DOCSLIB.ORG

Januar11981 on the Derivation of a Creep Law from Isothermal Bore Hole

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Januar11981 on the Derivation of a Creep Law from Isothermal Bore Hole JANUAR11981 ON THE DERIVATION OF A CREEP LAW FROM ISOTHERMAL BORE HOLE CONVERGENCE BY J. PRIJ J.H.J. MENGELERS ECN does not assume any liability with respect to the use of, or for damages resulting from the use of any information, apparatus, method or process disclosed in this document. Netherlands Energy Research Foundation ECN P.O. Box 1 1755 ZG Petten INH) The Netherlands Telephone (0)2246 - 6262 Telex 57211 ECN-87 SEPTEMBER 1980 DISPLACEMENT AND EXCHANGE REACTIONS IN RADIOANALYSIS BY P.C.A. OOMS Proefschrift Vrije Universiteit Amsterdam, 30 september I980 - J CONTENTS Page CHAPTER 1. INTRODUCTION 9 1.1. Classification of separation methods 10 1.7.1. Reaction with a free reagent 10 1.1.2. Displacement 11 1.1.3. Isotopic exchange 12 1.2. Analytical criteria 12 1.2.1. Activation analysis with a spe­ cific reagent 13 1.2.2. Isotope dilution analysis with a specific reagent 14 1.2.3. Activation analysis with a non­ specific reagent 14 1.2.4. Isotope dilution with a non-speci­ fic reagent 14 1.2.5. Isotopic exchange 14 1.3. Selection of procedures 15 1.3.1. Liquid-liquid extraction using a non-specific chelating agent 16 1.3.2. Amalgams 16 1.3.3. Loaded active carton 18 1.3.4. Coulometry 19 1.4. List of symbols 21 1.5. Summary of contents 23 1.6. References 25 CHAPTER 2. APPLICATION OF DISPLACMENT - AND EXCHANGE REACTIONS IN NEUTRON ACTIVATION AND ISOTOPE DILUTION ANALYSIS 27 2.1. Introduction 28 2.2. Calculations of equilibrium concentrations 28 2.2.1. Definitions 28 2.2.2. Theoretical considerations 29 - 6 - Page 2.2.3. Numerical calculations 31 2.2.3.!. Programmes 31 2.2.3.2. Precision of the calculated q-values 33 2.2.4. Application 34 2.2.4.1. Activation analysis 34 2.2.4.2. Isotope dilution analysis 34 2.3. Experimental 35 2.3.1. Chemicals and apparatus 35 2.3.2. Procedure 35 2.4. Conclusions 36 2.5. References 37 CHAPTER 3. RADIOMETRIC DETERMINATION OF THE EXTRACTION CONSTANTS OF SOME METAL DIETHYLDITHIOCARBAMATES IN THE SYSTEM CHLOROFORM/WATER 38 3.1. Introduction 39 3.2. Theory 40 3.3. Experimental 41 3.3.1. Chemicals and equipment 41 3.3.2. Procedure 42 3.4. Results 42 3.5. Discussion 45 3.6. References 47 CHAPTER 4 CALCULATIONS ON PARTITION EQUILIBRIA IN LT/^JID- LIQUID EXTRACTION SYSTEMS, APPLIED TO THE SEPARATION OF METAL IONS FROM AQUEOUS SOLUTIONS 48 4.1. Introduction 49 4.2. Theory 51 4.2.1. Definitions 51 4.2.2. Theoretical considerations 51 - 7 - Page 4.3. Calculations 54 4.3.1. Computer programmes 54 4.3.2. Applications in activation analysis 54 4.3.3. Application in isotope dilution analysis 55 4.4. References 56 CHAPTER 5. MULTIELEMENT ISOTOPE DILUTION ANALYSIS BY MEANS OF RADIOMETRIC TITRATION 71 5.1. Introduction 72 5.2. Principle 73 5.2.1. Definitions 73 5.2.2. Theoretical considerations 73 5.2.3. Optimization of the Kl -values 75 5.3. Experimental 76 5.3.1. Chemicals and equipment 76 5.3.2. The titration vessel 76 5.3.3. Procedure 78 5.4. Results 79 5.4.1. Experiments to check the apparatus 79 5.4.2. Radiometric titrations of some solutions of metal ions 81 5.4.2.1. Titration of a 3.2xl0~4 M Cu(II) solution with a 2 l.Oxlo" M Zn(DDC)2 solution in chloroform 81 5.4.2.2. Titration of a mixed solution of 3.15xl0~6 M Cu(II) and l.OxlO-1 M Pb(II) with 4 2.5xlO~ M Zn(DDC)2 dissolved in chloroform 81 5.5. References 84 CHAPTER 6. ISOTOPE DILUTION ELECTROANALYSIS 85 6.1. Introduction 86 6.2. Principle 86 6.2.1. Procedure I: two electrolytic cells connected in series 86 6.2.2. Procedure II: electroysis in one single cell 87 6.3. Experimental 88 6.3.1. Apparatus 88 6.3.2. Reagents 91 6.3.3. Procedures 91 6.4. Results 92 6.4.1. Results from Procedure I 92 6.4.2. Results from Procedure II 92 6.5. Discussion 93 6.6. References 93 APPENDIX I DESCRIPTION OF THE COMPUTER PROGRAMMES QFORW AND QPLOT 95 APPENDIX II TEXT OF THE COMPUTER PROGRAMMES QFORW AND QPLOT 111 APPENDIX III DESCRIPTION OF THE COMPUTER PROGRAMME QBACK 139 APPENDIX IV TEXT OF THE COMPUTER PROGRAMMA QBACK 147 APPENDIX V DESCRIPTION OF THE APPARATUS FOR SEMIAUTOMATIC LIQUID-LIQUID EXTRACTION 159 SAMENVATTING 163 CURRICULUM VITAE 1 - 9 - CHAPTER 1. INTRODUCTION SUMMARY The application of displacement and exchange reactions in radioanalysis is discussed. A few cases are selected for further investigation. The contents of the other chapters are suimarized. - 10 - 1.1. Classification of separation methods Many analytical procedures involve an isolation of the compound of inte­ rest effected by its transfer to another phase. Usually this implies dissolution of the sample. One might then summarize these determinations by the following scheme: sampling —• dissolution —> separation —•• measurement The separation procedures, based on reaction between the compound to be determined and a reagent, have been distinghuished into three types accor­ ding to the "reagents" which are used: a) reaction with a free reagent (section 1.1.1.) b) displacement reac­ tions (section 1.1.2.) c) isotopic exchange reactions (section 1.1.3.). From the point of view of radioanalysis one should make a second dis­ tinction by the amount of reagent which may be present in excess or in a substoichiometric quantity. Both situations are met in activation ana­ lysis. Isotope dilution methods are based on the addition of a sub­ stoichiometric amount of reagent. In this thesis attention will be restricted to one step separation pro­ cedures. 2i]>iJK_Reaction_with_a_free_reagent The reagent R may react with the compound C according to aR + C t R C (1) where a represents the stoichiometric ratio. An equilibrium constant is defined by equation (2) [RC] a = K (2) [Rf[C] eq Separations based on adsorption belong to this class, in that sense that a is no longer the stoichiometric ratio, but the (variable) ratio of the amount of adsorbent and the component to be adsorbed. Usually the product K [R] is very large and thus the recovery of C vir­ tually complete. Examples of this situation are found in the determina­ tion of mercury in air by adsorption to active carbon |l|, or Mn02 |2J, and that of trace elements in dry biological material by dissolution, - 11 - dilution and adsorption to active carbon |3|. Adsorption has not been applied in isotope dilution analysis since the reproducibility in taking substoichiometric amounts of the adsorbent in case of very low concentrations of the compound to be adsorbed is very poor. Electrodeposition belongs also to this type of reaction. It has been applied in activation analysis for the determination of |4|. The use of coulometry has been reported for the isotope dilution analysis of Cd |5|. lili^ J)is£lacement The reagent R is added as R A which is present in a separate phase. A h^s to be displaced by the analyte B; that is: |RQA + B i RgB + §A (3) Again one can define an equilibrium constant. [RHB][A]I 3 = K (4) I eq [R A]°[B] a There are many applications of displacement reactions in chemical sepa­ ration. A further classification may be brought about by defining the reagent phase. The most common case is addition of the reagent dissolved in an organic liquid, immiscible with the aqueous phase containing the element(s) to be determined. A survey of the procedures is given in ref. |6|. In radioanalysis this approach is used in activation analysis as well as in isotope dilution methods. In the latter case the reagent should be specific or the interferences should be removed first |7|. In activation analysis specificity is not imperative but it may be so if it is necessary to obtain a radiochemically pure counting aliquot or at least a convenient group separation. Another group of displacement reactions is based on ion-exchange. Again the applications in activation analysis are numerous. A survey may be found in refs. |8| and |9|. The use in isotope dilution has been restricted to the determination of a single species |10|. - 12 - A third class of displacement reactions is presented by the isomorphous exchange between an aqueous solution and a insoluble salt. The experi­ ments in this domain belong to the oldest part of radiochemistry |il, 12f. Applications in activation analysis have been reported for the lanthanides |13|. The possibility of separating manganese has been discussed [I4|. This principle cannot be used in isotope dilution. 1.1.3. Isotopic exchange The interest of this group of separations is restricted to analytical methods with the aid of which isotopes of a nuclide can be disting­ uished, i.e. radioanalysis and mass spectrometry. It is characterized by the reaction C + C* t C* + C (5) where the bar denotes the second phase and the asterisk the species with a particular isotopic composition. The equilibrium constant is about equal to unity. Small but distinct differences, known as the isotopic effect, may exist for light elements |l5|. The application of isotopic exchange in radioanalysis is mainly found in activation analysis. The isolation of iodine from irradiated rainwa­ ter may be cited |l6|. The exchange between an aqueous solution of a lanthanide and one of its insoluble salts, mentioned above, is another example. The interaction between an aqueous solution of a (heavy) metal ion and an amalgam presents a third type of exchange reactions |17|.
Load more

Recommended publications
  • Chapter 3 the Measurement Technique of Isotope Dilution
    Chapter 3 The measurement technique of isotope dilution inductively coupled plasma mass spectrometry (ICP- MS) 3.1 Introduction Total metal analysis, including trace and ultra trace elemental analysis of geological materials, have traditionally been performed using analysis methods such as atomic absorption spectroscopy (AAS), X-ray fluorescence (XRF), instrumental neutron activation analysis (INAA)[22]. Other methods include flame emission spectrometry, spectrophotometric analysis, ion selective electrode potentiometry, UV/VIS spectroscopy, candoluminescence, etc[10, 11]. Over the past 30 years more versatile measurement techniques have been developed in the form of inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). The first requirement for this study was to re-certify SARM 1 to 6 using a definitive technique with the potential to be a primary reference measurement procedure (primary method) as defined in Chapter 1[2]. Firstly, the method must be performed at the highest level of accuracy (trueness and precision)[2, 23]. Secondly, a complete measurement model must be defined in terms of SI units to facilitate the complete evaluation of all contributions to the measurement uncertainty in accordance with the Guide to the Expression of Uncertainty of Measurement (ISO GUM)[4]. Isotope dilution mass spectrometry is a direct ratio method which has been identified by the Consultative Committee for Amount of Substance (CCQM) of the International Committee for Weights and Measures (CIPM) to have the potential to be a primary method [1]. Isotope dilution measurements can be made with inductively coupled plasma mass spectrometry (ICP-MS), which is specifically suited to trace and ultra trace elemental analysis of geological materials.
    [Show full text]
  • Calibration Graphs in Isotope Dilution Mass Spectrometry Pagliano, Enea; Mester, Zoltán; Meija, Juris
    NRC Publications Archive Archives des publications du CNRC Calibration graphs in isotope dilution mass spectrometry Pagliano, Enea; Mester, Zoltán; Meija, Juris This publication could be one of several versions: author’s original, accepted manuscript or the publisher’s version. / La version de cette publication peut être l’une des suivantes : la version prépublication de l’auteur, la version acceptée du manuscrit ou la version de l’éditeur. For the publisher’s version, please access the DOI link below./ Pour consulter la version de l’éditeur, utilisez le lien DOI ci-dessous. Publisher’s version / Version de l'éditeur: https://doi.org/10.1016/j.aca.2015.09.020 Analytica Chimica Acta, 896, pp. 63-67, 2015-10-08 NRC Publications Record / Notice d'Archives des publications de CNRC: https://nrc-publications.canada.ca/eng/view/object/?id=c963874f-036a-4da0-9def-eead416e46d9 https://publications-cnrc.canada.ca/fra/voir/objet/?id=c963874f-036a-4da0-9def-eead416e46d9 Access and use of this website and the material on it are subject to the Terms and Conditions set forth at https://nrc-publications.canada.ca/eng/copyright READ THESE TERMS AND CONDITIONS CAREFULLY BEFORE USING THIS WEBSITE. L’accès à ce site Web et l’utilisation de son contenu sont assujettis aux conditions présentées dans le site https://publications-cnrc.canada.ca/fra/droits LISEZ CES CONDITIONS ATTENTIVEMENT AVANT D’UTILISER CE SITE WEB. Questions? Contact the NRC Publications Archive team at [email protected]. If you wish to email the authors directly, please see the first page of the publication for their contact information.
    [Show full text]
  • Calorimetry Has Been Routinely Used at US and European Facilities For
    10. PRINCIPLES AND APPLICATIONS OF CALORIMETRIC ASSAY D. S. Bracken, and C. R. Rudy I. Introduction Calorimetry is the quantitative measurement of heat. Applications of calorimetry include measurements of the specific heats of elements and compounds, phase-change enthalpies, and the rate of heat generation from radionuclides. The most successful radiometric calorimeter designs fit the general category of heat-flow calorimeters. Calorimetry is used as a nondestructive assay (NDA) technique for determining the power output of heat-producing nuclear materials. The heat is generated by the decay of radioactive isotopes within the item. Because the heat-measurement result is completely independent of material and matrix type, it can be used on any material form or item matrix. Heat-flow calorimeters have been used to measure thermal powers from 0.5 mW (0.2 g low-burnup plutonium equivalent) to 1,000 W for items ranging in size from less than 2.54 cm to 60 cm in diameter and up to 100 cm in length. Calorimetric assay is the determination of the mass of radioactive material through the combined measurement of its thermal power by calorimetry and its isotopic composition by gamma-ray spectroscopy or mass spectroscopy. Calorimetric assay has been routinely used at U.S. and European facilities for plutonium process measurements and nuclear material accountability for the last 40 years [EI54, GU64, GU70, ANN15.22, AS1458, MA82, IAEA87]. Calorimetric assay is routinely used as a reliable NDA technique for the quantification of plutonium and tritium content. Calorimetric assay of tritium and plutonium-bearing items routinely obtains the highest precision and accuracy of all NDA techniques.
    [Show full text]
  • ICP-OES, ICP-MS and AAS Techniques Compared
    ICP OPTICAL EMISSION SPECTROSCOPY TECHNICAL NOTE 05 ICP-OES, ICP-MS and AAS Techniques Compared Geoff Tyler Jobin Yvon S.A.S, Horiba Group Longjumeau, France Keywords: atomic spectroscopy, detection limit, linear dynamic range, interferences, precision, cost of ownership, sample throughput 1 Introduction Inductively coupled plasma-optical emission 7. What sample volume is typically available? spectrometry (ICP-OES) is an attractive tech- 8. What other options/accessories are being nique that has led many analysts to ask whether considered? Why? 9. How important is isotope information to it is wiser to buy an ICP-OES or to stay with their you? trusted atomic absorption technique (AAS) (1). 10. How much money is available to purchase or More recently, a new and more expensive tech- lease? nique, inductively coupled plasma-mass spec- 11. What is the cost of ownership and running trometry (ICP-MS), has been introduced as a rou- costs for the techniques to fulfill the require tine tool (2). ments? 12. What level of skill operator is available to you? ICP-MS offers initially, albeit at higher cost, the advantages of ICP-OES and the detection limit advantages of graphite furnace-atomic absorp- For many people with an ICP-OES background, tion spectrometry (GF-AAS). Unlike the famous ICP-MS is a plasma with a mass spectrometer as prediction by Fassel, "…that AAS would be dead a detector. Mass spectroscopists would prefer to by year 2000….", low cost flame AAS will describe ICP-MS as mass spectrometry with a always have a future for the small lab with sim- plasma source.
    [Show full text]
  • Two-Dimensional Infrared Spectroscopy of Isotope-Diluted Ice Ih
    http://www.ncbi.nlm.nih.gov/pubmed/21639454. Postprint available at: http://www.zora.uzh.ch Zurich Open Repository and Archive University of Zurich Posted at the Zurich Open Repository and Archive, University of Zurich. Main Library http://www.zora.uzh.ch Winterthurerstr. 190 CH-8057 Zurich www.zora.uzh.ch Originally published at: Perakis, F; Widmer, S; Hamm, P (2011). Two-dimensional infrared spectroscopy of isotope-diluted ice Ih. Journal of Chemical Physics, 134(20):204505. Year: 2011 Two-dimensional infrared spectroscopy of isotope-diluted ice Ih Perakis, F; Widmer, S; Hamm, P http://www.ncbi.nlm.nih.gov/pubmed/21639454. Postprint available at: http://www.zora.uzh.ch Posted at the Zurich Open Repository and Archive, University of Zurich. http://www.zora.uzh.ch Originally published at: Perakis, F; Widmer, S; Hamm, P (2011). Two-dimensional infrared spectroscopy of isotope-diluted ice Ih. Journal of Chemical Physics, 134(20):204505. Two-dimensional infrared spectroscopy of isotope-diluted ice Ih Abstract We present experimental 2D IR spectra of isotope diluted ice Ih (i.e., the OH stretch mode of HOD in D2O and the OD stretch mode of HOD in H2O) at T = 80 K. The main spectral features are the extremely broad 1-2 excited state transition, much broader than the corresponding 0-1 groundstate transition, as well as the presence of quantum beats. We do not observe any inhomogeneous broadening that might be expected due to proton disorder in ice Ih. Complementary, we perform simulations in the framework of the Lippincott-Schroeder model, which qualitatively reproduce the experimental observations.
    [Show full text]
  • A Stable Isotope Dilution Method for a Highly Accurate Analysis of Karrikins
    Hrdlička et al. Plant Methods (2021) 17:37 https://doi.org/10.1186/s13007-021-00738-1 Plant Methods RESEARCH Open Access A stable isotope dilution method for a highly accurate analysis of karrikins Jakub Hrdlička1,2, Tomáš Gucký3, Johannes van Staden4, Ondřej Novák1* and Karel Doležal1,2 Abstract Background: Karrikins (KARs) are recently described group of plant growth regulators with stimulatory efects on seed germination, seedling growth and crop productivity. So far, an analytical method for the simultaneous targeted profling of KARs in plant tissues has not been reported. Results: We present a sensitive method for the determination of two highly biologically active karrikins (KAR 1 and KAR2) in minute amounts of plant material (< 20 mg fresh weight). The developed protocol combines the optimized extraction and efcient single-step sample purifcation with ultra-high performance liquid chromatography-tandem mass spectrometry. Newly synthesized deuterium labelled KAR1 was employed as an internal standard for the valida- tion of KAR quantifcation using a stable isotope dilution method. The application of the matrix-matched calibration series in combination with the internal standard method yields a high level of accuracy and precision in triplicate, on average bias 3.3% and 2.9% RSD, respectively. The applicability of this analytical approach was confrmed by the suc- cessful analysis of karrikins in Arabidopsis seedlings grown on media supplemented with diferent concentrations of KAR1 and KAR2 (0.1, 1.0 and 10.0 µmol/l). Conclusions: Our results demonstrate the usage of methodology for routine analyses and for monitoring KARs in complex biological matrices. The proposed method will lead to better understanding of the roles of KARs in plant growth and development.
    [Show full text]
  • Determination of Selenium in Biological Materials by Stable Isotope Dilution Gas Chromatography-Mass Spectrometry
    University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln U.S. Department of Agriculture: Agricultural Publications from USDA-ARS / UNL Faculty Research Service, Lincoln, Nebraska 1981 Determination of Selenium in Biological Materials by Stable Isotope Dilution Gas Chromatography-Mass Spectrometry Donald C. Reamer Beltsville Human Nutrition Research Center Claude Veillon Beltsville Human Nutrition Research Center Follow this and additional works at: https://digitalcommons.unl.edu/usdaarsfacpub Part of the Agricultural Science Commons Reamer, Donald C. and Veillon, Claude, "Determination of Selenium in Biological Materials by Stable Isotope Dilution Gas Chromatography-Mass Spectrometry" (1981). Publications from USDA-ARS / UNL Faculty. 309. https://digitalcommons.unl.edu/usdaarsfacpub/309 This Article is brought to you for free and open access by the U.S. Department of Agriculture: Agricultural Research Service, Lincoln, Nebraska at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in Publications from USDA-ARS / UNL Faculty by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. 2166 Anal. Chem. 1981, 53, 2166-2169 Table 11. Ionization Range Ri for Electrons pendence on electron energy and the nature of the target gas are in accord with expectations from considerations of stopping He Ne Ar Kr Xe N, aira power, energies required to form an ion pair, and ionization 300 eV cross sections. Ri9,,pg/cmZ n.d. n.d. 1.55 2.74 3.43 1.24 1.63 LITERATURE CITED Ri,,, cm at -- -- 0.61 0.51 0.41 0.69 0.88 (1) Cole, A. Radiat. Res. 1969, 38, 7. 1 torr, (2) Polley, C. W., Jr.; Illies, A.
    [Show full text]
  • Determination of Lithium in Human Serum by Isotope Dilution Atomic Absorption Spectrometry
    Determination of lithium in human serum by isotope dilution atomic absorption spectrometry Alexander Winckelmann1,2, Dalia Morcillo1,2, Silke Richter2, Sebastian Recknagel2, Jens Riedel2, Jochen Vogl2, Ulrich Panne1,2, Carlos Abad2* 1Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, 12489 Berlin, Germany 2Bundesanstalt für Materialforschung und –prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, Germany *E-mail corresponding author: [email protected] Abstract The therapeutic dose of lithium (Li) compounds, which are widely used for the treatment of psychiatric and hematologic disorders, is close to its toxic level; therefore, drug monitoring protocols are mandatory. Herein, we propose a fast, simple, and low-cost analytical procedure for the traceable determination of Li concentration in human serum, based on the monitoring of the Li isotope dilution through the partially resolved isotope shift in its electronic transition around 670.80 nm using a commercially available high-resolution continuum source graphite furnace atomic absorption spectrometer. With this technique, serum samples only require acidic digestion before analysis. The procedure requires three measurements—an enriched 6Li spike, a mixture of a certified standard solution and spike, and a mixture of the sample and spike with a nominal 7Li/6Li ratio of 0.82. Lanthanum has been used as an internal spectral standard for wavelength correction. The spectra are described as the linear superposition of the contributions of the respective isotopes, each consisting of a spin-orbit doublet, which can be expressed as Gaussian components with constant spectral position and width and different relative intensity, reflecting the isotope ratio in the sample. Both, the spectral constants and the correlation between isotope ratio and relative band intensity have been experimentally obtained using commercially available materials enriched with Li isotopes.
    [Show full text]
  • Determination of Creatinine in Human Serum by Isotope Dilution-Mass Spectrometry : Definitive Methods in Clinical Chemistry, IV I \ by L
    L. Siekmann: Determination of creatinine by isotope dilution-mass spectrometry \ 37 J. Clin. Chem. Clin. Biochem. Vol. 23. 1985, pp. 137-144 Determination of Creatinine in Human Serum by Isotope Dilution-Mass Spectrometry : Definitive Methods in Clinical Chemistry, IV i \ By L. Siekmann i Institut für Klinische Biochemie, Universität Bonn jl l (Received September 12/October 29, 1984) Summary: A method for the determination of creatinine in human serum by isotope dilution-mass spectrometry is described. The analytical procedure comprises the following Steps: (1) Addition of [13C,15N2]creatinine to the serum sample; (2) ion exchange chromatography on the cation exchange resin AG 50W-X2; (3) formation of the trimethylsilyl derivative; (4) gas liquid chromatography-mass spectrometry (GC-MS); selected ion monitoring (SIM) at the m/z-values 329 and 332; (5) calculation of the amount of creatinine in the serum sample from the isotope ratio, äs measured by GC- MS. 13 15 [ C, N2]Creatinine was prepared by chemical synthesis. The substance is then used äs internal Standard for the measurement of creatinine in serum samples. The imprecision of the method was in the ränge from 0.35 to 1.05% (coefficient of Variation) äs determined by repetitive measurements of creatinine in 13 different control sera on different pccasions. The lower limit of detection of the mass spectrometer in the selected ion monitoring mode is about 0.5 ng creatinine with a signal to noise ratio of 3: l The accuracy of the method is achieved by the use of the isotope dilution principle in combination with GC- MS.
    [Show full text]
  • Isotope Dilution Spaces in Mice 2841 Regulated at 30±1 ¡C and the Photoperiod Was 16 H:8 H L:D
    The Journal of Experimental Biology 202, 2839–2849 (1999) 2839 Printed in Great Britain © The Company of Biologists Limited 1999 JEB2221 ISOTOPE DILUTION SPACES OF MICE INJECTED SIMULTANEOUSLY WITH DEUTERIUM, TRITIUM AND OXYGEN-18 ELZBIETA KRÓL AND JOHN R. SPEAKMAN* Aberdeen Centre for Energy Regulation and Obesity, Department of Zoology, University of Aberdeen, Aberdeen AB24 2TZ, UK *Author for correspondence (e-mail: [email protected]) Accepted 28 July; published on WWW 30 September 1999 Summary The isotope dilution technique for measuring total body reproductive mice. In addition, the hydrogen tracer water (TBW), and the doubly labelled water (DLW) employed had a significant effect (deuterium spaces were method for measuring energy expenditure, are both 2.0 % larger than tritium spaces). Deuterium and tritium sensitive to small variations in the ratio of the hydrogen to dilution spaces, expressed as a percentage of body mass, oxygen-18 dilution space. Since the dilution space ratio were highly correlated. Dilution space ratios ranged from varies between individuals, there has been much recent 0.952 to 1.146 when using deuterium, and from 0.930 to debate over what causes this variability (i.e. physiological 1.103 when using tritium. Dilution space ratios based on differences between individuals or analytical error in the deuterium and tritium were also highly correlated. isotope determinations), and thus which values (individual Comparison of standard deviations of the dilution space or a population mean dilution space ratio) should be ratio based on deuterium in vivo and in vitro indicated that employed for TBW and DLW calculations. To distinguish only 4.5 % of the variation in the dilution space ratios between physiological and analytical variability, we observed in the mice could be accounted for by analytical injected 15 non-reproductive and 12 lactating mice (Mus variation in the deuterium and oxygen-18 analyses.
    [Show full text]
  • Sk98k0228 Utilization of Atomic Emission Spectroscopy
    P31 SK98K0228 UTILIZATION OF ATOMIC EMISSION SPECTROSCOPY METHODS FOR DETERMINATION OF RARE EARTH ELEMENTS Jana Kubova, Jozefa Polakovicova, Jan Medved', Vladimir Stresko, Geological Institute, Faculty of Natural Sciences, Bratislava The intensive priority of utilization of the rare earth elements (REE) has started since seventy years. The great importance of high purity compounds of REE has found their utilization first of all in electrical industry, nuclear energetics, optics, ceramics, engineering, chemical industry and other. The importance of data on REE for petrogenetic classification of rocks since it provides information on magma differentiation and the metamorphic or other geochemical processes is well recognized [1]. The new analytical techniques and procedures which were developed in eighties for determination of ultra-trace contents of REE have led to their wide popularization not only for many geochemical and petrogenetic investigations but for the environment monitoring as well. Requests for REE determination have therefore become common in most geoanalytical laboratories in spite of the fact that analysis of usual concentration levels is in the least not a simple task. Many years ago only two analytical techniques, namely neutron activation analysis (NAA) and isotope dilution mass spectrometry (EDMS), were available for the determination of REE at chondritic abundance levels in rocks and minerals, but use of these techniques remained confined to a few well-established laboratories, mainly because of the high cost of the equipment. In the seventies, inductively coupled plasma (ICP) spectrometry had a great impact in this field in its optical version and more recently in its ICP-MS form [2-4]. Despite considerable progress in REE determination as witnessed by numerous publications, several problems have still remained and may cause errors if not properly handled.
    [Show full text]
  • Method 6800: Elemental and Molecular Speciated Isotope
    METHOD 6800 ELEMENTAL AND MOLECULAR SPECIATED ISOTOPE DILUTION MASS SPECTROMETRY SW-846 is not intended to be an analytical training manual. Therefore, method procedures are written based on the assumption that they will be performed by analysts who are formally trained in at least the basic principles of chemical analysis and in the use of the subject technology. In addition, SW-846 methods, with the exception of required method use for the analysis of method-defined parameters, are intended to be guidance methods which contain general information on how to perform an analytical procedure or technique which a laboratory can use as a basic starting point for generating its own detailed standard operating procedure (SOP), either for its own general use or for a specific project application. The performance data included in this method are for guidance purposes only, and are not intended to be and must not be used as absolute quality control (QC) acceptance criteria for purposes of laboratory accreditation. 1.0 SCOPE AND APPLICATION For a summary of changes in this version from the previously published draft method 6800, February 2007 Rev 0, please see Appendix A at the end of this document. 1.1 This method consists of two approaches: (1) isotope dilution mass spectrometry (IDMS) for the determination of the total concentrations of elements and molecules and (2) molecular speciated isotope dilution mass spectrometry (SIDMS) for the determination of elemental and molecular species. IUPAC defines speciation analysis as “analyzing chemical compounds that differ in isotopic composition, conformation, oxidation or electronic state, or in the nature of their complexed or covalently bound substituents, which can be regarded as distinct chemical species.” This method is applicable to the determination of total elements as well as elemental species and molecular species at parts per billion (ppb), parts per trillion (ppt) and sub-ppt levels in samples of various types; in waters, solids, blood, foods or in extracts or digests.
    [Show full text]