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RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 89 three investigated sites form rather similar pat- Laboratory for Radiological Protection, confirms terns, though their values differ much in some cases the method reliability. like for Sb, Co, Se, Cr and Zn. Some elements like Sb, W, As, Se and Zn are highly concentrated in References APM when compared with their occurrence in the [1]. Boubel R.W., Fox D.L., Turner B.: Fundamentals of Earth’s crust. This shows their anthropogenic oc- Air Pollution. 3rd edition. Academic Press, London currence in APM. Elements like W and Zn are 1994. mainly associated with the steel industry and may [2]. Seinfeld J.H., Pandis S.N.: Atmospheric Chemistry come from Polish as well as from the neighbouring and Physics: From Air Pollution to Climate Change. countries’ sources. The other ones like Sb, As and John Wiley & Sons, 1997. [3]. Environmental Development. IAEA Bull., 38, 2 (1996). Se are mainly associated with coal combustion and [4]. Air Pollution and Its Trends. UNDP/RCA/IAEA motor vehicle exhausts [1,3-5]. Project RAS/97/030/A/01/18, 1997. This could be explained by the fact that over [5]. IAEA/ANL Interregional Training Course on Nuclear 80% of energy production in Poland come from Related Analytical Techniques in Air Pollution Mo- coal burning and that in the neighbourhood of the nitoring and Research. Lectures. Argonne National Polish big cities, power/heating plants are located. Laboratory, Argonne, USA 1993. It is perhaps worth to conclude that high EFs for [6]. Steinnes E., Rambaek J.P., Hanssen J.E.: Chemo- the same elements has also been observed by the sphere, 25, 735 (1992). authors when analyzing fly ashes coming from [7]. Kuik P., Wolterbeek H.Th.: Water, Air, Soil Pollut., Polish power plants [12]. 84, 323 (1995). [8]. Compendium of Methods for Determination of Inor- The method reliability ganic Compounds in Ambient Air. Center for Envi- A significant analytical problem encountered ronmental Research Information, U.S. Environmental in the analysis of APM collected on filters may arise Protection Agency, June 1999. from a blank, i.e. filter itself [5,15,17]. It may con- [9]. Dybczyński R.: Chem. Anal. (Warsaw), 46, 133 (2001). tain some elements at measurable levels (roughly [10]. Barnett V., Turkman K.F.: Statistics for the Environ- from one tenth up to one third) of the content of ment. Vol.3. Pollution Assessment and Control. John these elements in APM. In this work, it was the Wiley & Sons, 1997. case for Yb, Cs, Sc, Sb, Rb, and As. For Br, the [11]. Hopke P.K., Gladney E.S., Gordon G.E., Zoller W.H., relatively high and changeable content of this ele- Jones A.G.: Atmos. Environ., 10, 1015 (1976). ment in filters has made its quantitative determi- [12]. Szopa Z., Dybczyński R., Kulisa K., Sterliński S.: Chem. Anal. (Warsaw), 39, 497 (1994). nation unreliable. [13]. Bysiek M., Biernacka M., Jagielak J.: Zanieczyszczenie Analyzing two CRMs along with the APM promieniotwórcze przyziemnego powietrza atmosfe- analyses has assessed the method reliability. Un- rycznego w Polsce w 1998 roku. Centralne Labora- fortunately, CRMs of the same or similar matrix torium Ochrony Radiologicznej, Warszawa, 2000, like APM have not been available. Therefore, two Raport CLOR Nr 142, in Polish. others, well known CRMs of geological/environ- [14]. Szopa Z., Dybczyński R., Kulisa K., Bysiek M., Bier- mental origination namely SOIL-5 (International nacka M., Sterliński S.: The use of INAA for the evalu- Atomic Energy Agency – IAEA) and CTA-FFA-1 ation of air pollution at three urban sites in Poland. (Institute of Nuclear Chemistry and Technology – Chem. Anal. (Warsaw), 49 (2004), in print INCT) have been analyzed in course of the present [15]. Szopa Z., Dybczyński R.: Simple PC software for rou- tine analysis of gamma-ray specta. In: INCT Annual work. Generally, the results showed a good or at Report 2000. Institute of Nuclear Chemistry and Tech- least satisfactory agreement between them. Addi- nology, Warszawa 2001, p.70. tionally, the agreement of K results, which have [16]. Heide F., Wlotzka F.: Meteorites, Messengers form been obtained on the one hand using INAA at the Space. Springer-Verlag, Berlin 1995. INCT and on the other hand, using the 40K mea- [17]. Bem H., Gallorini M., Rizzio E., Krzemińska M.: surements within ASS-500 network at the Central Environ. Int., 29, 421 (2003). CENTRAL EUROPEAN CRYSTAL GLASS OF THE FIRST HALF OF THE 18th CENTURY Jerzy Kunicki-Goldfinger, Joachim Kierzek, Piotr Dzierżanowski1/, Aleksandra J. Kasprzak2/ 1/ Faculty of Geology, Warsaw University, Poland 2/ National Museum in Warsaw, Poland Since 1998, a project of investigation into 18th cen- tative chemical analysis of the samples taken from tury central European vessel glass has been under- selected objects. Some preliminary results of the way. Physicochemical analysis has been carried energy dispersive X-ray spectrometry analysis out, as well as stylistic analysis of over 1000 ob- (EDXRF) had been already discussed [2,3]. Here- jects of different provenience. A scheme of the under, some further results in regard to the elec- whole project has been built on three main steps tron probe microanalysis (EPMA) of the selected and had been already discussed in a previous pa- samples will be taken over, and we want to focus per [1]. These steps are historical studies, non-de- on the characteristics of crystal glass which were structive examination of the vessels, and quanti- recognized among the glass manufactured in cer- RADIOCHEMISTRY, STABLE ISOTOPES, 90 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY tain places in central Europe during the first half veloped probably somewhere on the French-Nether- of the 18th century. lands borderlands, chalk glass – credited to Michael In the 17th century, in some centers of northern Müller (1639-1709) in Bohemia, and lead-crystal Europe, new technologies of colourless glass were glass – ascribed traditionally to George Ravenscroft experimented with. It was the consequence of sci- (1618-1681) in England. The first two mentioned ence development of that time, and the migration quickly spread over the continent. But if chalk glass of glassworkers that caused the spread of techno- (later called Bohemian glass, too) became the real- logical innovations. In some glasshouses, new types ly “popular” one; the manufacturing of crystal glass of furnace construction, new kinds of fuel (coal), was characteristic of only a limited number of glass- new raw materials, batches, and so on, appeared. houses that mainly run under royal, ducal or aristo- Many written historical documents may direct our cratic patronage. Michael Vickers writes “No longer attention to certain territories, and information, were kings and princes the arbiters of taste, but revealed in recent years, might lead us to the state- this role was increasingly played by the middle ment that most of the late 17th and early 18th cen- classes of Europe and America. The eighteenth cen- tury luxury colourless glass in almost all of Europe, tury witnessed these important changes” [11]. He including English lead-crystal, could have their tech- writes in relation to the changing role of rock crys- nological roots somewhere on the French and Dutch tal and glass. It also seems true, however, in regard borderland. However, few results of the chemical to the differentiation of crystal glass as a most valu- analyses of these glasses have been known to clearly able metal at this time, and chalk glass as a cheaper support such statement up to now. one; but enough good to fulfil the new baroque The significant changes in the glass technology taste, which expressed itself in frequently dense can be observed already in the earliest 60s in the rich decoration. This decoration occasionally could Netherlands, Netherlands/French borderlands and even be used on metal of imperfect quality. Never- almost immediately on the British islands; in the theless, this simplified history of baroque glass tech- 70s, among other things, also in central Europe nology in northern Europe nowadays seems not [4-6]. Louis le Vasseur d’Ossimont (1629-1689), entirely accurate. Firstly, chalk was already in us- French native, was probably the first and most im- age in western Europe in time of Michael Müller; portant glassworker known to us, who transferred and secondly, lead compounds were used for col- new technology of crystal glass to central Europe. ourless metal in the continent probably indepen- He appeared in Bohemia in Buquoy service in dently of the influence of English technology. Trac- 1673 and established a glasshouse in Nové Hrady ing the succeeding steps of the introduction of the (Gratzen) [7,8]. The lists of raw materials used by new raw materials has, until now, been very puz- him there (which included, among other things, zling. quarz pebbles, saltpeter, arsenic, borax, chalk, wine The terminological context of this crystal glass stone) were characteristic of crystal glass batch. is no less complicated. It is not the intention of the This set of raw materials appeared in Nové Hrady authors to discuss this problem here, but at least at the same time when Johann Kunckel published two of its aspects need be highlighted. The first one crystal glass recipe in “Ars vitraria experimentalis” concerns the differentiation between the original [9]. At present, it is very difficult to state where technological terms and the terms introduced to and when this new batch appeared first in central the professional literature by art historians during Europe. But what is obvious, in the light of docu- the last two centuries. A term Bohemian crystal con- ments as well as of the results of the chemical analy- stitutes one of such examples – whereas crystal glass ses of glasses discussed below, is that these raw was manufactured in Bohemia only in a few glass- materials were characteristic of crystal glass in the houses in the last quarter of the 17th century and last quarter of the 17th century and the 1st half of then probably not before the middle of the 18th the 18th century, as well.