ tion have been studied. The method is based on hydrogen sulphide pre­ cipitation of bismuth with pH 0.&-1.0 in the presenoe of a IKS.

The method incorporates the possibility of double concentration of elements from the aqueous phage and combines extraction with sulphide precipitation. The lower limit of bismuth detection is lowered to 10"' - 10 JCt besides the time for sample preparation is excluded as the solidified organic phase-concentrate is a ready target for roent- genospectrum analysis.

26.3MC.4I3 Ml UTILIZATION 09 LOTF-MHLTIBG OROAMC BXTRAOTS I IH X-RAY SPBCTHAL ABALYSIS | XRS-65 F.I.Lobanov, A.I.Zebrava, K.*.Andreyevs, S.A.Logunova, T.A.Iasynkova, O.A.Hsnuilova, Xa.B.Kurilovloh Kazakh Stat» university, Alma-Ata, USSR The utilization of combined methods of analysis that include pre­ liminary extraction concentration of elements with the help of melts of organic substances and subsequent X-*ay spectrum determination is of interest from the point of view of expressiveness and lowering of the lower limits for metal detection. The utilization of low-melting reagents (LB) and their mixtures with nitrogen- and phosphorus bearing additions for extraction pro­ duction and concentration of cadmium, bismuth, lead, copper, scandium, yttrium, strontium, zirconium and the subsequent X-ray spectrum deter­ mination of metals in technological solutions, industrial sewage and natural water, alloys has been studied. The low-melting extractive solvents used were higher carbonic acids (HCA) and higher alcohols (HA) and the additions were amines, tributyl phosphate (TBP) di-2-ethylbexilphosphoric acid (D2EHFK). The extractive solvents used have small absorption factors of X- radiation which considerably lowers systematic errors due to matrix effects. Impregnation of the LH with polymer additions leads to an in­ crease of organic extract compactness, lowers losses of the main com­ ponent and allows to raise the degree of absolute concentration of me­ tals up to 300-500. A concentrate obtained after extraction is easily processed by pressing or melting whioh makes it possible to make a sample-radiator. To detect metals In solid extracts the methods of external stand­ ard and standard-background were used. Multlcomponent reference samples based on HOA or HA are made from standard metal solutionsI the; are stable during several years, the metal content in them does not change, the samples do not break down. The reproducibility of X-ray spectrum determinations in solid ex­ tracts is characterized by values of relative standard deviation (Sr) by the results of several parallel determinations. Extraction with the help of melts allows to lower the limit of X- ray spectrum determination of metale (C min, p) in the analysed ob- ijeot» by 1-2 orders.

402 ENERGY DISPERSIVE X-RAY FLUORESCENCE ELENENIAL ANALYSIS OF XBS-66 IttCROSAUFLES - TWO WAYS OF IMPROVEMENT OF THE APPARATUS V.N.Losev, H.Yu.Mironenko, K.P.GaleeT, V.G.Holoahin Physics Research Institute, Rostov State University, Rostov-on- Don, USSR

Application of the conventional energy dispersive X-ray fluores­ cence (ED XBF) analysis baaed on recording secondary atom fluores­ cence of a sample by a semiconductor detector in analysing micro- amounts of blood, animal and plant tissues, thin films, special ma­ terials, etc., is very difficult. Small amounts and areas of the spe­ cimens under study prevent from achieving sufficient counting rates on the analytical lines of elements. In this case the background produced by primary radiation scattered by the sample becomes the main source of noise because of which high sensitivity of determi- nantions can't be obtained. Possibilities of reducing the detection limit of ED XRP analysis by means of primary radiation' monochromatization by secondary tar­ gets, choosing an optimal geometry for the spectrometer chamber, ap­ plication of the filtration effect, polarization and X-ray external reflection have been thoroughly studied. For this purpose special apparatus have been designed and constructed. Recomendations have been made for the ohoice of the technique depending on the aim and object of the analysis. It has been shown that one of the simplest and at the same time highly sensitive techniques is ED XRF analysis using spectrometers

«1th secondary targets Cn~ 5-10~-% It becomes better with the spectrometers employing X-ray total reflection effect when thin films, including high temperature superconducting films, are ana­ lyzed. imLU-BLBUBUIiL X-BiX НЯГОВЕаСШСБ AKalXSIS CJ SULPUH I , XRS-671 OONIAHHttG PEOniOTS I 1 T.P.laugulova, £.7.Savina,T.F.Blashehulc, V.G.Eosttn Gintsvetmet, yoeoow.nSBE ЛИ ia lmown, systematic errors are inherent in direct X-ray fluorescence analysis of sulfur «ben it is present in samples in compounds. Therefore a necessity arises to level the effect of chemical and abase composition of products containing sulfur on the results of the analysis» A aost suitable technique in this case is sintering which levels differences in chemical,phase and granulometrio composition and mineralogical origin in a great variety of products. By applying thermal gravimetric analysis such a composition of the sister niztuxe waa found which provided representative samples without loss of eulfur.acperinental design was applied to choose duration and thermal regimes of sintering and proportions of the sinter mixture components.The sinter obtained was comminuted with binder material and pressed at 10 kP. Finally, a tabletted radiating sample was obtained applicable for X-ray spectrum analysis on both sides,which improved reliability of the analysis. Ihe analysis prooedure is based on reference standards. Reference samples subjected to multiple chemical analysis ware used to calibrate tested sinter specimens. The technique designed enables the following elements to be determined within the respective rangess в 4-50»; Cu 0.5-80»; Те 0.5-40*, Zn 5-10*. igreeablllty and repeatability of the analysis data is within acceptable limits.Validlty of the analysis can be checked by reference samples. Both X-ray spectrometers and qoantometora may be applied for the analysls.metxologloal characteristics of the prooedure depend on the class of the instrument applied.

404 PROSPECTS 0? THE USE OF 10W-TEHPERATURE FUSION METHODS XRS-68 FOR SAMPLE PREPARATION IH X-RAY FLUORESCENCE ANALYSIS

V.Haxlmov, Q.Savehenko diprotsement, Leningrad, USSR It le generally accepted that the fusion method used for prepara­ tion of heterogeneous silicate materials for the X-ray fluoresoence analysis provides more precise analysis results than those of the pressing technique.

But the high fusion temperature reaching 1600»C Li] makes it im­ possible to analyse such elements as S, CI, alkali metals. The use of phosphate fluxes f2], permitting the fusion to be carried out even at a temperature of 400aC, is not rational because of the low aggressivity of such fluxes to silicates.

The possibility of using lithium borate fluxes containing lithium metaborate, lithium carbonate with or without glass-forming additives has been studied.

The results of fusion at a temperature of about SOO'C obtained have proved the possibility of analyzing, together with the main ele­ ments, such oomponents as chlorine In silicates with much higher precision than In £У] as well as total sulphur present in the initial sample In a form of element or sulphide sulphur without presintering [4]. She time of sample preparation does not exceed 10 minutes. References

1. Ohle K.// Z.lnal.Chem. 1977.Vol.S86. Р.Э6. 2. Rinaldl *., Aguzzl P.// Speotrochlm. Aota. 1967У01.23В. P.IS. 3. Imamoto I.// Bunsekl Kagaku. 1982.Vol.31. Ho. 13. P.T101. 4. Peliltanova U.// Z.Anal.Chem. 1985.Vol.320. Р.ЭЭ8.

405 THE X-RAY FUJORESCEHT CONTROL FOR THE CRYOLYTE I AM> ALUMINUM FLUORIDE QUALITY |ma-6g. L.P.tiouraeheva, A.A.Nekludov, T.A.Syrina Research Institute of fertilizers, Moscow, USSR The aluminium metallurgy is one of the main consumers of fluo­ ric acid salts (cryolite and alumium fluoride) - the fluosilicic acid utilization products obtained in the manufacture of phosphate fertilizers. The purity of aluminium and the electrolytic process conditions depend on the quality of the products, that has to meet the special requirements as to the content of the main components: fluor, aluminium, sodium (for cryolite) and fluoride, aluminium (for aluminium fluoride), and also to the content of admixtures: silica, phosphorus, sulphur, iron. The methods applied in the analytical laboratories - the atomic absorption, photometric, chemical methods - are characterized by the low rapidness and insufficient accuracy. The present paper suggests that the express-analysis of cryolite and aluminium fluoride of different brands should be performed by the X-ray fluorescent method for the content of the following elements: silica, phosphorus, sulphur, iron. The quantometer CHl-25 and spectrometer VEi-30 with the com­ puter system "Eleotronioa 60" were used for measuring. While developing methods, the ways of preparing the emitters fox measuring, the influence of heterogeneity of compositions on the intensity of primary diffusion were considered, the optimal conditions of excitation and registration of X-ray eoittanoe were determined, a type of equation for the concentrations to be calcu­ lated according to the measured intensities of analytical lines were obtained. The compliance of the results obtained with the respective specifications пав shown that the arrows of the X-ray fluorescent analysis are in the permissible limits. She application of the given method for the quality control of the fluoric add salts would permit to have the time-used-f or analysing-one sample 10-20 time» shortened.

*M X-RAY PLVORESCBHCB ANALYSIS OP JEWELLERY OOLD ALLOYS I V.Y.ttrtov, L.P.Zhltenko \XSS-?Q (JINALKAZZOLOTO.Mosoow, USSR

X-ray fluorescence analysis (XBPA) is widely used in the produc­ tion control of various alloys, but it is not the case for jewellery alloys, the main reason snowed by several autors /i,27 being conside­ rable systematic errors and unsatisfactory reproducibility (repeat­ ability) of the gold determinations. Jewellery gold alloys are usually analysed by oupellatio.i method which is highly accurate but time- consuming. In this work, XBPA was successfully used for the analysis of jewel­ lery gold alloys. A technique was developed for the determination of An, Да, end Cu in gold jewellery with metrologies! characteristics compered favourably with those of the classical cupellation technique. Measurements were made using a Philips PW-1400 spectrometer equip­ ped with an Z-ray tube with tungsten anode ( 100 kV, 100 ml ) and a Li* 220 analysing cryatall. Reference specimens were prepared from fine gold, silver and eopper by fusing, flattening and finishing. A technique was developed for preparing of homogeneous reference speci­ men*. The investigations of samples of technological jewellery alloys snowed that the gold content in the surface layers was considerably more than that in a bulk of the sample. To deorease the systematic error of ХВ7Л it was nasossary to remove a layer of 0.2-0.4 ma from both bottom and upper surfaces of the sample. Measurements were made on both faces of the sample. the method was applied to the determination of Au, Ag, Ou in the 583° gold samples with standard deviation» of 0.053, 0.16 and 0.15 wt % respectively. She results were in good agreement with those obtained by the eupellation method. She time required for a complete analysis was oa. 15 «in.

References 1. Kick J.D., Caul H.J., Smith D.L., Sssberry S.D. // Appl.Speetrosc. 1967.Vol.21. P.324. 2. Antlla I.-*., Sihvonen M.-L. // Iresenins Z.anal.Chem. 1987. Bd.327. 8.799.

407 METHODS FOR OBTAINING OF BORATE BEADS FOR X-RAY ( FLUORESCENCE ANALYSIS | XRS-71

G.Panayotov Geological Institute, Bulgarian Academy of sciences. Sofia , Bulgaria

Different methods for obtaining of glassy borate beads for X-ray fluorescence analysis are known. With all methods certain quantity of material) meant for melting, is mixed with a borate flux and is then melted in platinum crucibles or in crucibles made of platinum with an admixture of another precious metal - Au, Rd, etc. The melt obtained is poured into preheated casting dishes, also made of platinum or a mixture of platinum and another precious metal, and then they are left to be slowly cooled. This method generally accepted in the laboratory practice has many disadvantages: low productivity, obtaining of the melt and its pouring into the casting dishes is done one by a time or consecutively. Elimination of a part of the melt stuck to the crucible requires additional chemical or another treatment of the latter. Also, there are other methods, with which the mixture of the material and the borate flux is melted into crucibles of graphite and glass-graphite. A disadvantage of these crucibles is that they quickly burn out in an air medium and polute the melt with graphite particles.

After research and experimental work of many years, in practice, a new method for obtaining of borate beads for X-ray fluorescence analys­ is is invaded. The same is highly efficient and provides a possibility for obtaining of an unlimited number of beads for one and the same time (from 3 up to 10 minutes). In practice, the number of the beads obtain­ ed is limited only by the heating surface of the oven used.

Platinum vessels and crucibles are not used for their making and it is done in devices constructed for this purpose. The beads obtained have a fire polished surface, ideal for an X-ray fluorescence analysis. The beads obtained do not require grinding and polishing.

4И METHOD OF X-RAY FIUORESCEHCE AHALYSIS OF THE I MULTICOHFONEHT MATEEIAIfi WITH COEHSCMOH FOB |XRS-72 BEBTUBBATIOH OF THE EUMEHTS G.V.Pavlineky, L.I.Vladimirova Research Institute of Applied Physics of Irkutsk State University, Irkutsk, USSR The majority of the methods of X-ray fluorescence analysis takes into account the influence of absorbing properties of material on X- rey fluorescence intensity. Incomplete accounting of the other pro­ cesses, determining the value of analytical signal, is one of the basic sources of the error of this method. It is offered by introducing the corrections for perturbation of the elements to convert the measured intensities of X-ray fluores­ cence into the observed intensities at the same Bass attenuation co­ efficient and absence of some other effects. The corrected intensi­ ties are converted into the grades of the elements of multicomponent sample by the next operation. The influence of X-ray background on the measured intensity is taken into account by its graduation in the samples of known composition. The potentialities of the offered method have been estimated dur­ ing determination of the grades of 12 elements in 59 standard samples of the high-alloy steels, varing their composition in wide range.Sta­ bility and small value of the theoretically calculated correctione for perturbation of the elements allowed to consider these correcti­ ons to be constant and tabulate their values for given conditions of analysis conduction. When using II graduated samples the accuracy of the analysis of the steels is turned out in 2-3 times higher for the most elements, than in wide-spread method of ^-correction. Segressive decision of the same task required to determine 7 ranges of chrome and nickel grades and to use 48 graduated samples for achievement sa­ tisfactory accuracy of the determinations. The method has been introduced in one of the metallurgical facto­ ries.

40* X-RAY FLUORESCENCE HICROELEMEHTS DHTERMIHATIOll IH пгаившзнт снгиш op ISSECTS XHS-73 O.Polivtsev, P.Talpalataky ЮТЯ Academy of Sciences,Kishinev, USSR There has been developed the analysis method for the determinat­ ion of sueh microelements as: Cu,Zn,P,S,K,Ca in intugement insek- ts ohitin. Radiators have been made by compressing (under pressure 300 kg/ em2) three grammes of reduced to fragments and undergone freege drying specimen. Caterpillars of turnip and cotton moths as spe­ cimen are taken from the oontrol group and treated by infrasound waves,reproducing seismic effect. Preliminary roentgenographs study displayed that infrasound flu­ ctuations,as seiamopredictors.are all cause the objectively registered changes in the structure of insects ohltin(caterpi- llars)[l]_ X-ray fluorescence analysis performed on the experimental materi­ al made it possible to stand out three elements-phosphorus, sulphur,potassium -carrying the main information data. Due to the method it is possible to oarry out the guantitative determination of a single or several elements without registering i-ray radiation intensities of the other elements oompositing the complex biological compound. The method is based oh the dependence of element(1) concentration (C) oontent on the experimentally fixed intensities K-relations

К-1Ц/ I;. Quantitative determination of a single or several elements in a complex biological compound opens up great possibilities in re­ cording changes in highly standardized biologies! objects, that may be assumed as a basis of one of the proepeot methods of seis­ mic prediction raonitorinting.

Reference 1. Druaja A.V..Salganile R.I.,Talpalatsky P.L.,Polivtsev O.P.et.al USSR Academy of Soienoes, Kishinev, 1989. P.36.

410 SPECTROMETRY DETERMINATION OF COMPOSITION I 1 IXHS-741 OF TTTAMUM ORES ' >

Aleksander Przepiera. Maciej JabtoAakl. Marek Wi*niewski

APPLIED INORGANIC CHEMISTRY CENTRE of Polish Academy of Sciences ul. Walki Wodych 1 72-010 Police. POLAND

A high sensitive and precise method for the determination of main and trace elements contents in titanium ores such as ilmenites and slugs has been developed. The increasing importance of titanium dioxide technology has led to a great interest in the development of rapid and precise analysis of main components of titanium ores as well as accompanied elements (e.g. Cr. №. Zn. Al. Zr) which have great influence on final product quality.

For the analysis a Philips sequential X-ray spectrometer PW-1480 was used. In the paper the method and calibration data are described and results of some samples of raw material analysis are presented in a form of computer reports.

411 ОВТВШПГАТДОН OP ICHOR AMD TRACE BbHIEUTS IM GEOLOGICAL I SJUIPLB5 ВУ. X-RAY FUTORESCESCE SPECTROMETRY | XRS-75 A.G.Revenko, C.P.Petrova, V.lI.Uovikov Institute of the Earth Cruet of the USSR Aoademy of Scienoea, Irkutsk, USSR In thie report we describe a determination method of minor and traoe elements In rooke, which requires only a simple preparation procedure and Information about the type of rock. An accurate analy­ sis of geological samples requires a closer Investigation of the ab­ sorption-enhancement effects. !№ls problem was solved with the help of a theoretical calculation of Intensities K^-lines of V, Cr, Co, N1, Rb, Sr, Zr, Ba. The types of rocks uaed for evaluation of matrix effects wares Amite, serpentinite, peridotite, basalt, gabbro, anor- thoslte, norlte, dlorite, syenite, latite, granodiorlte, granite.For the geologioal materials considered, the matrix Is supposed to oon- sist of the elements 0, Kg, Al, Si, K, Ca, Ti and Pe only. The error induced by this approximation in the calculation of the intensity is generally smaller than \%. The effect of the voltage applied to the tub* was examined, but no significant difference was observed throug­ hout the voltage ohange from 25 to 50 kV". All the measurements were oarrled out using a VRA-30 x-ray fluor­ escence speotrometer (Carl Zeiss, DDR), connected to a computer "Blee- tronlca-60". She measurement conditions were, Rh or W anode,40-50 kV, 40-50 ma, PU- or SS-deteetora, L1F(200), L1F(220) or PE crystall ana­ lyser. The Instrumental parameters have been carefully optimlzated for an element given. The detection limit achieved is about 1-5 ppm,provided that serious spectral interferences are absent. It is true for Cr, HI, Zn, Rb, Sr (the count time being equal to 20-50 s). The method has been applied to the analysis of series of geologi­ cal standard materials (igneous rocks, sediments, soils). A reference standard was gabbro SGD-1 or dunite ЗГО-1. Hatrlx effeots are correc­ ted by theoretical coefficients. The sample preparation consists of careful grinding and pressing the powder material into pellets. The Intensity data for different pellets of the same material indicate that the preolslon is satisfactory. A good agreement Is obtained bet­ ween the results and the reported data with accuracies typically of 5-10*. Some group of samples of widely varying composition are ana­ lysed also. Our x-ray laboratory produces, on the average, a two element analysis for 30-40 samples dally.

412 QUANTITATIVE DETERMINATION OF Pt, Re, Sh AND ТГ CONTENT IK REFORMING CATALrST BY X-RAY FLUORESCENCE SPECTROMETRY XBS-76 dr ing. Milgorzit* Ryoirtska-Gacak Institute of Petcoleum Processing 31-4» Krakow, Poland

It ns found that Pt end Re content in bimetalic ettelyst, determined by x-ray fluorescence method, did not cause an interelements effects. Therefore, quantities of these two elemnts can be estimated using two in­ dependent straight calibration lines, according to the following equations:

Cpt > O.OOlfl • 0,00186 Rpt (1)

Cg^ • 0.0021 + 0.00202 R№ (2) In this case, total estimated error at the confidence level (l-

- 0.002 % wt. for Pt - 0.003 % irt. for Re Fran the Plesch criterion which has been experimentely proved, Sn and Ti pre­ sence in Pt-Re catalysts has no influence on quantitative determinations of Pt and Re. However a considerable Interelements effects has been observed when Sn and Ti «ere estimated in presence of Pt and Re. This intarelements relationship was included i WcnoU-Hopper equation model:

Cg,, « 0.07JJ7 • 0.00024 Rj,,^ + 0.14736 C^ • 4.0833? Cpt • 0.00201 R^ ^

Cpt - 15.25724 Ср» C,,, (J) where t Св., С» - content of Re and Pt ли ™ fro» equations (1) and (2) Total estimated error of Sn, at the confidence level (1-eL) • 0.» is equal: - 0.004 % wt in pure support AljOj i 0.007 % wt in Pt-Re catalyst. Quantitative estimation of Ti in Pt-Re-Sn reforming catalysts can be calcu­ lated according to the following equation:

CT1 * 0.01366 • 0.00035 *1Ш+ 0.03715 C,^ • 0.00031 Cpt * 0.84151 C^ +

0.010*8 Я,ш C^ - 0.11117 RT1K^Cpt - 0.0010 R^Cg,, - 0.18»!

C^C^ • 0.1831 R^ - 2.2624 Cpt (^

Total estimates)error of Ti at the confidence level (l-oc) • 0.» is:

- 0.005 % wt in pun support A120, - 0.01 % wt in Pt-Re-Sn catalyst. In experiments a Philips X-ray fluorescence epeetrometerwith Cr-tube and U 200 amid was uasd. The examined catalyst нега prapated In the pellets tor* and benzoic add и a binding agent was applied.

413 МВГНОВ OP ЗРВСШВН PREPARAMOH TOR X-RAY AHALYSIS (—; -| XHS-77 OP POWDSR MATERIALS I " \ B.S.Salakhutdinov. T.A.Prlvelova, A.P.Hlkoleky ОЙТК "aoyuztsvetmetavtomatika", r.osoow, VSSA •J!he long-term experience acquired in specimen preparation of powder materials for X-ray analysis has shown that the rapidity and accuracy of X-ray analysis depends, in many ways, on specimen preparation rapidity and quality of the specimen. She present pa­ per, therefore , deals with a new method?" which improves sample preparation of powder materials, and apparatus for making the specimen. The apparatus is designed to get a fiat pellet of powdered materials in metal ringe. The rings are used repeatedly and the pellets can be made in them at both sides of these rings. The device is simple in design and operation. She output of the pellets made in the device is 5 to * times higher than that of usual way of manufacturing pellets in a cup (a die) made from boric acid by pressing. According to the new method the pellets are produced in the following way: prior to filling the powder bulk into the metal ring the base surface of the device is covered Ъу а 4-6% acgueous solution of polyvinyl alcohol with a layer thickness measuring 0.006 to 0,008 g/cm ; then the powder material is put into devi­ ce, as a layer having 4 to 6 mm thickness, and compacted under the pressure as high as 900 to 1400 kg/em during 20 to 50 s. The prepared pellete, compacted in the metal rings and made from varies powder materials with different densities, has a smooth and clean working surface, durable covering and a thick­ ness no less than 2.5 mm. The utilization of the method and device for making pellets from oxidized sulphide ores, oxidized nickel ores, waste slugs of shaft etc.haa shown the pellets are always of high quality, whereas the faulty ones are exclusively rare.

*'The method is approved through a decision taken by VNIIGFfi (All-Union Keaearoh Institute of State Patent Examination) to grant a Certificate of Authorship Acoording to application Я 4616882/23-26. 414 X-RAY FLUORESCENCE ANALYSIS OP RARE METAL OBJECTS I XRS-78 WITH THE BSE OP UHIFIED SAMPLE PREPARATIOH VARIAHTS ! 1_ Y,A.Shestakov, V.V.Golubchikov, I.A.Gerzkln, E.G.Namvrina State Scientific Research and Design Institute of Rare Metal Industry, Moscow! USSR A large variety of rare metal products, a different aggregate state of samples, relatively low (compared to other branches) produc­ tion volumes determine the necessity to develop universal methods with wide application possibilities. This relates also to the x-ray fluorescence analysis. The changeableness of the substantial sample composition can influence considerably the results of determination. The preparation of adequate reference samples becomes in this ease a difficult task. The above mentioned problems can be simplified when using diffe­ rent variants of the unified sample preparation for the analysis.The developed "layouts" for the combined x-ray floureseence analysis of rare metal products are baaed on the following techniques! - sorption extraction of elements from the solution, preparation of compact emitters by pressing and their analysis (determination of precious metals oontalned In concentrates and technological soluti­ ons, С • n.10"2 - n'109S, Sr • 0,02 - 0,04); - fusing the alloy chip with the blend based on potassium pyro- sulphate and lithium borates, analysis of produced рТчщ-Нке emit­ ters (determination of rare refractory metals oontent in alloys, с • n«10"1 - n»10%, Sr • 0,03-0,05)i - fusing the powderlike sample material with the blend based on lithium borates, analysis of glass-like emitters (determination of components In mining produote, С » n-10~ - n»10S6, Sr • 0,02-0,05)) - accelerated precipitation of rare-earth elements (RE) in oxa­ late form, production of a ooncentrate of RE-oxidea sum, mixing of the sample material with the bonding agent, preparation of emitters by pressing and their analysis (determination of RB-oontent in tech­ nological solutions, С a 20-350 g/1, Sr a 0,02-0,05). The developed techniques and variants of the analysis have been tested, evaluated metrologioally and are used In practice.

415 X-RAY AKALlfSIS OP ECOLOGICAL SAliPLES USIHG TERTIARY X-RAY PLUORESCEKCE SPECTRA ' ' V.i.'.Sinitsin, E.V.Semionova, O.M.Aleksanjan Institute of Physics, Institute of Pish Economy, Rostov-on-Don, USSR

Energy dispersive X-ray fluorescence analysis (XKFA) was applied to the problem of determination of heavy metals in water and sediments. Spectra of samples were excited by fluorescence of UoKoi,*. Voltage of X-ray tube was 40 kV, current - 40 и A for sediments and 50juA for water samples. Counting time was 1000 seconds. Spectra were registe­ red by semiconductor SiCLiJ-detector with energy resolution of 220 eV at the energy of 6.4 keV. Standard samples of water (S0V-2P, SOV-3, SOV-4) and sediments CSDO-1, SDO-2, SDO-3) were used as the external standards. The program based on the linear least squares method was developed for the spectra processing L11 • The computer time (SM-4) for this procedure was 2-3 min. (later samples were prepared from carboxymethylcellulose as thin films С2Л • Such preparation made it possible to determine elements with the detection limits of 0.1 - 0.3 mg/1 and relative standard de­ viation of 0.07 - 0.26. Following preconcentration methods were approved to lower the de­ tection limits! extraction as diethylditiocarbaminatев, precipitation by 1-(2-pyridylazo)-2-naphtol (PAD), sorption on the S,N-containing polymer reagents. It was shown that the last is preferable. Sediments after drying and grinding were pressed in tablets by pressure of 350 atm with diameter of tablets 30 mm. The method made it possible to determine K, Ca, Sc, Ti, V, Cr, Mn, Pe, Co, Mi, Cu, Zn, Ga, Pb, Br, Sr, Zr with detection limits of 10 - 10 J mg/g and re­ lative standard deviation of 0.02 - 0.06.

References 1. Geraoiraov S.A., Sorbenko T.P., Semionova E.V.//Tezisi dokl. II Vsea. Sovesoh. po Rentgenospektralnomu Analizu. 26-28 Sept. 1989. Irkutsk. 1989. P.123. 2. Volkov V.P., Semionova E.V., Seraelmov S.A., Sinltsin V.H.//Zavod. labor. 198S.Vol.54,lf 12. P. 46-48.

418 METHOD OF FOBUma OF SW1TOABD SAMPLES COMPLETE SET I TOE X-BAY FLUOBESCEHCE AHALYSIS OF STEELS I3"5"80

A.N.Smaeuaova,E.I.llolchanova,L.N.Pliner,l.V.Smaglinov Institute for OEMs,Central Besearch Institute for Ferrous Uetallurgy,Sverdlovek,Irkutsk state University,Irkutsk,USSR Today the system of standard samples of steels chemical compo­ sition created in USSR ie primarily aimed at emissive spectral analy­ sis. Under planing the composition of a suite of Btandard samples x- ray fluorescence ( XRF ) analysis we aspired to find such minimum num­ ber of needed standard samples which will allow to cover the total possible range of analysing materials chemicbl composition.The cali­ bration function is determined by W.K.de Jongba method using the common set of constant ^-coefficients for the whole range of element concen­ trations only. The method of forming of the standard sample set based on the simulation of the experiment with the help of theoretical intensities of XBF analysis is prpposed.In the set of standard samples for XBF analysis 36 types of standard samples are included.This standard sam­ ples allow to evaluate calibration function when determining 14 ele­ ments in 450 marks in low-alloy,medium-alloy and high-alloy steels. It is showed theoretically and experimentally that the accuracy of XRF analysis results of each type of steel received by particular and the united techniques are comparable.№en calibration function is constructed correctly the accuracy of XBF analysis depends inessenti- ally on chemical composition of sample used for the calculation of a - coefficients.One may suppose that a difference between data of XBF and chemical analysis is primarily caused by difference of the ana­ lysing samples and comparison eamples microstructure.as well as qual­ ity of certificate dates for standard samples.The procedure of control of certification quality of reference samples is propoasd.lt is showed that the influence of the samples microstructure on Intensity of ana­ lytic lines may be partially accounted by reducing the experimental intensities to theoretical. Experimental verification of efficien­ cy of the formed standard sample complete set is carried out.

27.3aK.4I3 417 INVESTIGATION OF METAL HISTORICAL OBJECTS BY MEANS f~ XRS-B1 OF ENERGETIC DJSPERSIV X-RAY FLUORESCENT ANALYSIS I

B. 5tverakt 0. Vavrikova, D. Tluchof Institute -for Research, Production» and Application of Radio­ isotopes, 102 27 Prague, 5SPR J. Klimes Office of President CSSR, 110 00 Prague, CSPR

The energetic dispersive X-ray fluorescent analysis with the radionuclide exciting source was used for the investigation of selected gold objects from the Prague Castle treasure and steel parts of Sn. Vaclav arms (Prague Castle*, The 24*Am in the ring form was used as the exciting aaurLi, the radiation was measured on planar Si(Li) detector in the con­ nection with multichannel analyzer Canberra Series 85. The obtai­ ned spectra was processed on the computer POP 11/23. The analyzed gold objects лге connected with the period of Charles XV government, the Czech king and Roman emperor 11** half of the 14** century). The coronation cross. Cross of pope Urban V and Zavis's Cross was analyzed. The method mentioned above was used for the determination of Ag and Cu as an alloying additions and the impurities of Zn, Sn, Ni and Co in the different parts of analyzed objects. The following steel objects from the arms of Sn. Vaclav, Czech prince <1** half of the if)**1 century) was analyzed* wire shirt, helmet and coronation sword. The obtained results are very valuable for art-historians and give a chance to find the origin of these precious historical objects.

4

416 APPLICATION OF ENERS£TIC DISPERSIVE X-RAY Г* FLUORESCENT ANALYSIS IN THE RESEARCH OF OLD | -82 PAINTINGS

O. Vavfikova, B. Stverak, D. Tluchof Institute far Research, Production, and Application of Radioiso­ topes, 102 27 Prague J. Klimes Office of President CS5R, 110 00 Prague, &SPR

The Research of old paintings was carried out. by means of energetic dispersive X-r*r fluorescent analysis /EDXRFA/ for the purposes of art-historian». The ring source of Am was used for the excitation of X-ray spectrum*. The emitted radiation was mea­ sured on the planar semiconductor Si

The paintings of the greatest Czech gothic painter Master The- odoricus from the 1** half of 14*** century were analyzed. The great collection of Theodoricus' paintings is exhibited in the Karlstejn castle. The results witch were gained by EDXRFA gave the useful information on the element composition of individual pigments. The obtained results give the chance to art-historians verifying of 'old paintings.

i

419 X-RAY MICROELEMENT AHALXSIS OP SOKE BIOLOGICAL MATTER XRS-8J V.F.Volkov.H. Yu.Hironenko, I.G.Arjanova Institute or Physios, Rostov State University, Rostov-on-Don, USSR

The methods for determination of microelements' concentration in blood, vegetations and flab are worked out. Spectrum of sample in­ duced by fluorescence of Sr or Ho is registrated by Si(Li)-detector. The following sample preparation methods are used: drying, dry ash­ ing, wet ashing, blood albumen precipitation with following centri- fugstion. For each method detection limit and reproducibility of re­ sults are found. Combination of monoenergetic spectrum excitation and pointed out sample preparation methods make it possible to carry out the analysis of about 20 elements. Comparative microelement analysis of rural residents' blood and welders' blood was fulfilled. It was found out that the welders' blood contained Cd and such amounts of fb, Br and Sr that exceeded the same in rural residents' blood for 3-4 times. The Cd concent­ ration is proportional to record of service. Various parts of vegetations (leaves, stems and others) have the typioal set of microelements with their concentrations.

420 THE XRF ANALYSIS OF FOODEIl INDUSTRIAL PRODUCTS |XRS..8*|

S.A.Volodin, A.I.Uvarov, I.V.Vorobjeva Scientific-Industrial Firm "Sibt3vetmetavtomatika", Irkutsk Branch, Irkutsk, USSR

An X-ray fluorescence method for determination the P, Ca, Kn, Fe, Cu, Zn, As, Pb in premix has been developed. The samples of premix was burnt. The Internal standards Ga and Cr were added in the ash. Cr was used for P, Ca» Hn, Fe.

Qa was used for Cuf Zn, As, Pb. The concentration of Zn was founded by the formula

b ( F, Zn Zn - a_ Zn Cu ),

where F„ was a ratio of ZnK-alpba to SaK-alpha radiation, d_ Zn Си was used for the correotlon of Cu effeot. The concentrations of the other elements were calculated by the formula

where 1 i» index of the element. The method was tested with the 30 samples of premix. The results were satisfactory. Detection limits of the elements in the ash were 0.004X Fe, Mn, 0.002X Cu, 0.001* Zn, As, Pb. The intensities of the elements were measured with X-ray speotrometer VRA-30.

«I ORE CbABSlFXCATIOH TO {TECHNICAL GRADES OH THE BASE OF DISPBflSIONLEiJS X-HAY ВРЕСМиИ METHOD USING IPUGE IDEHTIHCATIOK V.N.Zavgorodniy, I.A.Krampit XRS-85 Industrial Scientific and Technloal Complex "Soyuatsvetnietavtomatike", Moscow, USSR The method of ore classification to technical grades on the base of dispereionless X-ray spectrum analysis using image identificaton is examined. Functions of measured X-ray fluores­ cence intensities of registered lines that provide greatest informativity and mutual orthogonality are taken as criteria. Optimal decision rules were searched in hyperplane class within criterion space by means of teaching sampling. The classifica­ tion algorithm comes to diehotomoua hierarchy and here at each step discriminant hyperplane minimizes empirical risk and is maximally distant from dividing classes in the respect of uni­ form metric (City Block).

Content assessment ia made by graduation characteristics in which analytic parameters were selected individually for each element defined. The results for barium complex ore classifi­ cation to four technioal grades are given.

4» THB LOCAL X-RAY IHVBSTIOATIOI OP THB AHORPHOUS-CRXSVALLXlffi Cu-Pe-O-P PIIHS FORMED ON THB HBTAL SURFACES UBDBR FRICTION TRBABIBKT lxRS-86 Y.V.Gorsky, A.N.Gripachevsky, A.V.Vereahcbsk Institute of Metal Physics, Academy of Sciences of the Ukrainian SSR, Kiev, USSR Previously atomio and electron structure and interatomic cohesion in the new kind of amorphous-crystalline alloy Cu-Pe-0 formed on the metal work surfaces under friction were studied by modern methods of electron probe microanalysis, X-ray diffraction, X-ray eraission-Mos- abauer spectroscopy, Auger-electron spectroscopy) transparent elec­ tron microscopy Л7. Oxygen was shown to reveal in amorphous-crystalline Cu-Fe-0 alloy an unknown property to interact with metals without their oxidation and to stabilise small Fe clusters in Cu host due to the formation of the strong oovalent Fe-0 bond at the weak interaction of Fe-0 cluster atoms with Cu atoms» In the present work local X-ray spectroscopy studing of the amorp­ hous-crystalline Cu-Fe-0 alloy with additional element P, obtained also by friction treatment, was fulfiled. The main features of the ele­ ctron structure and interatomic cohesion in Cu-Fe-0-F alloy caused by fluorine were determined. Its influence on the physioal and mechanical properties of the alloy is discussed.

Reference 1. tiorsky V.V., Gripaohevaky A.H., Hemoshkalenko V.V. «t al.// Hetallo- fizika. 1987. Vol.9, H 5. Р.7Э.

423 SLBCIROH ионорновв лот X-RAY-FLUORESCENCE IMVESTIGATIOH Г—— OP CROHITITES 1 "S7 A.V.Quchova, L.S.Zholudeva, K.I.Ignatenko, N.H.Kononkova, H.A.Korovkina, M.A.Korovkin, E.J.Scherbevsky Vernadsky Institute of Geochemistry and Analytical Chemistry of the USSR Academy of Science», Moscow, USSR The ehromltit is a very valuable raw material for the national economy. The task of our Investigation was to determine the possibility of the utilisation of X-ray-fluorescence analysis (ДР-) of ohromltlt and to elaborate the technique of microcomponents determination and to choose the optimal conditions of sample preparation. For the optimisation of the conditions of ohromltite sample pre­ paration for the XRP, the chromite melts were investigated with the help of the electron probe microanalyses. The control sample of ehro- mitite (M 156) with the composition (2 wt.): MgO - 14.68; AljOj -

12,07; Si02 - 8,05; T102 - 0,23; Cr203 - 48,92; KnO - 0,26; FeO +

+ Fs20. - 19,96 was analysed. The melting with fluxes (LiBOj.LigB^Oy) in graphite cruelbles In silit furnace was done under the temperature of 90O°-135O°C. The dependence of melt homogenlty on time, tempera­ ture and melting time was investigated. The eleotron probe microana­ lyses XHA-5B, firm Hitachi and CAHEBAX-ICCROBEAH, firm Oamsca and eleotron aicrosoope OAHSOAN, firm Uniezport Co Ltd were used for the melt homogenlty Investigations. It was found that while melting with fluxes chromltites from non homogeneous melts in which together with uniform solution of Al and Kg over the surface and depth of melts the seprete fraotlons of Cr-Pe combination present. With the increase of temperature from 1050° to 1250° the distribution of Fe becomes more homogenloua and small particles of chromium oxides from larger com­ binations what leads the understating of the results of the large concentrations of Or.More the dilution of fluxes (1*1, 1+12, 1+16, 1+33) less the degree of agregate (Cr+Fe) isolation Is - from 20% to 0,50* of common surface. The precision of XRP analyses improves with the Increase of the dilution of ohromltltes with fluxes. The melt in­ vestigation with different fluxes (LIBOg, U^fy) illustrated the absenoe of the devitrification. The optimal conditions of sample pre­ paration were found and XRF-teohnique of ohromitite analysis for PW- 1600 speotrometr firm Philips was elaborated. The estimation of the technique metrologloal characteristics are given.

424 ELECTRON PROBE MICROANALYSIS OF THIH HUB ON SUBSTRATE S.V.Kazalcov, S.G.Konnikov, V.V.Tretjakov IRS-88 A.r.IOFFE Physioo-teohnioal Institute, Academy of Soiemoee of the USSR, Leningrad, USSR

Electron probe X-ray microanalysis (BPHA) gives a good pos­ sibility for simultaneous determination of the composition and and thiolmeBB of heterogeneous systems without destruction of the sample under study and Is an alternative method for suoh an expensive method as Rutherford baofceoattering(RBS). In ЕРШ the most perspective approach is based on analytical representation of the depth distribution function ф(рг) of the oharaoterletlo X-ray production, «here pz is the mass depth.The law of the depth oontlnuous distribution of the characteristic X-ray radiation had been taken as a principle of the Pouchou and Pioholr (PAP) method [1] for microanalysis of the 'film on substrate1 heterogeneous system, whioh gives satisfactory re­ sults for oaloulated intensity la layered samples. The present report deals «1th the Investigation of ф(рг) pa­ rameters taking Into account the electron baoksoatterlng in he­ terogeneous layered systems for a considerable difference bet­

ween mean atomlo numbers of the film z1 and the substrate гг . The electron baokacattering coefficient for the 'film-substrate'

system is expressed by means of z, and z2 , as well as the re­ duced film thickness y=pD/R ,anere R is the full range of elec­ trons. A new procedure for calculation of effeotive atonic number

zet is proposed. Variations of the shape of oaloulated function representing the depth distribution of the generated X-ray ionization with primary electron energies , atomlo numbers of the film and sub­ strate , layer thlokness are Investigated in the report.Results obtained on the basis of the proposed analytical model are oom- pared with experimental data and data taken from literature.

Referenoe I.Touohou J.L., Pichoir *.// Reoh. Aerosp. 1984. N 5. p. 47

41Б X-RAY MICROANALYSES OF MELT INCLUSIONS ( XRS-89 N.N.KQNONKOVA, A.V.60UZHQVA, A.A.GOURENKO l Vernadsky Institute of Geochemistry and Analytical Chemistry, USSR Academy of Sciences» Moscow, USSR

The results of the utilizaion of local X-ray analyses for the composi­ tion investigation of melt inclusions of limited dimensions ( <10 microns) in Minerals are considered. All analyses were made on electron probe X-ray microanalyser Camebax-microbean with POP 11/23 computer. The determination of 12 elements of silicate group were made in a scanning beam mode at IS kV accellerating voltage, 30 nA electron beam current.The sequence of the ele­ ments determination is chosen with consideration of their interaction with an electron beam. The electron beam microanalyses of glass is complicated by their instability under the electron beam what leads to the redistri­ bution of elements, especially of alkaline metals I Na and К ). The uti­ lization of scanning beam mode improves the stability of measurings. With due regard for the decrease of X-ray intensities with tie*, the necessary corrections in results of Na and К determination can be made. The estimation of the systematic error of determination of major petro- genic elements with concentration more than 0.5% wt. is given. Each inclu­ sion was analysed no less than three times, and about 150 analyses were made. The relative standard deviations are calculated. For Si, Al, Ca, Mg,

Fe < concentration range 3 - 60% wt. ) Sr» 0.01 - 0.02] for Na, Ti, К ( concentration range 0.5 - 50% wt* ) S» 0.02 - O.0S.

Sv0 MJ> JU u t*sk,' LIL * LLX*° k. .° **0

4r *%

4M DEF0CU5SED BEAM AS A METHOD DF UNEARTH SUBSTANCE'S ANALVSIS XftS-90 N.N.KONONKOvA, K.I.IGNATENKQ, A.A.YAROSCHEVSKY Vernadsky Institute of Geochemistry and Analytical Chemistry, USSR Academy of Sciences, Moяcow, USSR The defocussed beam s method is used for analysis of samples «nth little mass and we cannot use traditional methods. ZAF or PAP- correction are not applied for analysis of unhomogeneous samples. The samples with phases sice more than depth of X-ray's generation (

PI Op» 0 Chr Ill» By By Voix 11.» 41.8 is.e o.ie o.ie nin.r. ZAF N.z.rov utX IO.« 74.8 14.8 o.aa

Si03 45.ee so.ee ее.02 97.20 S7.10 57.90 Ti0 0.02 0.ЭВ 3.BB 93.27 2 - 0.44 о.эе O.44 «403 32. S« 0.40 О.ЭО 7.94 0.07 Э.78 o.o» 4.99

Cr 0.02 0.22 91.18 0.18 2°3 - 0.Э0 0.29 0.30 FaO 0.43 38.IO 0.37 34.04 43.93 21.IS 20.79 20.B8 HnO 0.03 o.ee 0.01 0.82 1.49 o.ee 0.97 0.98 MgO 0.01 14.91 O.Ol i.oe 1.Э4 10.7S 8.91 8.90 CO 18.ee 4.03 0.O2 -- 9.39 9.93 9.31 N> 0 1.00 0.03 0.09 0.31 2 -- o.ao 0.23 K2° 0.19 0.01 0.21 -- 0.09. 0.12 0.10

Raf.ranoe

l.Naiarov H. A., Ignatwiko K. !.*t al //Lunar and Planatary Scianc*. teee.p.gas.

417 THE PECUblARITIES IV I-HAX JUJAUCSIS OF ЫОНТ BbfflENTS | IH COHPOUHDS AHD «INBRAbS |XHS-91 I.H.Kullkova, R.L.Barinsky Institute of Mineralogy, Geochemistry and Crystallochemiatry of Rare Element», Mosoow, USSR la X-ray analysis the concentration of very light elements (from

В to P) la determined Ъу Кл line». Due to electronic tranaltlona from 2p atoaio valence state», the K^ Una (ita form and energy of main peak) la strongly influenced by the chemical bonds. On the high-energy aide of Kgi linea of light element» there are aatellitaa of multiple Ionization Kljjj-Ljjj.the lntenalty of satel­ lite» la function of the type of chemical bond and can amount 2656 of main line peak for В and 40* for P. On the low-energy aide of the В epeotra arises an additional peak which corresponds to the energy of 2s level of Uganda (H,0 etc.) and has been attributed In the В spectrum to the hybridisation of В 2p and llgand atataa» The Intensity of this peak In mineral» can amount 209C of the main line peak, to avoid the Influence of the chemical bond on the results of X-ray analysis we propose to measure the in­ tegral of the peak Instead of the lntenalty in maximum. In many oaaaa the effect mentioned above oaa draw additional conclusion» about type of chemical bonds of the atom, being analysed, with different 11- ganda, oovalenoy and phase composition of the probe. The abaorptlon ooeffioient» In this range of energies are very large (e.g., for В K^ line the absorption coefficient is 84000 cmvg in Si) and oan be measured with great difficulty. Hence, to calcu­ late the concentration with enough preoislon It follows the impor­ tance of taking Into aooount the correot oholoa of abaorptlon coef­ ficient and. In the ease of analysis by primary radiation, the cor­ rect value of the eleotron acceleration voltage (to regulate the depth distribution of the radiation). There Is alao a problem with the choice of computation model as the corresponding errors have bean found to lnoreaee with inoreaalng the value of absorption coef­ ficient for analytical line by matrix elements. With the factors, above mentioned, a method for microanalysis of В and 7 In different minerals has been developed. It la shown by com­ parison with wonoorystels of mineral» of known composition that the relative Inoertalnty In the concentration» can be aatlmated to less than \% for Г and 38 for B. The detection limit la 0.1* for T and 0.5» for B.

4» ELECTBONE-PROBE INVESTIGATIONS OF POWDER MATERIALS T.A.Kupriyanova Moscow Institute of Fine Chemical Теспоlogy, Moscow, USSR

Being the methods of undestructlve control of the composition and the structure of the materials, the electrone-probe methods SEM and EPMA are widely applied at different stages of powder- metels technology. The accuracy of EPMA methods is determined by the knowledge of systematic errors sources» that appear during" the preparation of powder-type objects for the investigationв, obtaining an analitycal signal and transition from an analytical signal to quantity of elements to be determined. The methods of sample preparation may be divided into two groups, when the meaning of particles is followed by the destruction of their surface and when the surface morfology is preserved,but the particle form should be taken into account. Depending on the method, analyses are also divided into ordinary ones of compact samples and analyses of indidvidual particles. The accuracy of analyses is influenced by the particles size and density achieved after pressing in the first case, and the size, form, porosity of investigated particles and the material attaching a particle on the layer in the second case. The standard samples analogous to investigated ones being actually unprepareable, compact samples are expedient to be used as the standards. However, when the differences in angles of primary electrones incidence and secondary X-rays radiation and decreasing an energy of primary electrones due to local charge, which appeared in area of X-ray generation, are ignored. the results of powder materials analyses are qualitative or half-quantitative as a rule. The development of quantitative analyses methods of single particles is limited by the absence of independent method for local determination of composition, that could assess the accuracy of the results obtained. The composition of original alloy being known,subtractive metallurgy method allows to calculate elements content in the powder and thus to check up experimental results. Investigations of systematic errors in porous materials and individual particle analyses and comparison of different methods for transition from analytical signal to the concentration of the element to be estimated showed that it is necessary to use methods that do not require a knowledge of experimental conditions. These are methods,that use speotral or integrated intensities of continious spectrum or analytical signal - accelerating voltage dependencies, The EPMA of powders showed, that accuracy of quantitative determination not less than 10* may be achieved, and it does not depend upon the particles sise ranging from 1 to 20 micrometers.

42» THE QUANTOHETRIC METHOD REALISATION IN X-RAY H1CROPROBE XRS-93

ANALYSIS OP MINERALS

A.I.fuJznetsova,Yu.G.Lavrent'ev,S.V.Letov,L.V.Uaova Institute of Geology and Geophysics, Novosibirsk, USSR

New possibilities arise in microanalysis with the quantometric method using. The particular features of quantonetric mineral analysis are : limitation of the number of determined components with respect to the number of real spectrometries1 channels, simultaneous analytical line registration (the background 13 calculated), the computation of concentrations by dynamical equation with functional coeffici­ ents for interelement influence correction , and preparation specimens as a prepa- rate uith hundreds of coins of one mineral row. As minerals present multicomponent compositions, and the number of spectrochenical channels are limited , experimen­ tally undetermined concentrations are calculated by stechiometrical relationship equations . The quantometric method has been realised in QUANT program for H Camebax Micro " microanalyser with 4 wavelength spectrometers controlled by PDP 11/23 microcomputer. The program includes-. 14 separate quantometric tasks for a wide mineral field : chromspineleB, ilmenites, pyropea, garnets, olivines, carbonates, rutilee, native gold, and their number can be extended. The program contains more than 50 special subroutines and 2 libraries for terminal and printer service at well as a microprobe control library from " Camebax Micro ". The list of tasks represents for researcher the next variants : specimen analysis, standards or background standards chainging, crystall changing, peak searching for analytical line, standards and background standards data acquisition , measurement time and number of repeats changing , and other service possibilities. The reproducivity of the method in different coins range can be characterized by mr nearly It , when the determined component is not less that 10*. Of par­ ticular interest is determination of low concentrations of QjOj and CaO in olivine, where detectable limits 0.006-0.008* can be achieved. In comparing the relative intensities, determined by quantometric method and standard software supplied for " Camebax Micro " the results are characterised by less than 2*. As the experience showed , the used quantometric method allows to achieve high productivity X-ray microanalysis with 100 analyses by hour. The more effective application of this method can be achieved with multichannel device for primary X-ray spectrum analysis.

m QUANTITATIVE X-KAY ANALYSIS OF MINERALS I KITH AUTOMATIC ELECTRON HICROPROBE I _. Yu.G.Lavrent'ev. O.N.Majorova. V.F.Kakhotko et al. Institute of Geology audi Geopbyalcs, Novosibirsk. USSR Quantitative analysis vith modern automatic nicroprobe is produced with the help of beforehand formed and corrected programs. Many variations and complication of chemical mineral composition, specific of mineral-geochemical investigation require appropriate varietes of the same programs. In this report we discuss the experience software design for quantitative analysis of minerals using electron microprobe "Camebax Micro" under computer control PDF 11/23. On the first stage during analytical experiment planning we have help programs and programs, directed for various parameters, for example, the calibration dynamic equa­ tions coefficients, taking into account coefficients of line overlapping. The programs used for direct analysis in the'^on line'mode are the most essential. The basic universal program is RMA89 . The transformation of the measurements to ana­ lysis results Is produced selectively by ZAF or Pankratov methods. The background can be found by direct acquisition, as well as by Bocker-Hehenkomp computation method. The background charocteristical component (line overlapping) is provided. The analytical line registration from the specimens, unstable under the electron probe can be made in dynamical mode, when the analytical signal variation has been traced with its extrapo­ lations to the beginning! of analysis. The flexible program structure makes it possible to change analytical conditions. The changes of the correction method, standards, spe­ ctrum registration conditions, peak positioning, additional standard measurements, analytical lines set extention (up to 15) or, in contrast, shortening of this set are possible. On the universal program basis a number of special programs for several tasks solu­ tion are produced. Such programs, for example, PYROXK and OLIV07 are intended for the analysis of pyroxenes and olivines from kimberlites.These programs reduce the limit of detection to 0.005* for К in pyroxenes and for d. and Ca in olivines at the expense of redistribution count time. The other special program is DINCOT, where the measurement result correction is produced with the help of calibration dynamic equations (oC-para- metere method). It makes possible to analyse minerals, including up to 25 elements.!)» quantometric analytical program QUANT takes special place, allowing to increase measu­ rement productivity by order. It is intended for determination of four (number of spe­ ctrometers) elements in particular minerals and include 14 quantometric tasks itself, arised in composition determination of chromspinels and ilmenites, chromium's pyrope, garnet, rutile, olivine, amphibole, carbonates, feldspars, eordierite, native gold. As a rule, in conducting the analysis one correction method, may be not the best, can be realised, so it is worth to have a possibility of varying methods of ln%ff li- no'mode correction. New version of autonomounm program CARAT serves this purpose. This report does not consider specifleal computer software for processing and pre­ sentation of minerel-geochimical information contained in analytical results. Practical application of the mentioned pruytums is shown by the concrete examples.

431 possiBibrre иж вювмшииои or commtte or r» IOHS I WITH DIFSBRBBT VALBHCB n SILICATBS JUTO oimas вг I "9? SbBCTROB HICROPROBB S.V.Legkova Institute of Geoohemietry «id Physios of Minerals, Ukrainian SSR Aasdeny of Solenoas, Kiev, USSR

The connection of relative intensities of FelV- and L^- X-ray emission peaks Talent state pointed out by Andersen [l] serves aa the basis of an electron raioroprobe analysis of the iron ions with different valent state. The critical observation of the experimental data considered on the basis of [2] using information from \z, 3, 4, 5] and those obtained by the author with coworkers, allowed to establish the existence of a linear function between FeL^/Fel^-ratios and re­ lative fraction of two valence iron (Fe /Pe) in silicates (am- phibolee, pyroxenes, garnets, micas, chlorites) and oxides (he­ matite, ilmenite, spinel). The equation coefficients depend on the type of a chemical bond and the character of isomorphism. The obtained equations give the possibility of the rutine analysis performance of different valence iron .ions by EMPA in silicates and oxides having practical significance in the inves­ tigations in the field of geochemistry, petrology and material science.

References 1. Andersen C.A. // Brit.J.Appl.Phya. 19€7.fol.1S.P. 1033-1043. 2. Legkova G.V., Voytkevich V.O., Sharkin O.P. // Mineral.J. 1982.Tol.4iN4. P.90-93- 3. Albee A.L., Chodos A.A. // Amer.Miner. 1970.7ol.55tN 3-4. P.491-501. 4. Taskaev O.G., Struchaeva A.O., Pyatkov A.G. // Methods X-Ray An. 1986. P.154-158. 5. Paradina L.P. // Pros. I Ket.Seh.-Conf. 1989. P.32

4» BLBCTROJ? HICHOPROBB DBTBRHIHATIOH 0» Pe' .3+ О0И1Ш1Т 1Я QiBXBBS I -96 C.V.begkova, A. A.Vishnevsky, V.B.Soholev Institute of Geochemistry and Physios of Minerals, Technical Centre, Ukrainian SSfi Academy of Sciences, Kiev, USSR

A dependence has been confirmed of PeLjs..- and Fel^-X-ray ratio on iron content with different valence previously obtained for am- phiboles [l] and pyroxenes [2] on the example of minerals of garnet group. Experimental investigations have been performed using "Super- probe-733" microanalyzer. Garnet compositions have been determined using ZAP-OXIDE standard program at 20kV (accelerating voltage) and at 5-10 A (probe current). Bleotroneutrality principle has been used to divide total iron In the analyses. Fe /Fe ratios {Fe=Fe2++

3+ Fe ) have been calculated from those data. Measurement of РеЬл- and FeL^-lines has been made at 15kV and 5*10" A, then the ratios of FeLjb,- and L^-X-ray emission peaks (n-FeL^j/PeL.,) have been calcu­ lated allowing for background correction. Experimental and calculated data have been used to plot graduated curves n»f(Fe /Fe). Linear character of dependence between n and Fe /Fe has been established in garnets of pyrope-almandine and grosaular-andradite series. The above investigations clearly demon­ strate possibility to ex­ perimentally determine Fe and Fe'* oontent in garnets of different com­ position.

Dependence of FeL^ anid I^-ratio1ц-п s on Fe2+/Pe ones In gar- nets (I - pyrope-almandine series, II - grossular-andradite series)

Referenoss 1. Legltova С.У., Voytkevich V.G., 3harkin O.P.// Mineral.J. 1982.Vol. 4, N4. P.90-93. 2. Taskaev V.I., Struehaeva CO., Pyatkov A.C. // Methods X-ray An. Novosibirsk: fcuka, 1986. P.154-158.

28.3MC.4I3 «J ELECTRON PROBE IHVESTIGATIOBS OP OXIDE LAYERS f~" XHS-9? ORIGINATING IN OXIDATION OP TITANIUM ALLOYS I S.H.Petrov Central Research Institute for Structural Materials "Prometheus", Leningrad, USSR Stress-corrosion behaviour of a material is to a greate extent de­ pendent on the composition and structure of oxide layers (OL). The EPMA has been accepted as the main method of the OL investigation with a variation in the electron energy Б , and a layer-by-layer ana­ lysis using Auger eleotron spectroscopy (AES) has been carried out for some specimens. Micron and submlcron thiok oxide layers were tested. The objects of this type do not require to quantitatively restore the concentration profile. It necessitates accurate measurements of the intensity with a small BQ step and a considerable computering. The concentration pro­ file was roughly estimated, and the intensity was measured with a 1 kV step. The subsurface layer composition can therewith be determi­ ned and the element cementation variation traced to the depth of se­ veral microns. A method to estimate the emission zone depth at a givjn

E0 value is suggested whioh allows to evaluate the OL thickness as a function of I(E ) for the base metal. The thickness evaluation using the method suggested for the specimens of a known layer thickness has yielded satisfactory results. The greatest error was not more than 2СЙ. Binary titanium-aluminium alloys and alao VT5-1 alloy oxidized in air at the temperature of 800°C were tasted. All the OL have been fo­ und to be of an inhomogeneouB composition thioknesswise. The subsur­ face zone of OL is highly enriched in aluminium (2-3 times as much as metal). The thickness of the enriched layer and its aluminium content vary depending on the alloy composition and oxidation time. For the OL of the VT5-1 alloy it has been found that the zirconium distribu­ tion is antibatic to that of aluminium, whereas the vanadium concen­ tration is constant over the full OL thiokness, and its concentration oonforms to that anticipated for the oxide. Layer-by-layer analysis data obtained using the AES method are in good correlation with those of the EFHA.

434 ШСТЯШ-РЮВЕ МИЯЮАНАЫЕК от яиок-вшоик г— 1 XBS-9S I.M.RonBiienko ' ' "Glproecvetmetobrabotka". Moscow, USSR The electron-probe microanalysis ДОНА) has the ll*it of detec­ tion (for the different elements) 0.1 - o.ooix wt. approxlmatly. The BMl Isn't the hltfaaeneltivcanalytical method, though the aw limit of detection of ЕРШ 1в reached 10~M g. The poslbllltle of ИРМА for the trace-elements determination one can estimate by the ll»lt of detection dependence on the relatlonahlp of the analytical line intensity/background intensity (R) and the etaudard deviation of the background Intensity measurement (в). I.e. C(D.L.)-F(R,B). The X-ray characteriatlc lines (analytical lines) Intensity dependson the energy of electrons (KO.malnly.and on resolution of the X-ray spectrometer (r).Tbe value of the background intensity dependson the average atonic nunber of taget (Z) and energy of electrons. The standard deviation depends on background intensity and the period of the measurement. Ana, at last, background depends on the structure of the background emission. The limit of detection, as the function of the relationship peak/background and the standard deviation is confuted for X-ray energy dispersive spectrometer simply ID. But the compute of the limit of detection of the X-ray wave dispersive spectrometer is more complicated and it Is connected with the undetermlni of the resolution depend on the value Bregg angle and the quality of mauufected cryatall-analyser.

Reference 1.Reed S.J.B.//Blectron Microprobe Analysis, Cambridge University Press, Cambridge. 1975

4S5 STATISTICAL APPROACH TO THB ASAMSIS OP raHOMOGBUBOUS I - MATERIALS LOCAL X-RAY HICROFROBB A1CALISIS 1 "" S.I.Shevtsova, A.T.Kosakov Physios Research Institute, Rostov State University, Roetov-on-Don, USSR

A new technique within the Х-гаУ mieroprobe method for the analy­ sis of inhomogeneous samples has been developed* The technique allow determination of the charaeter and type of lnhomogeneAty.the number of phases, their bulk concentration, interelement relationships, the degree of inhomogeneity. The technique consists in recording X-ray line intensity of se­ veral chemical elements in a great number of randomly chosen points and in analysing the obtained set of distributions. Analysis of the distribution parameters and shape allows detection of inhomogeneity and determination of its degree. With the help of correlation technique the character of the inhomogeneity (presence or absence of separate phases, contamination, porosity, different thickness of the costing, etc.), interelement relationships (in­ cluding chemical composition of separate phases) and the number of phases свп be determined. Besides to determine the bull: concentration of the chemical phase (or pores) the procedure, that takes into consideration finite phase dimensions and analysed region, has been developed. In addition the statistical approach within the framework of the local X-ray mlcroprobe analysis makes it posible to determine either the average chemical composition of the whole sample or the compo­ sition of separate phases. The statistical approach in X-ray mleroprobe method has been successfully applied for the chemical phase analysis of active ce­ ramic materials, high temperature superconductors and microelectro­ nics materials [1,2] .

Referenoee 1. Shevtaova S.I., Kozskov A.T., fesenko E.G. et al.// J. Anal. Chem. 1989. Vol.44. P.45. 2. Varukhin V.B., Kozakov A.T., Demyanchenlco V.A. et al.// Super­ conductivity: phys., chem., tech. 1989. Vol.2, I 10. P.26.

4M X-RAY MICROANALYSIS DF PRECIPITATES IN Co-BASED ALLOY| 1 XHs-100 B.Surowska, A.Stefanovic* ' Technical University of Lublin, Poland »R0 MIN Institut, N19, Yu The Investigations were carried out on Co-baaed alloy Med- pol 2 used tor surgical implants in orthopaedic. This alloy consists about 20 pet Cr, 18 pet Ni, 3 pet Mo, 0.5 net Nb, D.01 pet C, max. 0.025 pet N^, balance Co. It was expected that the primary precipitates were niobium carbonitrides [l,2] . Contrary to expectation the X-Ray analy­ sis in microregions stated the presence titanium in these pre­ cipitates. Electron microprobe images and elemental profiles were made for Cr, Ni, Mo, Co, Nb and Ti. Only increase of con­ centration of Ti was observed in the region of precipitates. X-Ray fluorescence analysis verified the presence about 0.02 pet Ti as trace metallurgical impurity in this alloy. The phase analysis carried out by X-Ray diffraction was helpful in iden- tifity the primary precipitates as Ti(C,N>. Niobium is probably dissolved in Co matrix - such result is suggested by electron microprobe images of Nb segregation. However the investigation of the form of existence of niobium are continued because it is known fl,2,J} that in Mb-stabllised steels some .to-rich phases are observed. References

1. Powell D.J., Pilkington R., Miller O.A.// Acta Metall. 1»BB. Vol.36.P.713. 2. Voice W.E., Faulkner R.G.// Metallurgical Trans.A. 1?85. VO1.16A.P«511. J. Siweckl T.// Proc.VII Conf. on Electron Micr. of Solid State Cracow (Poland), 1789. P.111.

437 A DBVICB РОК OIH>B SAlttLB POSIOT I JUtS—101 A.L.Ivanov •

,, Research and Produotion Association "01i«metevtomatilca r Moscow, USSR Extensive application of the oxide sample preparation technique based on fusion of oxide material together with a glass-forming flux will further promote the employment of X-ray fluorescence spectrometry for the analysis of mineral raw materials in the metallurgical in­ dustry ЛЛ The automatic device developed by us is intended for high-frequency heating of a crucible containing the sample-flux mixture and for motor driven pouring out the melt into the mould. The device has been tested in experiments with flux-forming mate­ rials containing carbon within 7-IOS. The fusion was made in glass; - carbon crucibles at temperature of I200°C and the sample-flux ratio of I•5} the sample carbon was oxidized at the first stage of fusion in the same crucible. The glass structure of the resulting beads was con­ firmed by petrographic analysis. Ine be.- analysis was made by means of the X-ray fluorescence spec­ trometer type CPH-I8/CM-I with its software based on the fundamental parameters method and multiple regression equations /г, 5/. The calib­ ration coefficients were determined using the works standard samples with the following ranges of the oxide content: 25-50* of algO,;

40-60* of CaO; and I.0-12* of S102. The analysis standard deviations were I.OS*, 0.38* and 0.A-5* for Al^O,, CaO and Si02 respectively. Reference I.Fani S.S., Binhaaahapatra F.X., Tendon A.E. Applications of X-ray fluorescence spectroscopy in iron and steel industry. I.Iron ore and related materials //Chemical Bra. 1982. Vol.18, H 9. P.226-234.

4И PIBLD X-RA1 SPBCTfiOHBTER V.A.Koetln XRS-102 VHIIOkaanmeologiya, Leningrad, USSR S.R.lforlkov Leningrad nuclear Physios Institute, Gatchina, USSR J.Banner Hungarian Geophysical Institute, Budapest, Hungary

Problem of search, prospecting of elnerals, ecological check require to aproech laboratory aethods to a probe choice places, and, in rose cases, to carry out in situ analysts^?/. To this pro* pose X-ray fluorescence spsctrneeter "AJAK8''ls developed. It based on Si

Kefsrences 1. Wognan B.A., Hlsek H.G.//ITM. 1975. Vol.128. P.561-568. 2. Kostln V.A., Kraanyuk A.D., Jukovsky A.H., et al.//Ooeanology. 1989. H 5.

«39 DEVICES POR THE ANALYSIS OF FILMS AHD SURFACE LAYERS USIBC XBS-103 X-RAY IOTAL REFLECTION EFFECT V.P.Krasnolutsky, Y.N.Loeev Physics Research Institute, Rostov State University, Rostov-on- Don, USSR

Working out the technique for high temperature superconducting films production requires non-destructive and highly sensitive cont­ rol of the bulk and surface composition of films. It has been shown that this problem may be solved by energy dispersion X-ray fluores­ cence analysis using X-ray total reflection effect. In foreign ecological studies this method successfully competes with such highly sensitive methods as neutron activation analysis and induotively coupled plasma optical spectroscopy. Due to small penetration depth (10 ma), cutting ofx of the conti­ nuous spectrum shortwave section and reduction of the initial exci­ ting X-ray beam intensity by several orders it is possible to achieve the detection limit of several ng for the analyte. With the new design one can do without precision mechanical devi­ ces. Moreover the adjustment of X-ray optical system becomes consi­ derably easier. The spectrometer also allows the analysis of both surface layers and bulk sample composition. When surface layers are analysed the primary x-ray bean passing through the system of two parallel total reflection mirrors is Incident on the sample surface at an angle of 5' ... 10', and in analysing the bulk sample compo­ sition - at an angle of 45°. In the first case the primary beam that has experiences total reflection is reflected from the sample surface. In the second case the beam that has undergone double reflection from the mirror penetrates the sample to the depth of several mkm. The sen­ sitivity is increased by filtration (i.e. by cutting off) of the shortwave section of the primary spectrum in the ease of total re­ flection from the mirrors. Energy dispersive X-ray fluorescence analysis of the bulk and sur­ face composition by the same device allows the evaluation of the ele­ ment distribution over the depth in high temperature superconducting films. X-RAY FLUORESCENCE METHOD FOR IBB DETERMINATION XRS-104 op THE COMPOSITION. лш> iHiciaress OF шин FIXMS AND COATS N.I.Maehin, H.K.Rudnevsky, S.B.Belyaeva Chemistry Institute, tf.I.bobachevsky State University, Gorky, USSR The present development of computer and semiconductor engineering, quantum microelectronics and other technology Is connected with the usage of materials produced from one- and multilayer films. (The film properties are substantially determined by their composition and thickness. The X-ray fluorescence analysis is a nondestructive and proximate method, it being characterized by a sufficiently high accuracy of the analysis for the films of different types. The X-ray fluores­ cence determination procedure of the thickness of thin (< 1000 nm) one-layer (Si, Cr, Fe, Co and so on) and tiro-layer (Ou/Hl, Si/Ge, Si/Mo, Ge/Si and etc.) coats and of the composition and thickness of two-somponent one-layer thin films (Si-Ge, Fe-Ni, Ni-Co and so on) supported on ceramios and aluminium has been developed. It was shown that the surface density of one- and two-layer sup­ ported coatings consisting of elements with small atomic numbers can be estimated both from the relative and absolute Intensity of the analytic line fluorescence of the element detected. In the lat­ ter ease the analysis duration is decreased by several times. The different values of the density for the bulk samples and films for­ med by various spraying methods of the same samples have been found. With due regard for this fact it is possible to increase appreciably the precision for the determination of the film and multilayer coa­ ting thickness. The procedure suggested allows us to determine the composition and thickness of the films (15-1000 nm) supported on steel and ce­ ramics with an accuracy to 0.5-2*. She time of one determination is 1-2 min.

441 SCANNING X-RAY SPECTROMETER SRS-5 XRS-105

B.S.Verman, I.P.Zhizhin LNPO "BOURBVESTNIK", Leningrad, USSR

The SRS-5 spectrometer is a scanning X-ray fluorescence spectro­ meter with the Johansson focusing which permits to obtain the best combination of efficiency and resolution of the spectrometer and provide sufficiently high sensitivity when using an X-ray tube of 240 Ы* Due to this there reduced considerably the mass and size of such devices as a h.v. power source and a closed cooling system of the X-ray tube. The use of focusing X-ray optical system permits also to obtain high resolution (3-4 angular minutes) unatta­ inable for spectrometers with Seller's system.

Range of analyzed elements: boron-uranium. Number of automatical­

ly changeable analyzing crystals: 8 (LSD, LSD., RbAP, PETP LiF200, L1F220, Si422, GelllJ. The apparatus can be additionally equipped with crystals S1220 and Ge422. X-ray tube anode materials; Cr, Ho, Pd, Re. Number of simultaneously loaded specimens: 22. Spectrome­ ter massi 275 kg, power consumption: 2 kw.

The spectrometer is delivered with control programs providing the automatic calibration of the spectrometer, realization of qua­ litative and quantitative aralysie and results processing.

The enhanced program systems for qualitative and quantitative analysis can be delivered additionally. The qualitative analysis includes automatic identification of lines and standardises semi­ quantitative analysis. In the present paper there described principles of arrange­ ment of separate systems and results of tests. MISCELLANEOUS SPECTROSCOPIC TECHNIQUES AND LATE ABSTRACTS

4 DBTiSRHUfATIOH OP MICROBLEHSHTS COHPOSITIOlf 0? BOTTOK I DEPOSITS .".USPEHDgD JtATTBR ADD AEROS0LB3 BY THB HBUTRON- | HISC-1 ACTIVATION, ATOMIC-SMTSSIOM AHD ATOMIC-ABSORPTION METHODS OF АНАЫГ313 V.V.Anikeev*, L.N.Bannykh, O.M.Kolasov, S.K.Preead, E.M.Sedykh, !T.P.3tarshinova, B.H.Shumilin* Vamadaky Institute of Beochemistry and Analytical Chemistry, USSR Academy of Sciences, Moscow, USSR •Pacifio Ooesnologieal Institute, №r Best Branch of the USSR Academy of Sciences In order to obtain more information about the contaminants escape into environments and their isolation a whole complex of modern methods is required. ШАЛ, AE-ICP and BTAA-methods are used for investigation of ecosystem (aerosoles,suspended matters and bottom deposits) as an exam­ ple on samples selected in different climatic zones of South-East Asia shore. Samples of suspended matter were made by passing of I 1 of water through the filter with 0.45 mkm porosity, taken by plastic batometer; the bottom deposits were taken by bottom bucket and divided into frac­ tions by their size, eerosoles - by depositions on membrane filters. IHAA. She investigated samples of 10 -60 mg mass were placed into Al -foil,irradiated in the reactor by thermal (20 hrs) and epithermal (80 hrs) neutrons and the induced activity was measured on spectrometer with Ge(Li)-detector and 4096-channel pulse analyser. The gamma-spectra pro­ cessing and contents calculations were carried out according to the spe­ cially developed program. As s standard, samples of soil, bottom depo­ sits and model solutions were used. BBS, la, Hf, Bb, Ce, Cr, Co, So, Th, As, Sb, Ha and other elements (»20 ) were determined. AE-ICP, BTAA. The elements determination was obtained from aliquot solutions after the decomposition of bottom deposit samples by mixture of HF and HHO, acids, suspended matter - HNO», filters - by HH0.+ HgOg ashing, addition of I - 10 ml 1,5 К НПО, depending on weighted amount ( 5-50 mg ). The spectral superposition of separate lines were studied, the programmes of simultaneous determination of elements were composed. Al, Ba, Ca, Cd, Cu, Mg, lln, Ho, Hi, Pb, Sr, Xi, Zn, Zr, Co, Ре, К were determined by AE-ICP method on the polychromator ICAF-900; Co, Sn, Cd, Ho, Pb, Cu, Bi, Se, Те, Sb, As, Tl by the BTAA method on the spectropho- tometr 3OJ0 Z, HGA - 600. Reliability of obtained data, was evaluated by the comparison, with the results of standard sample analysis and deter­ mination of separate elements by the above methods. The application of a number of methods allowed to obtain the informa­ tion about the content of more than 40 elements, wioh are used in study on the mechanism of their distribution and exchange in aerial and water reservoirs of territorial sea zone.

444 ANALYTICAL PROBLEMS OF THE DETERMINATION OF MOLYBDENTO1 MSC-2 IN GEOLOGICAL SAMPLES BY DIFFERENT METHODS

E. Bertalan1, P. Fodor2, Za. Molnir5 l>Hungarian Geological Survey, Budapest, Hungary 2-University of Horticulture, Budapest, Hungary 5-Technical University of Budapest, Budapest, Hungary Within the framework of an exploration of the so-called etalon area Ree.sk (Hatra Mountain, Hungary) a number of analyses of ore bearing samples were carried out by optical emission spectrograph?. Analysis data were needed to be controlled by other methods, too, A series of control analyses for molybdenum are introduced* Л series of samples with different matrices (porphyritie, skarn, polyaatallic etc.) were select»1. Molybdenum content of about 100 samples was determined by F-AAfl and XCP-AES method and that of 27 samples by IMA method. Molybdenum in the samples was present in the form of molybdenite MoSg . Because the molybdenite occurring, in these samples was fine grained and built into the silicate structure, a full decomposition of samples was needed for AAS and ICP methods. For AAA aethod the powdered samples were decomposed in high pres­ sure teflon bomb with the mixture of cc. BC1-HH0,-HP acids. After decomposition 0,5* Al was added as releasing sgent. Determinations were carried out in a fuel rich (luminous) OgfU-HgO flame. For ICP method the powdered samples (after ignition) were decom­ posed by IdBOg fusion in platinum crucible. The sample solutions were analysed by a Jarrell Ash ЮАР 9000 spectrometer at the univer­ sity of Horticulture. The 1ЯАА analyses were carried out from the original powdered samples (withovt chemical separation) in the reactor of the Technical University, by a CAKBEBEA 60 analysator with HPGe detector. All of the methods ware controlled by С0МЕС0И standard rock aamp-

The results achieved by different methods are introduced. After control of homogeneity the analytical methods were compared. With the aid of the Solovov's criteria the systematic or random character of the deviation between the individual aeries of results was found. An attempt is made to explain the results.

448 APPLICATION OP FLAKB РНОЮМВТЮГ METHOD FOR ENVIRQHUEHTJU. Г COHTHOL Hf THE PROCESS OP CRYSTAL GROWTH I 3 N.V.Bondarera, V.G.Potapova Institute for Single Crystals, Kharkov, USSR The «alt» of таг* alkali (lithium, oesium), alkali earth (stronti­ um, barium) ant heavy (tallium, lead) bismuth) mstals are widely used for growing optical, sointillation, laser, supareonduotlng and other types of single crystals. It la well known that even the smallest amounts of suoh metals have a tozlo effeot on human and animal orga­ nisms. Therefore it is necessary to oarry out a systematic; environ­ mental control for the sold elements.

To develop a teohnique of determining the toxic metals Li, Cs, Sr, Ba, Tl, Bi, Pb in purified waste water and working area, air the me­ thods of atomic emission and atomic absorption flame photometry hare bean applied, sinoe the majority of enterprises possess the corres­ ponding equipment. The measurements hare been oaxrled out by means of "Saturn" spectrophotometer with acetylene-air, aeetylene-dinitrogen oxide, propane-butane-dinitrogan oxide flames.

Por the elements under consideration the dependence of emission sad absorption signals on the variation of the apparatus operating pa­ rameters has been studied. We have computerised the conditions for de- texmlnlng each metal (i.e. method,analytical line, flame type and ope­ rating conditions, registering system) for optimisation. The effect of varying impurity composition of waste water on measurement results has been investigated; the levelling conditions have been chosen. The methods of dissolving the Impurities , oonoentrated in the filter in the process of air eai~?ling have been studied. The detection limits for the normalised elements are leas than the corresponding values of their permissible oonoentratione. The measu­ rement errors are 1-5 rel. %.

44* COMPARISON OF DIFFERENT APPROACHES FOR ANALYSIS OF

A.DeliJska-Krushevska, S.Momtchilova, V.Gantcheva s Institute far specialty chemical», Vladaya, 1741 Sofia, Bulgaria

The possibilities of hybrid methods which combine chemical sample prmtrwmtmmnt with atoniс spectroscopy detect!on in the analysis of high pure chemicals were investigated. Different preconcentration approaches were used including extraction, ion exchange, sedimentation and destilation. Various measurement techniques were applied - AAS with flame and graphite furnace and AES with d.c. »rc and ICP. Using experimental design strategy optimal working conditions were chosen. The methods for determination of trace metals in H-60-, alkali—

and alkali earth carbonates, МНдН_РО. were carried out.

447 ITOLTICHAHIffib RECORDING SYSTEMS TOR MICROCOMPUTER-CONTROLLED АТЧШС-ABSORPTION AHD HUSSION SPECTROMETERS BASED OH LINEAR PHOTOSENSITIVE CHARGE-TRAKSPER-CIRCUITS HISC-5Л; S.P.Gorbachyov, A.P.Dyomin, V.K.Dyomin Institute of Applied Optics Kazan, USSR Different variants of multichannel recording systems based on home-produced linear photosensitive circuits are 'developed and inves­ tigated r'tl • Xhe analysis of the use of photosensitive linear arrays and different structures of charge-coupled devioes showed advantages of systems with separation of detection, storage end charge-transfer funotions in different registers.

With allowance for the above and the features of image forming in a spectral device, technical requirements are defined and, on the authors' request, a special-purpose photosensitive oharge-transfer devioe is developed. Using this device, a recording system for a spectrometer is produced and its characteristics in the conditions of a real-time speotral analysis in the emission regime, using an alter­ nating-current arc, and in the absorption regiae, using a flame ato­ mizer, are investigated. The operating speotral range of the system is 250 to 860 mm, the absolute sensitivity at a wavelength of 660 ram is 12-10° V/W. The miorooomputer software providing oontrol end pro­ cessing of data is developed.

References 1. Arutyunov V.A., Gorbachyov S.P., Dyomln А.Р.//ОИР. 1986. Vol.1. P.34. 2.Dyomin A.P.//РТЕ. 1988. И 6. P.150 swroias ои тнв соырозшов op su/r излю ATOMIC Гшас-б SPECTROSCOPIC LIBTHQDS I D.H.Ismailova, T.F.Mitina, E.P.Kaptenko, U.P.Abaahkina, H.H.Chebnn CAM of the Aoadeagr of Solenoes of the USSR, Kishinev, USSR Silt of sewage waters contains significant amounts of mineral and organic matter, which makes it useful. However, high concentrations of toxic metals in silt can negatively effects the ecological situation where it is used. This particular problem stresses the need to develop more aeurate analytical methods to determine the composition of silt. In the present work atomic absorption and emission spectroscopic analyses were used to study the silt. Priliminary studies were oarried out In different ways of decomposition of solid samples and conditions to obtain analytical signals with least matrix and background noise.

It was shown that treating samples with a mixture of H2S0. and 1Ш0, in the presense of vanadium pentoxide was more effective in bringing mer­ cury end arsenic into solution, whioh was used for their analysis. For a more complete extraction of cadmium, zinc, copper, manganese and iron, samples which were combusted at 450eC were treated with concent­ rated НПО, or the samples were fused with sodJ-= carbonate and borax (sodium tetraborate). However the former method Was more effective. For each element, optimal conditions for spectroscopic determina­ tion were worked out (Table}•

Conditions for the determination of toxic metals in silt element Wavelength, Instrument tetectlon Relative Atomlzation Tim Limit ii standard source deviation Ug 253-7 AAS-1H 5-10"8 0.05 Cold vapor As 193.7 Perkin-Elraei 1.7-10"5 0.12 Graphite furn. Cd 228.8 AAS-3 5 -10"5 0.14 Air-acet.flame Cu 324.7 ~n~ 7.5-Ю"5 0.056 Saw Zn 213.9 -»- 7-5-10"5 0.036 «ii- Pb 217.0 -»- 6.3-10"* 0,04 -ti— lin 279-5 -ii. 1.5'10"* 0.015 .ii- Pe 248.6 -ti_ 1.3-10"4 0.015 -H_ P 2?f-5 DPS-13 2.10"2 0.12 DC carbon arc Large scale analyses of silts of industrial sewage waters end ground waters (total as well as separate fractions) were carried out. Based on these analyses practical reoomendations were given on the use of silts in the national economy.

2Э.З*к.413 441 ATOMIC ABSORPTION AHD ATOMIC BMISSION SPECTROSCOPIC METHODS: APPLICATION РОЯ КЕУВАЫНО ТЖЗИЖРШС ' ' CHARACTERISTICS OF PLUORITE L.B.Krivoputskeya, I.I.tfrosov, L.B.Trofiraova, S.ll.Solnteeva, Z.K.Mazurova, Institute of Geology and Geophysics, Siberian Branch of the Academy of Sciences of the USSR, Novosibirsk, USSR The methods of atomic absorption and atomic emission spectro­ scopy as well as eleotron paramagnetic resonanoe have been used to analyze the dynamics of isomorphic admixture distribution in a fluorite zone crystal» There are six zones revealed in the sample under study from the chamber pegmatite nests (source: Kent) in the direction from the crystal centre (nucleus) to the periphery*

+ A pronounced trend was observed for v J( Hn , Gd*"' being de­ creased from Inner zones to outer ones. Changes in their con­ tents in fluorite structure cause changes in sample colouring» An Increase in their contents leads to the colour changing from light-blue to blue, violet and green» Differences In lb i Cd+' contents in fluorite structure also result in changing structural characteristics. An increase in эасЬ of these elements (Un and 0d+^, especially) causes a decrease in the unit cell parameter "a" (from 5.4641$ to 5.46306 A with a standard deviation of 5»10-5 A), a decrease in the "mosaic" blocks dimensions (from 1700 to 650 A), an increase in microdistortion value of crystal lattice (from 0.02 to 0.11) from the central zona to the periphery of the crystal» Thus, the analytical atomic spectroscopy methods allow us to reveal the fluorite typomorphic peculiarities (availability and quantity of Un, Gd*' «laments in a structure) and to un­ derstand changes in sample colouring as well as nature of mine­ ral forming medium» ANALYSIS OF ENVIRONMENTAL SAMPLES BY COMBINATION OF FLOTATION AND SPECTROSCOPIC METHODS HISC-6

S.Kunze, и.Dietze Research Institute of Mineral Processing Freiberg, Academy of Sciences of GDR, GDR In the course of time, with regard to trace analysis two approaches have developed on the international scale. On the one hand measurements are directly carried out by sufficently sensi­ tive methods, on the other hand there are the hyphenated methods based on preconcentration. The latter have the advantages that they are founded on reliable weXl-known determination techniques such as flame atomic absorption spectrometry, atomic emission spectroscopy and x-ray fluorescence spectrometry, often less expensive in investment than direct methods and simultaneous separation of element.traces from bulk. One possibility of hyphenated methods is the application of flotation methods following spectroscopic methods. The preconcen­ tration by flotation is known in the form of froth flotation [l], ion flotation [2] (bubble separation technique) and flotation spectrophotometry [з} (droplet separation technique). The froth flotation and flotation spectrophotometry are applied for the analysis of solutions from environmental waters to the element arsenic [4J and from benefication or hydrometallurgical processes to the elements tin, tungsten, gold, silver [5]. The following determination techniques are spectrophotometry, flame atomic absorption spectrometry, x-ray fluorescence spectrometry and direct-current polarography in their usual working ranges, thus reaching relative detection limits in ng/ml range. Reproducibili­ ty and accuracy of the results of these hyphenated methods of analysis are demonstrated.

References

1. Hizuike A.// Enrichment Techniques for Anorganic Trace Analy­ sis. Springer Verlag Berlin. Beidelberg. New York..1983. P.94 2. Sebba F.// Ion Flotation. Elsevier Publishing Сотр. Amsterdam. London. New York. 1963. P.127 3. Harczenko Z.// Pure ( Appl. Chem. 1985. V.57. P.847 4. Kunze S., Dietze U., Ackermann G./7 Microchim. Acta, in press 5. Dietze U., Kunze S.// Acta hydrochim. hydrobiol. 1986. V.16. P.473

451 SPICTBOSCOPIC INVESTIGATIONS OF HABK-BABTHS DOPED TERNARY SULPHATE GLASSES 1ЯБС-MI 9

S.V.J.l.afcnhman Vice-Chencellor, Sri Venkateswara University, Tirupati INDIA. Y.Subramanyam, L.Rama Hoorthy Spectroscopic Laboratories, Department of Physics, Sri Venkatenwara University, Tirupati - 517 502. IHDIA

Ternary sulphate glasses of the composition M - К - Zn (И - Mg.Ca.Ba) were prepared with 1HX of Pr**, Nds* Но9*. Кг** and Tm * ions as dopants in the glass matrices by adopting the quenching technique. The refractive indices and densities of these glasses were measured. Absorption spectra of these glasses «ere recorded in the OV-NIB regions at the room temperature. The spectral oscillator-strengths of the absorption bands were measured by the weighing method and correlated to the theoretical estimates determined from the Judd-Ofelt model. The significant influences of the glass compositions on the spectral intensities of the hypersensitive transitions and also the covalent nature of the rare-earths doped glasses were Investigated through the

phenomenological intensity parameter (;i2). Using these spectral intensity characteristic parameters, the radiative properties such am the transition probabilities, the fluorescent level lifetimes and the branching ratios were predicted theoretically for the different luminescent states of the five rare-earths studied in the present work. The radiative properties thus determined led us to identify a suitable chemical composition in generating the efficient laser emission properties.

482 .;• «цц ч»>..,.у-^'.-,; -^.^-^^-tvr-s i. •— — - - --- • ,

ATOMIC ABSORPTION ADD ATOMIC EMISSION ANALYSIS OF HIGH ГГ Ц PURITY GERMANIUM АШ) SILICON WITH SAMPLE VAPOUR-GAS I PHASE BREAKING UP IB AUTOOLAVB G.A.Hakaimov, V.G.Plmenov, D.A.Tiaonin Institute oX Chemistry of High Purity Subatancoa,USSR Aoadamy of Sciences, Gorky,USSR Til» properties of germanium and ailieon crystals are noticeably affeoted by the impurities even at the level lower than lO^-W"8*. The paper oonsiders the potentialities of atomic emission (AS) and atomic absorption (AA) analyses for nigh purity germanium and sili­ con with precoueentration of impurities by distillation when macro- component is ehemioally transformed into volatile compound. The purification of samples from surface contamination was car­ ried out in 100 class clean room. To tranfer the baae into volatile compound* hydroohlorio or hydrofluoric acids mixed with nitrio acids as well as xenon difluoride were used. An autoclave breaking up of monolithic samples has been done in vapour-gas phase directly in the electrodes of special design for AE analysis or on PIPE substrate. In the latter case the impurities oonoentrate was washed down with small volume of high purity water or aoids and transferred it into graphite furnace of atomio absorption spectrometer. The correction value for blank was mainly determined by the purity of electrodes and by the impurities earning from substrate material. The variants of impurities concentration on surface of the ana­ lysed sample are discussed which considerably decreases the conta­ mination level from auxilliary materials and surface impurities con­ tribution to the total results of analysis. The application of sample vapour-gas phase breaking up in auto- olave with maoroeomponent distillation for impurities concentration in combination with highly sensitive methods of atomic spectral ana­ lysis lowered the limit of impurities detection down to 10"7-10"11 wt.% which is by 1-3 orders lower than the known values ft-3) . References 1. Vasilevskaya L.S., Sadof'eva S.A., Omelyanovskaya O.D. et al.// у Hetody analyse, veshchestv vysokoy chlstoty. H.i Xauka, 196$. 3.119. 2. Yudelevioh I.G., Baplna T.S.//Iav. sib. otd. AH SSSR. Ser. khim. nauk. 1983. Vol.3, н 7. 3.74. 3. Fhelan V.J., Powel R.I.«.//Analyst. 1984. Vol.109. P.1269.

4И ANALYSIS OF ALLOYS ВТ ATOMIC ABSORPTION (FLAKE OR FURNACE) AND ATOMIC EMISSION (ICF) SPECTROMETRY METHODS WITH ELECTRIC SPARK SAMPLE PREPARATION IMISC-11 A.I.Pehelkin, E.V.Shipova, I.P.Kharlamov Institute of Technology and Machine Balding, Moscow, USSR Methods of atonic absorption (AA) and atonic emission (AE ICP) spect­ rometry were introduced into analytical practice in combination with chemical sample preparation, i.e. solid materials must be dissolved be­ fore analysis. But it is well known that acid», its salts and other co­ mpounds in analyzed solutions presented, cause serions matrix interfe­ rences. Moreover, chemical sample preparation, as a rule, is much ti­ me-consuming procedure. In this connection it was proposed to use di­ rect analysis of beforehand dispersed solid samples. One variant of such approaches is sample preparation, based on electric spark disper­ sion principle of conductive materials in liquid dielectric media. This principle was realized for alloys [1] . As a result of investigations carried out, conditions, that provide high aggregative stability of colloidal systems (so-called "liosols" or briefly "sols") formed in dispersion process were ascertained) optimum spark generator parameters were defined; unified sample preparation te­ chnique and commercial model of apparatus were proposed [2] . Factors having an influence on analytical signal forming from dispe­ rsed systems were studied. It was shown, that determination sensitivity of elements from sols and true solutions by furnace AA spectrometry ie much the same. Sensitivity decrease in comparison with solutions (by 5-50% depending on determining element) is observed for flame AA and AE (ICP) spectrometry of sols. At the same time the use of electric spark sample preparation for analysis of alloye by spectrometric methods men­ tioned above provides: - improved metrologies! characteristics; - reduction to minimum of blank analytical signal and any matrix in­ terferences ; - possibility to prepare calibration sols from any available stan­ dard alloy, including elements of interest; - shortening of overall analytical cycle time (single sample prepa­ ration procedure takes 10-30 minutes).

References 1. Pohelkln A.I., Kharlemov I.P., Gusinskll U.N., Shipova E.V.// Zh.Anal.Khim. 1987. Vol.43. P.2138. 2. Zavod.Lab. 1989. Vol.55, H 5. P.112.

454 ATOMIC-SPECTRAL METHODS РОЙ ATTESTIHO THE MINBRAL [HISC-12 SUBSTANCE STANDARDS I—— L.L.Petrov, L.A.Persikova, A.Z.Prolcopjeva Institute of Qeocnemlstry, Siberian Branoh of the USSR Academy of Sciences, Irkutsk, USSR

The multi-element referenoe samples, their creation, study and optimal nomenclature are olosely related to the «ell-developed and widely used analytical methods. The data on certified reference samples show the real situation In the analytical experience, I.e. a number of reliably analysed elements, the list of laboratories possessing a set of modern methods, the quality of enalyses.The bank of data on interlaboratory experiments (ILE) for 20 years' period and available results of some well-known foreign elaborations allow the comparison of various analytical methods (nuclear, atomic and molecular) for a number of parameters. The major bulk of Information on attesting (both in the USSR and the USA) is obtained In the recent decade through atomic-spectral methods and the proportions of emission and absorption versions are different. The main part of results in the national ILE la obtained through chemical (using molecular characteristics) metb.ods.This part however, reduced from 50 to 25JC during 15 years' period. The amount of analytical information obtained through these methods using the nuoleus features (neutron aotivation analysis, mass spectrometry) is extremely small. The change in time of a number of elements analysed by a oertain method, is reeognized. The list of elements analysed by each method and controlled by HE is due to a sum of some factors. The main faotors are metrologicel Indices of competing methods, rapidity and oost of analyses. Out of a total number, the proportion of elements for which experimental results have been recently obtained,constitu­ tes 0.3-0.4 for the group of chemical methods and 0.45-0.5 for the group of "nuolear" methods and a wide spectrum of values for the group of atomic speotral methods. The comparison of national and foreign results shows a significant dlfferenoe in the indices for the group of atomic-spectral methods and a good concurrence for chemical and nuolear-physical methods. She preoision charaoteristioe for individual analytical methods are oompared for the elements having sufficient statiatios in the bank of eaob ILE used.

485 SBROBS НТО OTTBCTIGH LIMITS ESTIMATION И FLAME kaiso-13 SPECTROKWRT E.D.Prudnikov Leningrad Stat* University .Leningrad, USSR In order of aetimatlon of the random errors and detection limits Is flame spectrometry the «ore correct defined theoretical expres­ sion has Dean applied.This expression connects the instrumental end metrologies! parameters of analytical method*

/10 2 а ,Л ••*Фт * <2B» Svox+kd)Svo + А*в$о / » (D

nhere в is the standard deviation;on la the detection limit;с is

the element cancentrationjSv is the Instrumental sensitivity!с is

the blank value;kd and A are the shot and flicker noises coeffici­ ents |R la the co-correlation eoefflcientilMM.Tlie relative stan­ dard deviation may Ъе described Ъу the following иаапаг: •„•(ef/lOe2 + кд^/е + A2)1'8 (a) •here k^ is the coefficient of common shot aeiaea with taking In­ to account of the со-oorrelation moments. According to the expressions (1) and (2),the estimation of the instrumental sad noninstrumental errors and aluo the detection li­ mits in flame spectrometry may Ъе realised on Use of the experi­ mental values of the standard deviation for throe concentrations of element.They must ha on the herders and in centra of the diapa­ son of meesured concentrations.The investigations confirmed the good eggreenent of theoretical and experimental data.It is shown that the well known linear approximation of the standard deviation is valid for the instrumental atsnderd deviation in presence of in­ terferences and for K«1.In thia ease it is enough to have the expe­ rimental data of the standard deviation for two concentrations of element. On* concentration must he near to detection limit.The herders of the application of known emplrio expressions for the standard deviation have Ъееп examined.The practical methoda of es­ timation of the detection limits and random errors in stomic spec­ trometry have been proposed.Theory allows to offer the united ap­ proach to the aatimatlon of the characters for. different analyti­ cal methods.

*st NEW KNOWLEDGE FROM THE PREPARATION OF MINERALIZATION SAMPLES OV MEANS OF GASSES £Z1

P.Pdechel, A.StuchlikovA, Z.Forman?k

Research Institute for Brown Coal, Host, Czechoslovakia

New method /17 of mineralization by utins of gasses la utilized during three /«art. Tha principle is th» action of mineralized mi« of gaasat composed fro» the oxydt of nitro­ gen, ozone if naad be furthar gasses and oxygen for tha sanple altll tha weight up to 5 g, that it placad in the mineralized flask fro* glass, quartz of PTFE. Those cells trt programmed heated for mineralized temperature selected up to maximum value 400° С /PTFE 320s C/. The mineralizater is dissolved by mineral acid or before dissolution in addition by mineral acids treated. The poster presents sees леи knowledge froa this way of mineralization, it refers to analytical data its usefulness of application in analytical system, it submits also the representation of apparatus lij enabling the way of minerali­ zation. References Л/ PUschsl P. and coll.//АО 261 S75. CSSR. 1986. (ZJ PttSChel P. and Coll.//АО 263 302. CSSR. 1987.

«7 FLASH! SFBCWKHCOJIC ВШ1ГОШ. AIALISIS 0» OHGAKC tOSO-K

I.A.Hevelaky, S.T.SOICOIOT, Г.К.КихоопкШ, R.e.Koatyanoralqr Institute of Chaateal Physios, 03SH Aoadionr °* Soloneo», Moscow, USSR

The possibility of atomic ratio determination (for C,H,D,0,B in molecules of organic compounds was investigated by different researchers £t-2% with the help of microwave plasma detector and GO. Ibis research is devoted to the investigation of possibility of atomic ratios determination for such elements as C,H,N,0,F,C1, Br, I,P, S,D with the help of capillary GC and microwave plasma detector model "MPD-e^O1* of ACS Ltd. (with vacuum and atmospheric helium plasmacells} The model organic compounds has contained ele­ ments mentioned above. It has been shown that C/H ratios can be determined with the accurasy about 155 relative as with vacuum and atmospheric plasms, but sensitivity in the latter саве was higher about one order of magnetitude. The accurasy of the determination of carbon end other elements atomic ratios was about 5# rel. with vacuum and 3% rel. - with atmospheric plasma. Minimum quantity which is nesessary for the atomic ratio determination was about 7 -4 10 -10 3.for most elements(depending on pie вша, element and value of atomic ratio) and about 10" -10"'^- for nitrogen and oxygen. The possibility of high sensitive and element selective deter­ mination of organic component concentrations without calibration of the MPD has been shown too. The new opportunities from the point of «lew of organic compo­ nents identification and quantitative determination appear when MFD is used in combination with GC. ВАтеи 1. McLean W.R., Stanton D.L., Penketh G.E.// Analyst. 1973.Tol.98. P. 432-442. 2. Uden P.O., Barnes R.H. //J. of Chroma t. 1984. Tol.302. P.277-287.

4M INVESTIGATION OP INDUSTRIAL Al SAHFLES BY METHODS MISC-16J OF ANALYTICAL ATOMIC SPECTROSCOPY S .lH.Ryzhkova, L.U.Krivoputskaya, L.B.Trofimova, S.M.Solntseva Institute of Geology and Geophysics, Siberian Branch of the Academy of Sciences of the USSR, Novosibirsk, USSR The industrial Al samples obtained under various technological conditions have been investigated to optimize the technology of production of aluminium of a required composition and quality. The samples investigated have the crystal structure of a various perfectness which depends on dimensions of "mosaic" Mocks, de­ fect size, quantity and nature (ion size) of elements .nat enter Al structure as isomorphs»

In crystal structure perfectness, these samples form a series with one of the extreme terms being of a high degree of perfect­ ness ( £• 67), low value of defects (x- 0.27) and having the largest "mosaic" blocks (D • 690 A). The other extreme term is characterized by a low perfectness (f > 24), high value of micro- deformations (об» 0*63) and small-size blocks (D • 260 A), The dependence of Al quality (values £,u , D) on nature and quantity of impurity elements has been investigated» Using the methods of atomic absorption and atomic emission spectroscopy the following isomorphic impurities have been revealed: Ca, Fb, Cu, tin, Ga, Ti, Cr, Ba, B, Si, Ug, Fe.

The Al quality has been stated to be essentially affected by such elements as Fe, Cu, Ga, Tl, Si, that enter its structure. The defect value U6 ) of Al depends directly on iron contents in the structure» The results obtained allow some recommendations to be given to optimize the production technology of aluminium of a required composition and quality» The most effective method of the pro­ duct quality testing is the atomio absorption spectroscopy which is of a high sensitivity and allows the element composition to be determined in complex-composition solutions in a wide range of concentration».

45» ELECTROTHERMAL ATOMIC ABSORPTION DETERMINATION OF ARSENIC. TE1LURIUM, SELENIUM. GOLD AND SILVER ШЗС-17 IN GEOLOGIC OBJECTS AFTER AUTOCLAVE DIGESTION

E.M.Sedykh, L. N. Bannykh, N. M. Kuzmin, V. A. Orlova, V. P. Hvostova, V. V. Smirnov GEOHI, GIREDICT, Moscow, USSR

Electrothermal atomization atomic absorption spectrophotometry with preliminary sample autoclave preparation have been applied to analyze carbonaceous slates, carbonaceous sulfidic ores, oils and bitumens for origin bounded elements: arsenic, tellurium, selenium, gold and silver II]. All five elements simultaneous quantitative separation conditions are discovered: by nitric acid and perhydrol mix wetted sample is treated in the two chamber analytical autoclave reaction volume by hydrochloric and fluorochloric acids vapours mix. Silicon extraction by distillation and separate condensation occures with analyte elements remained in the solution. The atomic absorption analysis of the solution was perfoiuced by Perkln-Elmer model S030Z AA Spectrophotometer with HGA-600 graphite atomizer. Unselective absorption was accounted by Zeeman effect. Thermostabillzed graphite furnace with platform served as atomizer. Nickel and palladium were used as modif.icators to determinate arsenic, selenium and tellurium, and ascorbic acid was employed for silver determination. The lower limits of determination were 0.001- 0.01 ppm (0,5 g sample weight, n-10, p-0,95). The separation conditions accuracy have been approved by standard samples and synthetic mixtures analysis.

•tftNDU

1. Orlova V. A., Sedykh E. M,, Smirnov V. V., Bannykh L. N., Fetrov- skaja I.N.. Kuzmin N.M, //J. Anal. Chlm. 1990. Vol.46, P.933. ТИК USK CF THE ..J3CA USTHOD FOR T1UJ JBHiRiuIMATiCN OF Г~~ MISC-18 PHOSPHCaUS IM bOOS C0«J«KR0IAL AND HATURAL OBJECTS I I S.N.Baron Odessa Stnta University, Odessa, USSR lie ..JiOA method is one of the jiost promising end interesting ones for the determination of various non-jietals, including P, in objects of industrial production and in the environment. How­ ever, as a result of an Insufficient study of the factors which determine the value of an analytical signal (the radiation inten­ sity of lu>0 particle Л =528 №n) as well as due to the differen­ ces in construction designs and peculiarities of proper devices for the introduction of tne samples to be analyzed into a cavity has not found v/ide application in analytical practice so far. This work gives the results of the studies, the peculiarities in the behaviour of phosphorus and its various compounds in a cold diffusion flame of Ks-Ko-the air. The data obtained have been scientifically verified in tile light of approximate thermodyna­ mic models of the formation of analytical HPO particles while taking into consideration equilibrium compounds and the tempera­ ture of the above-mentioned flame. for the Introduction of the latter a developed by us has been used. To our opinion. Its use allows to obtain more reproducible results than with the help of other analytical devices. The effect of various components of the objects to be analy­ zed: mineral acids (HNO,, HOI, HgSO., cations of various metalsi Cu, Hi, Zn, Fe, etc.) on the value of radiation intensity of HPO has been studied. It has been found out that the above-men­ tioned substances exercise a depressing effect on the value of an analytical signal even in insignificant quantities ^ 1*10~ . To eliminate the above-mentioned effect, phosphorus has been sug­ gested to be separated with the help of ion exchangers from the macrocomponents of the samples to be analyzed. We have established optimum conditions for the determination of phosphorus in some alloys of ferrous metals (bronze, brass, german silver) as well as in chemical reagents (H-FO, of various makes), superphosphate acid, and in natural waters and sewage. The method proposed is remarkable for its simplicity and suf­ ficient reliability. The lower limit of the phosphorus concentra­ tes to be determined is 2.5

«I LASER-ItJDUCED FLDORESCENOE MEASUREMENTS OP INERT GASES IN A HOLLOW-CATHODE DISCHAROB taS0-19l M.V.AIChfflBiiovs, I.V.Bykov, S.G.Ivanov, A.I.Kholodnikh, A.S.Khomyak Vernadsky Institute of Geochemistry and Analytical Chemistry, Academy of Sciences of the USSR, Mosocxr, USSR Laser-induced fluorescence measurements (IIP) of inert gases (Xe, He) in a hollow-cathode discharge here been done at dye-lasers based spectrometers pumped by excimer or YAG-laaers. Energy of dye- -lasers radiation was equal to 0.2-0.3 mJ with 0.2-0.3 cm'1 spect­ ral band width. In xenon it has been excited transition from the

metastable 6е[з/г|| level to the 6p'{3/2j2one with > =452.468 nm. LIF measurements hare been created at warelegths of >• =473.415 nm andX «834,682 nm. Рог ЫР line with Л «834.682 nm signal/noise relation was equal to approximately 400. Baaed on absolute calibra­ tion of registration system by Raman scattering in liquid benzene it has been estimated the population densities of 6в£}/г]° metastasis

9 3 level of Xemga« 2.5-10 atoms/em . Possible ways of the detection limit decreasing of xenon excited atoms up to amount ng^xlO-'atoms/cnr

are discussed. For helium under exoiting of 3d^D. , ,-2p'Pg . г transition (A =587.562 nm) optical saturation of LIP and optogalvanio signals have been realized in hollow-cathode discharge. It allowed to estimate the stationary 2p level population densities in discharge at the amount rig*3-10 atoms/cm • Electron temperature calculated from the relation of 2p and 3d levels population densities is equal approximately to 0.24 eV. Estimation of population density of 2p level performed on the saturation of optogalvanlc signal has value two times greater than one from the LIP data. Also removed LIF in helium discharge has been obtained for the ЗР-^л i ->-2s3S.,{A =388. •а ч о и, I %tL 1

J 865 nm) and 3s S1-2p-'P0 1 g{ A«t06.519 nm> transitions through col­ lisions!, disactiration of 3d level to 3P and 3s levels. It has been shown the", under laser action the populations of the 3p and 3s levels аге larger than stationary values on 2-3 orders of magnitude. Detection limit for excited helium atoms ia equal to 10 -10'atome/enr for our spectrometer.

4*3 ANALYSIS OF STEELS USING 1CP-MS IM1SC-2OI

H.-M.Kuss,M.Muller Department of Analytical Chemistry, University Duisburg, D-4100 Duisburg, FRG

Inductively coupled plasms mass spectrometry (ICP-MS) has been used for the determination of trace and ultratracc amounts of about 70 elements in different sample types. ICP-MS combines the speed of the multielement emission spectrometry (ix. ICP-OES) with the very low detection limits of the atomic absorption technique (GF-AAS). For about 70 elements the detection limits are about 10-100 ng/L, In comparison with toe multielement simultaneous ICP-OES with a potychromator the main advantage of ICP-MS is to determine nearly all elements in one run as dissolved sample solutions. Till now a few experiences are published dealing with steel analysis by means of 1CP-MS. In this paper we present the capability of the qualitative or the so-called 'semi­ quantitative' analysis (analysis with lower precision) and compromised instrument settings for the determination of more than 40 elements. The element concentration of the steel samples reach from the lower ppm amount to the extent of about 10 or 20 %. Without doubt ICP-MS is a method for trace analysis, but likewise we have got good results for the determination of elements in higher concentrations (i.e. %- values). Matt interferences of isobars are also discussed as those of molecular ions. The effects of die sample matrices and the interferences of the dissolution reagents are minimized by different kinds of internal standardization. The results are compared with the certified values of several Standard Reference Material steel samples, which were dissolved using the rapid microwave digestion method.

The project is greatly supported by the European Communities, Project №. 7210- OD/107

463 IHTRACAVITY LASBR SPBCIROSCOFY. [UliclEl BARB BARTH DBTBRHIHAIIOir BY MBTHOD3 OP IHtRACAVITY LASER I — SPBCTROPHOTOMBTR* ABD ATOMIC ABSORPTIOB WITH ELECTROTHERMAL ATOHIZATIOB H.S.Stroganova, S.G.Ivanov, I.P.Galkina, ti.Y.Akhoanova Vernadsky Institute of GeoohemlBtry and Analytical Chemistry, USSR Academy of Solenees, Moscow, USSR It «as shown earlier by tbe intracavlty laser spectrophotometry (IIi-SP) tbat rare earth elements (REE) may be determined in solution using individual absorption spectra [1]. Detection limits are of 2-3 orders lower than ones for ordinary spectrophotometry and equal to about 10"5 - 10"7 g/ml. It was established also that IL-SP method permits more effectively to resolve the structure of KEB absorption bands. IL-SP method may by used for studying of state and form of existence of elements in different media [2]. In the present work results of REE determination were obtained by means of the first USSR automatic IL spectrometer "Minsk-2" [i]. The device allows to use two modes of operation: spectrophotometrical re­ gime and regime of atomic absorption with electrothermic atomization. In both oases photoelectric registration of signals provides quick recording and following computerized processing of IL spectra» Dyes of three types (derivatives of coumarin, rhodamine and oxazlne) were employed as active laser media for appropriate selection of spectral area* Optimal temperature conditions for dehydration and decompositi­ on of RBE compounds (chlorides, nitrates, acetates and oth.) were predetermined in 25-1500°0 interval by differential thermogrsvimetric method. Optimal atomization temperatures for REE oxides were estima­ ted experimentally. At these conditions analytical relations were obtained connecting the relative gap depth in IL spectra (al/I0) or equivalent absorption band width (S/I0) and quantity of element to be determined. Linear interval of RBE concentration, for example neodimi- 8 um.'is limited between 5-10" g/ml Gsl/I0»0,2) and 1.10"° g/ml (л1Л„- 0.6). Detection limit for neodlmiura (№1 A."562,054 пш) is 1.10~S g/ml.

Relative standard deviation (Sr) is 0,15. References 1. JUcbmanova M.V., Galkina I.P., Ivanov S.G., Stroganova H.S.// J.Appl.Spectroscopy. 1967.Vol.47t N 4. P.559-563. 2. Stroganova U.S., Galkina I.P., Akhmauova 11.V., Ivanov S.G. // Analytical Chemistry of Rare Blementa. H.: Пайка, 1988. P.69r-7B. 3. flurakov V.S., Gvordev A.A., Kovalev A.JTa., lUsakov P.Га., Roykov S.H.//J.Appl.Spectroscopy. 1989. Vol.13,Я 9. P.712-719.

4M HE» LIGHT SOURCES TOR ATOM ABSORWIOH ANALYSIS | 1 HISO-23 A.Q.Lutokhin I 1 Rostov State University, Rostov-on-Don, USSR To determine low concentrations of toxic elements the atom absorb- tion spectrometers (AAS) with spectral light sources (SLS) emitting analytical lines are widely used. The efficiency of the spectrome­ ters used is to a large extent determined by a set of SLS for vari­ ous elements, parameters of emitting lines, their width and stabili­ ty. In Rostov University an unconventional design for constructing SLS has been proposed in whieh the glow of near electrode HP of dis­ charge is applied CO • On the basis of this scheme a number of SLS modifications for AAS have Ьегп worked out. These sources have some advantages over other ones: they have lower self-reversal vi re­ sonance lines| the nonstability due to metal migration on the light emitting surface of the lamp is eliminated; low dependence of buffer gas pressure on emission parameters enables the increase of the sou­ rce service time without enlarging the vessel volume. Comparative testing of commercial and experimental SLS sources fox As have shown that the disoharge in the experimental souroes glows steadily over a considerably greater range of metal vapour pressures, and that by its spectral and analytical characteristics the source is not worse than BDL (USA.) and surpasses HCL (Japan) and VSB-2 (USSR) (see the table). Analytical characteristics obtained In determining As concentrations for various SLS

SLS Relative standard deviation Determination limit of the observation result (20 measurments) Absolute mkg/ml Experimental SIS 0.10 0.15 0.16 2.3 EDL 0.10 0.17 0.15 2.5 HCL 0.15 0.2Э 0.23 3-5 VSB-2 0.13 0.32 0.20 4.8 Atomiser HCA-74 flam» HflA-74 flame

Refarenoe

1. Lutokhin A.G.//froc. XI Nat.Conf. on Atom.Speotroao. Vaxoa-Drujba (Bulgaria), 1986. Р.385-Э87.

Э0.3»к.413 4И SPECTRAL ANALYTICAL CHARACTERISTICS MIS0-2* AND PLASMA DIAGNOSTICS OF GLOW DISCHARGE SOURCES /GDL/ PARAMETRES A. PETRAKIEV AND D. MOLLOV SOFIA UNIVERSITY/ FACULTY OF PHYSICS* DEPARTMENT OF OPTICS AND SPECTROSCOPY/ SOFIA, BG-1126 BULGARIA

THE INFLUENCE OF GLOW DISCHARGE PARAMETRES (POWER* VOLTAGE AND INERT GAS PRESSURE) TO INTENSITY OF SPECTRAL LINES HAS BEEN IN­ VESTIGATED. ATOMIC/ IONIC AND MOLECULAR SPECIES HAVE BEEN OBSER­ VED DEPENDING UPON THE EXPERIMENTAL CONDITION IN THE GDL SOURCE. RESEARCH OF MUTUAL DEPENDENCE BETWEEN INTENSITY CHANGES OF SPEC­ TRAL LINES AS A FUNCTION OF POWER UNDER CONSTANT VOLTAGE AND

PRESSURE OF THE INERT GAS/ AS WELL AS THE DEPENDENCE OF THE IN­

TENSITY CHANGES AS A FUNCTION OF VOLTAGE UNDER CONSTANT POWER

AND INERT GAS PRESSURE/ HAS BEEN CARRIED OUT.

THE PERFORMANCE OF THE DISCHARGE SOURCE WITH RESPECT TO THE IN­

FLUENCE OF VARIONS PARAMETERS ON INTENSITIES AND INTENSITY RA­

TIOS ON SPECTRAL CHARACTERISTICS HAS BEEN INVESTIGATION IN ORDER

TO OPTIMIZE CONDITIONS LEADING TO THE HIGHEST LINE INTENSITY/

THE LOWEST BACKGROUNDS/ AND MINIMAL INTERFERENCES.

THE OPTIMUM PARAMETERS WHICH GIVE THE POSSIBILITY FOR DETERMI­

NING MINIMUM AND MAXIMUM CONCENTRATIONS OF THE ELEMENTS HAVE

BEEN ESTABLISHED. PLASMA TEMPERATURE AND ELECTRON NUMBER DENSITIES HAVE ALSO BEEN

EVOLUATED USING SPECTROSCOPICAL D1AGN0STICAL METHODS.

THE EXPERIMENTS HAVE BEEN CARRIED OUT BY AUTOMATIC EMISSION SPECTROMETRE OES 3520 / GDL/ ARL FIRM/ SWITSERLAND. THE BEHAVIOUR OF ANTIMONY IN GFAAS WITH PALLADIUM MODIFICATION UISC-25j H.-J. Heinrich, G. Emrich, E. Schierhorn Central Institute of Physical Chemistry, Analytical Centre, Academy of Sciences of the GDR, Rudawer Chaussee 5, Berlin 1199, GDR It is well known that palladium is most effective when it is reduced to the zero oxidation state early in the thermal pretreatment step. The exact function of the modifier has not been clearly understood. In an effnrt to evaluate the analytical performance and mechanism af stabilization of antimony using the Pd modifier atomic absorption measurements were complemented by scanning electron microscopy (5ЕЮ and energy dispersive X-ray fluorescence (EOXRF) microanalysis. The different behaviour of Pd and Sb on a glassy carbon (GO platform and on a tantalum surface as sampling substrate in a pyrolytic graphite coated tube was compared. Using GC for Sb determination with GFAAS the amount of Pd added determines - 'the maximum pretreatment temperature - the delay of the 5b peak and its profile - the sensitivity (peak area absorbance) - the extent of the interference by chlorine (PdCb, HC1). SEM and EOXRF inspections of GC platforms after different pretreatments with the Pd modifier revealed strong surface reactions at the Pd-C interfacial area covering several stages during the temperature increase. Above 1000'C always droplets or spherical particals containing Pd and 5b with an encapsulating carbon layer are formed. This is the result of the catalytic Gasification and graphiti/ation of car­ bon in the presence of Pd. Combined with the formation of Pd-Sb phases these pro­ cesses allow a very efficient stabilization of 5b. The shifting and shape of the Sb and Pd signals caused by different Pd masses may be explained by a carbon film formation during the catalytic development of thu Pd vaporization from a carbon substrate via the PdC mechanism [l]. The presence of CI inhibits the Pd-catalysed reactions on a carbon surface. The

addition of Ht to the Ar purge gas in GFAAS helps to overcome the CI interference. Using Та as a sampling surface the above cited phenomena are not observed. The stabilization can be interpreted as formation of a Ta-Pd-Sb alloy.

Reference

1. L'vov 6.V.// Spectrochim. Acta 1989. V.44B. P.1257.

447 AN OPTIMISED APPROACH TO AUTOMATED LOW LEVEL 1-26 MERCURY ANALYSIS

C.B. MuUins, Varian UK. Ltd, 28 Manor Road walton-on-Thames, Surrey KTI2 2QF, England and J. Moffett, Varian Techtron Pty Ltd, 679 Springvale Road, Mulgrave, Victoria 3170, Australia

Mercury may be determined directly using flame AAS but the sensitivity is not good. A far better approach (1) is to generate the mercury as in atomic vapour which can then be used for atomic absorption measurements. This approach produces a high sensitivity with detection limits around 0.1 parts per billion. Mercury и в highly toxic element and has received considerable recent attention in environmental studies. Current European regulations reqoire measurements to be made at levels as low as 0Л5 parts per billion which is a concentration frequently encountered in many analytical reagents. A system is proposed which automatically analyses samples for mercury at the sub parts per billion level and which avoids contamination from mercury in reagents and in the laboratory environment.

Reference 1. N.S. Puluektov et al./Zh. Anal. Khim.,18,33,(1963)

468 OPTICAL COLLECTION EFPICIEHCY OP LOUeiTUDIHALLY r~ П HISC-27 EXC1TBD PIiTOEBSCBfCE Iff A ORAPHITB РШНАСЕ TUBE | _ AS CALCULATED КС A HAY TRACING APPROACH P.B.Farnaworth, B.W Smith, N.Omenetto Joint Researoh Centre, Environment Institute lepra (Varese), Italy

We have developed a computer program «1th which It 1» poeeible to calculate the collection efficiency of an arbitrary combination of lenses and apertures from a single point. Because the program is based on a rigorous ray-tracing algorithm, its- output accounts for the effects of lens aberrations. The program has been used to evalu­ ate and compare three f/3 lens combinations configured to collect longitudinally excited atomic fluorescence from a graphite furnace. A symmetric biconvex lens «as modeled as the simplest case a pair of piano convex lenses was used as an Intermediate case, and a pair of matched achromats «as included to illustrate ideal behavior. Calculated single-point collection efficiencies differ signifi­ cantly from those calculated based simply on the solid angle subten­ ded by the lens. They range from 14% of this ideal value for the bi­ convex lens to nearly 100$ for the aehromats. Differences in perfor­ mance are smaller «hen the efficiency is Integrated over the 2-ma laser beam diameter and the length of the furnace. The utility of the efficiency calculation algorithm extends beyond the particular geometry modeled In this study. It should be useful In a variety of applications Where optimization of collection efficiency la important or «here a detailed knowledge of the spa­ tial origins of a signal within a source Is desirable.

«ft Author's Index

Abashkina И.Р. HISC-6 Balkin R.s. ALS-29 Abdul Una т.н. AAS-13 Belov V.H. AAS-5 Afonin v.p. PLN-1 XRS-39 XBS-16 Balaki N.K. AAS-64 Agullar J.F.caaunaa AES-58 Balyaav Vu.I. AAS-92 Akhnanova M.v. ALS-28 Balyaava E.E. XRS-104 MISC-19 Balyanin V.P. PLN-2 MI5C-21 Baraan s.s. AAS-56 Alekaanjan O.H. XRS-79 Berndt я. AES-3 All F.H. XRS-1 Bartalan E. HISC-2 Alparovich V.P. XRS-2 AES-75 XRS-50 Bertels P.c. AAS-7 Alrazak N.H. XRS-1 Berzinya O.K. AAS-65 Altuhov V.A. XRS-47 AAS-66 Andreyevs N.N. XRS-65 Betin U.P. XRS-7 XRS-64 Bazlutakaya I.V. AAS-118 Andric G. AES-29 Bichaev V.B. AES-76 Androsova H.v. AAS-55 Blank A.B. XRS-48 Anlkiev V.v. MISC-1 Blaacbuk T.P. XRS-67 Anoshin G.N. AAS-55 XRS-49 Antanavicius R. AES-1 Blinova E.s. AAS-67 Antipenko A.G. ALS-27 Blokhin S.M. XRS-8 Antonov V.N. AAS-67 Bobkov A.V. AES-5 Antulskaya N. AES-91 ABS-4 Arjanova I.G. XRS-83 AES-77 Arpadjan s. AAS-1 AES-6 AAS-109 Booharov V.A. AAS-80 AAS'112 Bodrov N.V. ALS-12 Artaaonova E.o. ALS-2F Bogdan i.e. AAS-80 Artyukhovich A.N. AIS-1 Bogdanova I.V. XRS-50 Atnaahev Yu.B. AAS-2 Boitaov A.A. AES-78 AAS-34 Bol'ahakov A.A. ALS-31 Back И.Н. AAS-7 Bolahov И.А. ALS-30 Bagdi G. AAS-3 Bondaranko B.Vu. XRS-9 Bakaleinikov L.A. XRS-3 Bondarava N.V. MISC-3 Bakhtiarov A.v. XRS-4 Borkhodoav V.Ja. XBS-19 BakinaN.N. AAS-83 Borkovaka-Burnecka J AES-73 Bannykh L.N. MISC-1 Bouaana P.W.J.M. PLN-3 HISC-17 Bozaai G. AAS-68 AES-121 Branch s. PLN-5 Baranov S.V. AAS-4 Brovko I.A. AAS-69 Baranova O.V. AES-95 Buchbindar G.L. AES-7 Barinaky R.L. XRS-91 AES-122 Baraina L.I. AAS-83 AES-123 Bamaa R.M. ABS-2 AES-88 Baron S.N. MSC-18 Buhl F. AES-23 Barriobero 0. AES-45 Bukhantaova V.G. AAS-37 Baraukov v.I. AAS-10 Bulaka E. AAS-70 AAS-17 AAS-81 Bartha A. AES-75 AAS-100 Baachanko o.A. XRS-5 AAS-S1 XRS-8 Burakov v.s. ALS-2 Batzuav S.A. XRS-6 ALS-33 Backar-Roaa в. AAS-52 Buravlyov Vu. ALS-32 Baiaal H.F. AAS-116 AES-8 Bakov G.I. ALS-29 Burilin И. AAS-71 ALS-27 Butaikia R. AES-1 Baliaa c.F. XRS-59 Buzlaava I.p. XRS-53

nt Author's Index

Bykov I.v. HISC-19 Dllektorski A. A. XRS-56 Bykovsky Vu.A. ALS-l Dinitrov N. AES-104 cajkova 0. AAS-85 Dlttrioh K. PLN-4 Carnriok G.R. AAS-105 Dittrich P. XRS-14 Castillo J.R. AAS-6 Dobrovolakaya G.L. AES-11 AAS-72 Dobrowolaki R. AAS-74 AES-4S Dogan K. AAS-75 Chakrabarti C.L. AAS-7 Doabrovakaya И.А. AES-44 Chanyahava Т.Л. AES-124 Dorofayev v.s. ALS-34 AES-125 Drobyahev A.I. AES-12 Chaplygin V.I. ALS-7 Druz V.V. XRS-10 charykov A.K. AAS-29 XRS-11 Cheban N.N. HISO-6 Druzenko T.v. AES-112 Cheblakova E.G. XRS-51 Druzhenkov v.v. AES-13 chabotareva Ы.А. ALS-17 Dudsk J. AAS-104 Chebotaryav A.N. AAS-63 Dudnikov S.Yu. AES-14 Chekalin N.V. ALS-22 AES-15 ALS-41 Duinakaev S.I. XRS-12 ALS-23 XRS-13 ALS-34 Duiaakaeva T.G. XRS-12 Cherevko A.S. AES-127 Dunduchenko E.Y. XRS-42 chernetsky S.H. AES-25 Durinov I.u. AES-89 Cherniavskaya N. ALS-32 Dvorkin v.i. AES-10 AES-8 Dyaglleva Ye.v. AES-S4 Chttrnova N.V. AAS-97 AES-83 chlllaov A. AES-136 Dyoain A.P. HISC-5 chlstyakov A.A. ALS-l AES-69 Chokoav E.S. AbS-24 Dyoaln V.H. HISC-5 Choporov D.I. AES-91 Bbdon L. IPLN AES-25 Egorova V.A. AES-S5 Chudlnov E.G. AES-9 XRS-51 AES-S Ehrhardt H. XRS-14 AES-70 Elagln A. AAS-58 AES-8 Elci L. AAS-75 AES-77 Elnazarov S. AES-86 AES-126 Elokhin V.A. AES-25 Chuaakova N. AES-102 Eael'yanova i.v. AES-71 Chuaakova V.A. AES-33 Enaljanov A.A. AAS-11 Churaina O.D. AAS-117 AAS-10 chuvina G.I. AES-33 Enrich s. HISC-25 claos E. AAS-26 Engalaht V.s. AES-17 Czakow J. AES-80 AES-16 Daahin S.A. ALS-35 Eraakov A.F. XRS-52 Davirov A. AAS-69 Erahov Yu.A. XRS-15 Davydova I.Vu. AES-82 Eznov O.N. ALS-36 AES-S1 rabalinaky Yu.i. AES-94 Davydova S.L. AAS-8 Fable N. AES-23 Da qiang Zhang AAS-107 Falk H. ABS-Z2 Dadina J. AAS-9 Fang Z. AAS-62 Dagtarijcva I. ASS-91 Far» M. AAS-76 Dalava A. AL3-38 Farkaa A. AES-139 Dal1j aka-Kruahavaka MISC-4 Farnaworth P.B. PLN-10 Daaarin V.T. AAS-73 MISC-27 Daaant'av A.V. AAS-28 Faaaatt J.D. ALS-4 Daniaova N.V. ALS-3 rathudinov R. AES-110 Diaz o.Duqua AAS-40 Fadoaaankov A.N. AES-47 AAS-41 Fartikov V.I. XRS-15 Diatza U. HISC-8 Faachanko I.A. AES-142

471 Author's index

AES-87 HISC-S Filatova Ye.I. ALS-21 Gorbatenko A.A. ALS-7 Finkelshtein A.L. XSS-16 Gordayav A.M. AES-S9 XRS-19 Gorav J.A. AAS-36 Florek S. AAS-52 Gorkovoy v.v. AES-25 Florian K. AES-18 Gorlavkaja H.G. AAS-113 Fodor P. AES-19 Gorlov V.S. AES-99 MISC-2 Gorlova H.N. AAS-15 AES-75 Gornushkin I.B. ALS-39 Fogelson M.S. XRS-17 Goraky v.v. XRS-86 Foraanek z. HISC-14 Grazhulena S.S. AAS-16 Foraanovsky A.A. AES-109 Grebannikov H.V. AAS-17 Foulkes H. PLN-5 Greanshtain I.L. AAS-25 Freedaan G.I. AES-20 AAS-24 Fugol i.ra. ALS-S Gribovskaya I.V. AES-90 Funk W. AES-21 Grigorjev v.F. AAS-18 Funtov V.N. ABS-49 AAS-11 AES-4S AAS-22 Fyodorova N.D. AAS-83 Grigorovich I.V. XRS-15 Galas w. AES-23 Grinkina 6. AAS-71 GaXeev K.R. XRS-66 Gripachevaky A.N. XRS-86 Galkin A. XKS-S5 Grishko V.I. ALS-6 Galkina I.P. MISC-21 ALS-37 Ganeyev A.A. AAS-12 Grishko V.P. ALS-37 AAS-54 Grobenski 2. AAS-100 Gantch«va V. HISC-4 AAS-S1 Gardashnikov L.E. AES-47 Grohmann I. XRS-36 Gavrilova N.G. AAS-117 Gromozova I.к. XRS-54 Gayazova I.H. AB5-142 Groot J.de XRS-38 Gaguach H. AAS-78 Grun и. AAS-87 Gerzkin I.A. XRS-78 Gru2d«va Т.н. AES-117 Gil'bart B.N. XRS-53 AES-118 AES-88 Gubanova V. AES-120 AES-122 Guall O.A. AAS-20 AES-123 Gulko N.I. AES-134 AES-7 Gunicheva T.N. XRS-19 Gil'autdinov A.Kh. AAS-111 XRS-16 AAS-14 XRS-29 AAS-13 Gunko N.A. XRS-20 Giael'farb F.A. XRS-18 Gurenko A.A. XRS-89 Gisbrecht A. ALS-38 Gusaraky v.v. AES-26 Glukhan E.V. ALS-34 AES-20 Godlawska B. AAS-70 Guzeyev I.D. AAS-67 Golloch A. AES-21 Guzhova A.v. XRS-87 Golovankov N.V. ALS-31 XRS-89 Golovko S.B. AES-24 Gvozdav A.A. AbS-2 AES-65 Haaa У. ALS-9 Golubchikov v.v. XRS-78 Halachava Z. XSS-43 Golubav A.A. XBS-32 Haaza Haaza B. AAS-106 XRS-33 AAS-108 Goaaz J.S.Hinoao AAS-41 Han wan sun AAS-107 AES-54 Hartalzov A.o. AAS-91 AAS-40 Haaal И. AAS-100 Gonchakov A.s. AAS-16 AAS-51 Goncharova L.X. AAS-102 Rashchina H.V. AAS-SO Goncharova H.N. AAS-79 Havaraach-Kock M. AES-21 Gorbachavskaja N.V. AAS-79 Havazov I. AAS-19 Gorbachev S.F. AAS-13 AAS-9B

471 's Index JTT 1 ГЦ.^^ =,.=- = Д•——•—» • mnn^m "== :ssas3=3BE; AAS-82 XRS-23 Havezova P. XHS-43 Kalinin s.K. AES-35 Keadrick K.L. AAS-7 Xalugbin A.G. XRS-16 Heinrich H.-J. MISC-25 XRS-24 Helan V. XSS-40 Kamaeva L.v. AAS-83 Heltai Gy. AES-27 Kamenshikov А.Б. AES-36 Hieftie G.M. PLH-6 Kano B.R. ALS-26 Hoffmann V. AES-131 ALS-36 Holcla j tner-Antunovi AES-29 Kantor T. AES-37 AES-68 AES-54 Holcombe j.A. AAS-20 AES-139 Holoshin V.G. XRS-66 Karadjova I. AAS-1 Horlick G. PLH-7 AAS-109 Horn R. AAS-99 Karaivanova E. XRS-43 Hots H.S. AES-61 Karpov V.s. ALS-28 Hulanicki л. AAS-S1 Karpov Yu.A. AES-38 Hurst G.5. ALS-8 Karpova s.u. ALS-25 Hussein F. AAS-8 Karpukova O.K. XRS-37 Hutton J.C. AAS-7 Kartasheva H.A. AES-40 Hvostova V.P. HISC-17 AES-1S I.Lakatos I. AAS-3 AES-78 Xgnatenko K.I. XRS-90 Karyakin A.V. AES-94 XRS-87 Kashkan G.v. AES-95 Ikrenyi K. AAS-21 Katskov D.A. AAS-23 AES-75 AAS-25 Ilic Z. AAS-59 AAS-24 Iljitchova I. AES-91 Kazakov s.v. XRS-88 Ishaiyarova G.R. AES-92 Khadjiaukhanedova I. XRS-55 Ishnijazova Sh. AAS-69 Khaazin z.z. AES-39 Ishutov A.V. AES-3 3 Kharcisov A.D. AES-11 Isaailova D.N. MISC-6 Kharlamov i.P. MISC-11 Ivaldi J. AES-63 Khokhlov V.V. AES-79 Ivanov A.A. ABS-31 Khokhryakova Z.A. AES-97 AES-30 Kholodnlkh A.I. ALS-28 Ivanov A.L. XRS-101 MISC-19 Zvanov B.H. AAS-22 Khoaiak A.s. MISC-19 AAS-18 Khooutova E.G. XRS-57 Ivanov S.G. HISC-21 XRS-56 MISC-19 Khovalig N.K. AES-101 Ivanov V.G. XRS-37 Khraaov R.A. XRS-47 Ivanova E. AAS-82 Khrulav A.A. AES-47 Ivanova T.I. AES-32 Xhvostkikov V.A. AAS-16 Ivanova V.E. AES-95 Xhvostova V.P. XRS-58 Izidinov CO. AES-55 Xireav A.D. XRS-6 Jablonaki M. XRS-74 Kitov B.I. XKS-35 AES-114 Kliaant v. AES-96 Jaron I. AES-34 Kliaaa J. XRS-82 Jasaia O.A.A. XRS-1 Klok Ad AES-98 Jaxa-Bykowaki W. AES-93 Knapp G. PLN-8 Jian hui Shao AAS-107 Robzav A.P. XBS-47 Jin jia Zhang AAS-107 Kocbatkov A.s. ALS-23 Jordanov N. AAS-82 Kolecov G.H. XRS-59 Jordanova L. AAS-1 MISC-1 Jotov Tav. AAS-BB Kolaiova L.V. AES-61 Juravlav V.H. AlS-5 Xoliah S.M. AES-117 Jurczyk j. AAS-115 Koloaiaky V.R. ALS-17 Kabirov Y.V. XRS-42 Koloahnikov V.G. ALS-30 Xalinin B.D. XRS-22 Koaarak J. AAS-85

473 Author's Index

Komissarova L.N. XRS-15 Kulikova I.K. XRS-91 Konakhina A.I. AES-138 KUlikovskaja E.v. XRS-61 Xondrat'ev I.I. XRS-52 Kunock V.N. AES-95 XRS-25 Kunze S. MISC-8 Konnikov S.G. XRS-88 Kupriyanova T.A. XRS-92 Kononkova H.N. XRS-89 Kuras T. AES-80 XRS-90 Kurilovich Ya.E. XRS-65 XRS-87 Kuroohkin v.K. HISC-1S Konyshev N.H. ALS-29 Kuss Н.И. BISC-20 Kopcakova H. AAS-96 Kuteinikov A.F. AES-8S Koptenko E.p. HISC-6 XRS-51 Kopyl L.V. AES-60 Kuz'nin N.M. AAS-30 Koreckova J. AAS-84 AES-116 Korobeynikov s.i. XRS-60 AES-115 Korobeynikova L.P. XRS-60 JHSC-17 XRS-4 AAS-86 Koroluk V.N. XRS-94 AAS-28 Korovin Yu.I. PLN-2 AES-109 AES-13 Kuzmenko N.E. AES-101 AES-44 Kuzmina T.G. XHS-63 Korovkin И.А. XRS-87 Kuzner D. ALS-5 Korovkina N.A. XRS-62 Kuznetoov A.V. ALS-17 XRS-61 Kuzneteov I.P. AES-6 XRS-17 Kuznetsova A. AES-102 XRS-87 Kuznetsova A.I. XRS-93 Korovyatnikov G.F. AAS-16 XRS-94 Kostin V.A. XRS-102 Kuzyakov Yu.Ya. AES-103 Kostin V.G. XRS-49 ALS-7 XRS-67 AAS-101 Kostyanovaky R.G. MISC-15 ALS-25 Kosyakov V.I. AES-125 Kyleshov V.I. AES-83 Kovacs Z. AAS-39 L'vov B.V. AAS-71 Kovalenko A.s. AAS-110 PLN-9 Xovalenko N.L. AES-88 Laborda F. AAS-72 Kovalev A.Va. ALS-2 Lakatos I. AAS-31 Kozakov A.T. XRS-99 AAS-31 Kozlov д.A. AES-99 AAS-3 Kozlov V.A. XRS-37 Lakshnan S.V.J. MISC-9 Krakovska Б. AAS-27 Laseeva G.S. AES-42 Kranpit I.A. XRS-85 AES-138 Krasavchikov v.o. XRS-6 Latikainen V.I. AES-79 Krasilshchik V.z. AES-IOO Lavrent'ev Vu.G. XRS-94 Krasnolutsky v.P. XRS-103 XRS-93 Rrasnspolskaya N.N. XRS-26 Lazarev V.B. AAS-64 Kratka B. AAS-76 Lazarova A. AES-104 Krivoputakaya L.M. HISC-7 Lazarova V. XRS-40 MISC-16 Lachon J.N. ABS-4S Kruglyak A.L. AAS-15 Laduc Joel AES-43 Kuban V. AAS-8S Legaza S.s. AES-105 Kubrakova I.v. AAS-86 Lagkova G.V. XRS-95 AAS-28 XRS-96 AES-116 Latov S.V. XRS-93 Xuchanev A.N. AES-41 Lindeaan E.v. AES-1P6 Kuchuk G.M. AAS-29 Liaienko D.G. AES-44 Kuchunov V.A. AES-13 Littlajohn D. AAS-32 Kudinova T.F. AAS-28 Ljubiaova L.N. ALS-1 Kulagin N.A. XRS-27 Lobanov F.I. XRS-65 Xulashov V.I. AES-95 XRS-64

474 Author's Index

XRS-18 Mikliahanaky A.Z. XRS-59 Loginov Y.H. ALS-17 Hinchenko B.I. AES-10 Logunova s.A. XRS-64 Mir J.M. AAS-6 XRS-65 AAS-72 Lopaa K.Diaa AAS-101 Mironcnko М.У. XRS-83 Lopez-Molinero A. AES-45 XRS-66 Loranz L.A. XKS-59 Misakov P.Ya. ALS-33 Loaev V.H. XRS-66 ALS-2 XRS-103 Miakaryanta v.G. AAS-67 Loaava A. P. AES-46 Hitina T.F. MISC-6 Loaava T.A. AES-46 Mladenov G. AES-104 Lunyov O.S. ALS-40 Hoffatt J. MISC-26 Luong v.T. AAS-S6 Holchanova E.I. XHS-29 Luaa Ya.L. AAB-S6 XRS-80 Lutokhin A.G. KESC-23 Hollov D. HISC-24 Lyaapaaova T.P. AES-132 Molnar Za. HISC-2 Madin M.I. ALS-10 Moachilova S. AAS-112 Hadina S.Sh. ALS-10 HISC-4 Hajorova L.v. AAS-5 Morgan C.G. MISC-22 Majorova O.N. XRS-94 Moshkovich C.N. AES-78 Hakarov V.L. AAS-13 Mosichev V.I. AES-76 Makhotko v.F. XRS-94 ABS-31 KakaiBOv D.Ye. ABS-107 AES-30 Makaiaov G.A. MISC-10 XRS-34 Halaknov S.K. AAS-90 AES-11 Halanuk v.V. AES-11 AAS-91 Maligina D.v. AES-9» XRS-32 Mamulova T.P. XRS-67 XRS-33 XRS-49 Moakalanko N.I. AES-132 Hanuilova O.A. XRS-65 Moakvin L.N. AES-47 Marchut A. XRS-28 Mouraahava L.P. XRS-69 Karkova H.L. AES-142 Hullar M. NISC-20 Martin H.-L. AAS-87 Hullin» C.B. MISC-26 Martina» L.J. AES-2 Muradov V.G. AAS-33 Marunkov A.G. ALS-41 Huraahkina V.N. XRS-51 ALS-34 Hurziava 6.S. AAS-111 Maryanov v.H. AES-84 Muzgin V.N. AAS-34 Maryutina T. AES-115 AES-44 Kaahin N.I. XRS-104 Hyaaoadova G.V. AES-92 Haahkovich L.A. ..ES-85 Nagdaav V.K. AAS-90 Matanova E. AAS-88 Nagdaav V.K. AAS-3S Hatuaavitch s. AES-121 Nagulin K.Yu. AES-33 Hatvaav o.I. ALS-15 Nagulin Yu.S. AES-33 Havlyutov К.И. AAS-111 AAS-111 HaxiBOV D.E. ALS-40 Nalobin D.P. XRS-37 Maxiaov G.A. ALS-27 Naavrina E.G. XRS-78 Haxiaov V.H. XftS-68 Napolaa C.A.da la Fc AAS-41 XRS-50 AAS-40 MaxiBOva E.v. ALS-21 Hartova Z.M. XRS-48 Maydurov A.D. AAS-54 HaiiBankov P.A. ALS-33 Mayo 8. ALS-4 ALS-2 Mayorov I.A. ALS-35 HaiiBova L.M. ALS-42 Maxurova Z.K. HISC-7 NauBtaav Т.Е. XRS-30 Maxzucotalli A. AAS-89 Nazarov V.N. AES-55 Kanandai A. AES-58 Nadlar V.V. PLN-2 Markuahav v.A. AES-106 Netadov V.I. XRS-5 Harkuahav v.A. AAS-45 Nakludov A.A. XRS-69 Hiarzwa J. AAS-74 Naaata V.M. AES-48

47* Author's Index

AES-49 Pavlova V.N. AAS-93 Nenets A.H. ALS-12 Pavlutakaya V.I. ALS-41 Nenchev H. ALS-38 ALS-22 Naradovakaya N.V. AES-83 Pchalkin A.I. HISC-1J AES-84 Pachav z. ALS-38 Nickolaav G.I. ALS-12 Paliava L.A. AAS-37 Nickolaichuck T.A. AES-108 Paplinaki B. XRS-36 Hicolaev в.I. XRS-33 Paravartun V.M. AES-110 Hicolov T. AES-104 AES-35 Niaaa* K. ALS-11 Parahin N.V. XRS-32 Nikitin N.N. AES-126 XRS-34 Nikitina H.F. AES-79 XRS-33 Nikitina 0.1. AES-108 Paraikova L. MISC-12 Hikolaky A.P. XHS-7 Petrakiev A. HISC-24 XHS-31 Patrov A.A. AES-51 XRS-46 AES-48 XRS-77 ALS-26 Novichyhin A.v. AAS-91 ALS-36 Novikov N.F. AES-117 Patrov L. HISC-12 AES-118 Petrov S.J. AES-40 Hovikov S.R. XRS-102 Petrov S.N. XRS-97 Novikov V.M. XRS-75 Petrova в.P. XRS-75 Novoayolova M.M. AAS-118 Petrovskaya I.N. AES-92 obrazovaky E.G. XRS-53 AES-121 ochertianova L.I. AAS-64 Petukhov s.v. AAS-49 Odineta V. AAS-2» Pimanov V.P. HISC-10 Olanovicb N.L. AAS-117 Plaackach L.I. AAS-38 Omenetto N. FLN-10 Pliaaovaka N. AES-111 HISC-27 Plinar L.N. XRS-80 Orcahkin V.N. AAS-92 Plotnikov R.I. XRS-22 Orlov V.V. XRS-70 XRS-23 Orlova V.A. AES-38 Plcko E. AES-52 HISC-17 Podaoehenakaya S.V. AES-53 Oaheakov S.v. ALS-36 Polikarpova N.V. AAS-94 ALS-26 Polivtaav o. XRS-73 ALS-31 Popke R. AAS-95 ALS-40 Poplavakaya E.N. AAS-94 Oahurko V.8. ALS-1 Popova T.B. XRS-20 Oaipova V.A. AES-26 Portnov И.А. XRS-35 AES-20 Portnova T.V. AES-142 Oatrlk P.N. AES-72 Portnova Ya.v. AAS-73 Otaaehova Z.I. AES-84 Portuondo H.R.Cataau AES-54 AES-83 AAS-41 Pachadzbanov D.N. AAS-102 AAS-40 AAS-103 Poata J. AAS-39 Panaiotov 6. XRS-71 AAS-8 Panichav N.A. AAS-36 Potapova v.G. AES-112 Panov V.A. AES-101 HISC-3 Panova E.I. AES-141 Fraaad S.K. HISC-1 Pantelayav G.P. AES-109 XRS-59 Pantelayav v.v. ALS-14 Pravtchava с ALS-4S ALS-43 Preobrazbenaky N.G. ALS-3 ALS-13 Pribytkov v.A. ALS-1S Papp L. AE5-50 Prieto M.Alvarez AAS-41 Paaynkova T.A. XRS-65 AES-54 Patrikov T. ALS-38 AAS-40 Paukert T. AES-119 Privalova T.A. XRS-77 Pavlinaky G.v. XRS-72 Prokopchuk S.I. AES-113

471 Author's Index

Prokopjeva A. HISC-12 Rubaaka I. AES-119 Ptostyakova L.A. AAS-86 Rudnev S.H. ALS-30 Prudnikov E.D. MSC-13 Rudnevaky A.N. AES-107 AAS-79 ALS-40 AAS-53 Rudnevaky N.K. АЕ8-в7 Przeprlera A. XRS-74 XRS-104 AES-114 ALS-21 Pazonioki L. AAS-42 AAS-73 AES-34 AES-117 Pukhovzkaya V.H. AES-116 Ruaaava E. AAS-98 AES-115 Ruetaaov s. AES-86 Pukhovaky A.V. ALS-17 Rybalko Yu.I. ALS-S Pupyshav A.A. AAS-43 Rybinaka-васак M. XRS-76 AAS-34 Ryeev A.p. XRS-56 Puachal p. HISC-14 Ryzhkova S.H. HISC-16 Puahkareva E.A. AES-51 Sadagov Yu.M. AAS-49 Puahkina G.Ya. XRS-15 Safina R.A. AAS-111 Putninya S.Ya. AAS-65 Saichenko A.N. AES-17 AAS-66 AES-16 Ptitranko 0.1. ALS-14 Saichenko L.A. AES-17 Pyatigina L.B. AES-103 AES-16 Radaev V.N. ALS-27 Salakhov M.Kh. AES-57 ALS-29 AES-56 Sadamayer C.J. AAS-44 Salaknutdlnov M.S. XRS-77 Raikov S.H. ALS-33 Saachuk A.I. AAS-50 ALS-2 Saaohvalov S.G. ALS-17 Razyapov A.Z. AAS-45 Saaual B. AAS-78 AES-S5 Sanchaz-Uria J.E. AES-58 AE5-106 Sandrik R. XRS-47 Rebalda G.V. AAS-66 Sanz-Hadal A. AES-58 Raitznarova E. AAS-96 Saparova L.V. AAS-97 Rannar J. XRS-102 Saphronova U.S. ALS-28 Ravalda G.V. AAS-65 Sapoahnikov D.Yu. XRS-S9 Ravalaky I.A. HISC-15 Savchenko G. XRS-68 Ravanko A.G. XRS-75 savina E.v. XRS-49 Razchikov v.G. ABS-117 XRS-67 AES-118 Savlnova E. AES-120 Richtsr K. XRS-36 Savitchav Л.Т. XRS-17 Rigin V.I. AAS-46 Savranakaya I.A. AAS-US AAS-48 schapin S.H. ALS-27 AAS-47 Schelkova v.P. AES-61 Slabakov S. AES-136 Scharbovaky E.Ya. XRS-87 Riah И.А. AAS-69 Schiarhorn E. HISC-2S Rsava N.N. AAS-97 Scbikora T. AAS-99 Roaananko I.H. XRS-98 Scblaaaer G. AAS-100 Roaanova O.G. AES-8S AAS-51 Roaaabkina O.A. AES-10* schaidt It. p. AA5-52 Rone V.P. XRS-62 Schubert-Jacoba M. AAS-66 Roahina I.A. XRS-C2 Schwartz E.H. AES-101 XRS-61 Schuantnar N. ALS-5 XRS-18 Sedykb E.H. AES-121 «S-X7 HISC-17 Roabzina o.V. AES-122 AAS-60 AES-123 AES-134 Roaain A.E. AES-124 AES-92 AES-125 AES-109 Rozantcav v.A. ALS-43 Salaznav V.V. XRS-3S ALS-13 Saaananko K.A. AAS-101

477 Author's Index

AES-103 AES-63 AES-lPi Slickers K. AES-64 senionova E.V. XRS-79 Slovak Z. AAS-57 Serapinas P. AES-1 snagounov A.V. XRS-35 Sergeev A.Ku. ЛЙ8-77 Snagunov A.V. XRS-80 Sermin D.F. PLH-11 smagunova A.N. XRS-37 Severin E.N. AES-59 XRS-80 AES-60 XRS-29 Severin V.I. AAS-110 Snirenkina I.I. ALS-30 Shabanova L.N. AES-1Z2 salrnov K.v. AES-128 AES-123 snirnov v.v. HISC-17 AES-7 snirnov Yu.M. AES-41 AES-BB snirnova E.v. AES-GS shaidullin S.A. AAS-111 AES-24 Shakirova D. AAS-69 suit H.H.A. XRS-38 Shapkina Y.S. AAS-53 smith B.H. PLN-10 Sbaplygin I.S. AAS-64 MISC-27 Shapovalov D.A. AAS-45 sobolev v.B. XRS-96 SbatkowsJcaya N.A. AAS-102 sokolov s.V. HISC-15 AAS-103 AES-61 sbchelchkova S.G. ALS-42 sokolova E.A. AES-66 Shcherbakova N.K. AES-57 soldatenko G.G. AES-88 shcherbakova 0.1. AES-124 solntseva S.M. MISC-7 Shelpakova I.R. AES-124 MISC-16 AES-125 soloviov A.A. AE5-49 shestakov V.A. XDS-7B AES-48 Shevtsov H.I. XRS-48 soltas P. AES-111 Shevtsova S.I. XRS-99 Sorokin H.v. AAS-16 Shipova E.V. HISC-11 souleva A.N. AES-129 Shiriaeva O.A. AES-126 soylak И. AAS-75 Sbirokanov A.D. ALS-13 sparling И. AAS-62 Shiahov V.N. AES-B9 Spiridonova I.M. AES-133 Shmanenkova G.I. AES-61 spirkova R. AAS-76 Sholupov S.E. AAS-54 spivakov B. AES-115 Sbpolaynsky А.У. XRS-13 Stahlberg U. AES-131 XRS-12 stakhaav 4a.1. AAS-106 Shtapan A.M. AAS-24 AAS-108 Shtitel'man Z.V. AES-141 starahinova N.p. AES-121 AES-112 AES-92 Shumilin E.H. HISC-1 AES-109 Shumakaya T.V. AES-134 HISC-1 Sibaeva I.N. ALS-17 Stefanovic A. XRS-100 sidncv V.I. AES-87 Starlich F. ALS-44 Siaxmova L.V. AES-94 stocv K.N. XRS-44 Siatonova V.I. AAS-5S stroganov D.N. XRS-4 AES-127 stroganova N.s. HISC-21 Sinitsin V.N. XRS-42 stuchlikova A. MISC-14 XRS-79 Sturgeon R.E. AAS-56 Sinizin U.K. XRS-57 stvarak B. XRS-81 Sinyaav I.G. XRS-59 XRS-82 Skorakaya O.L. AAS-1S subkhankulov E. ALS-46 Skotnikev S.A. AES-62 sukhanov v.A. XRS-39 AES-128 AAS-S Skudra A.ya. AAS-65 sukhov L.T. ALS-16 AAS-66 sukmv v.s. AES-130 Skwara N. AAS-104 AES-97 Slavln F.I. AES-36 ALS-42 Slavin N. AAS-105 suknava L.S. AES-130

4» Author's Index

Sultanbekov F.F. AES-69 Turkin Yu.I. AES-47 sumarokov S.U. XRS-4S AAS-12 Surikov V.T. AES-132 Tursunov A. AAS-69 Surowska B. XRS-100 Tverdokhlebova s.v. AES-133 Suvorova E.A. AES-87 Tynochovicz S. AES-SO Svardalova B. XRS-40 Uchevatkina L.A. AES-121 Svechnikova Т.Е. AAS-94 uitbeijerse E. AES-98 Sveshnikov G.B. AAS-S4 Ul'yanova V.P. AES-127 syirina Т.Д. XRS-69 Unger Ph.G. XRS-39 Szucs L. AAS-39 AAS-S Tagiltsev A.P. AES-127 Unger W. XRS-36 Talpalatsky P. XRS-73 Urmanbetov X. AES-136 Tarnopolsky M.G. XRS-12 Urosov I.I. HISC-7 Tatsy Yu.G. AAS-108 Usachova V.I. AES-46 AAS-106 Uskova A.I. AA5-111 AES-134 Usova L.V. XBS-93 Terechovich S.L. AES-35 XES-94 Terentyeva E.v. ALS-1 Ostimenko V.N. AAS-110 Terpakova E. AES-1B ustyugova T.T. AES-90 Thonnard N. ALS-18 Uudelevich I.e. AAS-116 Thorne E.H. AES-2 Uvarov A.I. XRS-S4 Tianyan Gu AAS-77 Vakhobova R.U. ALS-46 Tie ling Zhang AAS-1D7 XRS-5S Tikhonirov S. AAS-58 AAS-103 Tikhonirova E.I. AES-134 Valdes-Hevia с AES-S8 Tilch J. ALS-20 Valeev G.V. AAS-111 Tintofeeva L.N. AES-20 Varga I. AES-139 Tiaofeeva L.T. AES-26 Varshal G.H. AES-106 Tinofeyev A.D. AAS-12 Varvanina G.V. AES-70 Tinonin O.A. MISC-10 AES-77 Timonin I.M. AES-10 Vasielyeva V. AES-104 Tischenko E.A. AAS-64 Vasil'ev V.V. XRS-32 Tkachev Ku.A. ABS-32 Vasil'eva I.E. AES-71 Tluchor D. XRS-81 Vasilieva L.A. AAS-25 XRS-82 Vaasileva E. AAS-112 Toctogonov s.A. ALS-24 Vavrikova 0. XRS-82 Todorovic H. AAS-59 XRS-81 Traktuev O.N. AES-47 Vecsernyes L. AES-137 Travis J.С ALS-4 Vereahchak A.V. XRS-86 ALS-19 Verhovcky B. XRS-31 Tretjakov V.V. XRS-88 Veruak I. AAS-44 Tripkovic H. AES-68 Veraan B.S. XRS-105 AES-29 Veraan N.A. XRS-4 Trofinova L.B. «IBM vidovic S. AAS-59 HISC-16 Virtsava D.X. XRS-62 Trojan-Golovjan G.N. XRS-27 virtsavs H.V. XRS-62 Tropp E.A. XRS-3 Vishnevsky A.A. XRS-96 XRS-20 Vladinirova L.I. XRS-72 Troshkova G.P. AES-135 Vladiairskaya I.N. AES-126 Trunova V.A. XRS-58 Vlasov A.A. XRS-8 Tscrovaki E. AAS-109 Vlaaov I.I. ALS-23 Tsolov T. ALS-45 ALS-22 Tsvatyansky A.L. XRS-45 ALS-34 Tayain G.I. AES-109 Vlaaova T.A. AAS-93 Tuaanova A.N. ALS-21 Vnukovskaya G.L. AAS-92 Turk G.c. ALS-19 Vodopoanko V.A. AES-72 Turkin V.V. AES-69 volkov V.F. XRS-83 AES-33 XRS-42

47» Author's Index

XRS-41 zakharov V.N. XRS-52 XRS-26 zakharov Vu.A. AAS-14 XRS-30 Zakharya A.N. AAS-63 volodin s.A. XftS-84 AAS-117 Voloshin A.V. AAS-14 Zanarayev v. AES-8 Volyneky A.B. AAS-58 Zanoxina V.F. AES-87 AAS-60 AES-142 Vorobjeva I.v. XRS-84 Zaray Gy AES-139 Voronkova H.A. AAS-113 ABS-37 Voroshilova T.A. AES-138 Zavgorodniy V.N. XRS-46 Voskresenskaja V.S. AAS-113 XRS-85 Vuchkov И.К. XRS-44 XRS-7 XRS-43 Zabreva A.I. XRS-65 Vulfson E.K. AAS-61 Zelentsova L.V. AES-140 Vykhreatenko N.I. AAS-16 Zelyukova Yu.V. AAS-118 Walker R.J. ALS-4 Zeaakova I.A. AAS-4 Hatters R.L. ALS-19 AAS-49 Welz B. AAS-62 Zemtsova L.I. ALS-1 AAS-68 Zengyuan Gan AAS-77 Willie S.N. AAS-56 Zheenbaev Zh.Zh. AES-136 Wisniewaki M. XRS-74 ALS-24 AES-114 Zhitenko L.P. XRS-70 Wrobel к. AAS-70 zhizhin I.p. XRS-10S AAS-S1 zholudeva L.S. XRS-87 Mycislik A. AAS-115 Zil'baratein Kh.E. AES-78 AAS-114 Zivbalist v.G. AAS-55 Xakiaova V.A. AES-138 Zolotov Yu.A. AES-115 Yankovaky A.A. ALS-43 AES-109 ALS-13 Zolotovitskaya E.s. AES-141 Yaroachevaky A.A. XRS-90 Zorin A.D. AES-142 Yeaelyanov A.A. AES-87 AES-87 Ycaelyanova O.A. AES-142 Zorov N.B. ALS-25 Veritanko A.N. XRS-45 ALS-7 Yarykalina N.v. A1S-21 Zybin A.V. ALS-30 yevjanov H.N. AAS-97 Zymieki W. AES-73 YU L. ALS-19 Zytanko L.p. XRS-56 Yudelevich I.G. AES-135 AES-127 oeiirmis Plenary Lectures (Fill) 5 Atomic-absorption Spectroscopy CAAS) •••• • • 21 Atomic-emission Spectroscopy (ASS) ...... 143 Atomic laser Spectroscopy (ALS) •,.» • •••• 2e? X-Лау Spectroscopy (XRS) ••••• 337 Uiscellaneous Speotroacoptc Techniques and lata Abstracts (IЛ SO 443

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