Twenty-one galena specimens from 16 mineral deposits in the Kootenay district analysed isotopically in replicate have a linear relationship of isotopic compositions on a Pb²º⁶/Pb²º⁴ versus Pb²º⁷/Pb²º⁴ graph. Twelve of the galenas, including two from Sullivan mine (East Kootenay district), were analysed by an intercomparison technique; the first application of the intercomparison method to an anomalous lead suite. Intercomparison results verify the linear compositional pattern (slope = 0.1084 ± 0.0033). These results indicate that: 1. Kootenay arc leads are multi-stage leads. 2. Sullivan-type lead is the parent common lead from which the anomalous suite developed. 3. Kootenay arc mineral deposits formed during one major mineralizing episode. Time of anomalous lead mineralization, tm, is probably Jurassic as deduced from potassium-argon dates and crosscutting relations of ores and igneous rocks. Assuming tm = 180 m.y. time of emplacement of uranium and thorium that produced the radiogenic component of the anomalous leads is approximately 1700 m.y., possibly the age of Lower Purcell strata of the East Kootenay district. Lead isotopic compositions show no obvious correlations with age of wallrock, type of wallrock, geological nature of ore deposits, or minor element content of galena. Post-ore thermal metamorphism and hydrothermal alteration do not appear to have changed lead isotopic compositions. The history of evolution of Kootenay arc anomalous leads is interpreted as follows: 1. Formation of source rocks containing uranium and thorium about 1700 m.y. ago. 2. Introduction of Sullivan-type lead into source rocks about 1340 m.y. ago. 3. Mixing of Sullivan-type lead with radiogenic lead formed by decay of uranium and thorium, and transportation and deposition of these "lead mixtures” to form anomalous lead deposits during Coast Range orogeny. Geologic and isotopic data from Sullivan mine are reconciled most easily with an epigenetic origin of the Sullivan orebody, and probably with a genetic relation of Sullivan ore fluids with the source magma of Moyie Intrusions. Holmes-Houtermans model age for Sullivan ore, based on intercomparison data, is 1340 m.y. Sullivan lead evolved in a source with U²³⁸/Pb²º⁴ = 9.02, Th²³²/Pb²º⁴ = 36.71, and Th/U = 4.07 (in terms of present day abundances). A method of estimating volume of source rock of anomalous lead deposits is outlined. Calculations for Jersey, Reeves Macdonald and Bluebell mines indicate that the radiogenic lead component of these deposits could have been derived from 1 to 10 cubic kilometers of source rock containing 3 ppm uranium (and approximately 12 ppm Th) if only one-third to one-half of the radiogenic lead in the source were extracted during a period of concentration and mineralization. Kootenay arc deposits can be divided into two classes on the basis of minor element contents of galenas. This division closely corresponds to the following geological types of deposits: 1. replacement deposits with no evidence of open space filling, and 2. deposits with evidence of open space filling and variable amounts of wallrock replacement. Minor element contents of galenas from Salmo-type replacement deposits suggest but do not prove a fairly low temperature of mineral deposition. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

No description available.

Submitted by HENDRYK GEMEINER null (h.gemeiner@gmx.net) on 2016-11-11T17:05:34Z No. of bitstreams: 1 tese_mestrado_hendryk_gemeiner.pdf: 13978829 bytes, checksum: 08b385f98431fd9c29309e3aeb7cb1b2 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-11-11T17:52:30Z (GMT) No. of bitstreams: 1 gemeiner_h_me_rcla.pdf: 13978829 bytes, checksum: 08b385f98431fd9c29309e3aeb7cb1b2 (MD5) / Made available in DSpace on 2016-11-11T17:52:30Z (GMT). No. of bitstreams: 1 gemeiner_h_me_rcla.pdf: 13978829 bytes, checksum: 08b385f98431fd9c29309e3aeb7cb1b2 (MD5) Previous issue date: 2016-09-13 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação para o Desenvolvimento da UNESP (FUNDUNESP) / The toxic metal lead (Pb) can be harmful to human health in various manners, but is also considered as a distinguished tracer of environmental pollution, since the relative abundance of its four stable isotopes with the atomic masses of 204, 206, 207 and 208 varies with the emission source. This study is focused on the lead concentrations and isotope ratios in the particulate matter of the Brazilian cities of Goiânia (GO) and Rio Claro (SP), in order to determine the main Pb pollution sources. Particulate matter samples were collected on clean Teflon filters during the rainy and dry season between 2014 and 2016 on the campus of the State University of São Paulo (UNESP) in Rio Claro city and in the centre of Goiânia city near main roads with a high traffic volume. The Pb concentrations as well as the 206Pb/207Pb and 208Pb/207Pb stable isotope ratios of the particulate matter samples were analysed by Inductively-Coupled Plasma Mass Spectrometry. To apply this analytical technique successfully, it was necessary to optimize parameters in case of acquisition time, detector dead time and mass discrimination, which affect the measurement accuracy and precision. Results showed that lead concentrations in Goiânia were different between rainy and dry season. In Goiânia, Pb concentrations showed higher values in dry season than in rainy season, while Pb concentrations were more similar in both sampling periods in Rio Claro. Back trajectories were analysed with the HYSPLIT model to investigate associations between Pb concentration levels and the direction of incoming air masses. However, the comparison of the obtained 206Pb/207Pb and 208Pb/207Pb isotope ratios data with data of potential Pb sources from previous studies indicated that gasoline may be considered as main Pb sources in the particulate matter of Goiânia and Rio Claro. Pb isotope ratios in Goiania were slightly different between dry and rainy season, while in Rio Claro, 206Pb/207Pb isotope ratios showed markedly higher values in dry season than in rainy season. Hence, Pb in Rio Claro in dry season also seems to be influenced by industrial emissions. These assumptions were supported by the calculation of 208Pb/206Pb-207Pb/206Pb diagrams and the contribution factor of Pb coming from gasoline by applying binary mixing equations. / CNPq: 372125/2014-0 / FUNDUNESP: 0050.0092854.14.9

Applications of lead and strontium isotope analysis were made on archaeological materials from three different contexts in both the Old and New Worlds. These materials comprised pre-Hispanic glaze painted ceramics from Arizona, U.S.A., glass beads from late first millennium AD Igbo-Ukwu, Nigeria, and copper-based metals from early first millennium AD Kissi, Burkina Faso. All materials contain lead at major, minor, or trace concentrations, and lead isotope analysis was employed to determine a provenance for that lead. Strontium isotope analysis also was applied to glass beads from Igbo-Ukwu to determine provenance(s) for strontium found in the glass. Furthermore, application of elemental composition analysis was or had been employed on all samples for additional data comparisons within assemblages and with comparable archaeological materials.Results of these analyses determined, in most cases, regional provenance with high degrees of confidence for lead contained in the analyzed samples. Strontium and elemental composition analysis data also proved valuable in confirming the regional provenance of the raw glass used to produce the glass beads. Leads in the glaze paints from Arizona, which demonstrated a range of resources exploitation, were confidently restricted to a few regions for their procurement. Likewise leads in most glass beads from Igbo-Ukwu were confidently restricted to two main source regions, with a third strong contender also being identified. The elemental composition and strontium isotope data determined with confidence the production regions for the primary raw glasses used to make the glass beads. Finally, leads in copper-based metals from Burkina Faso also were restricted to a few regions, although some inconclusiveness in provenance determination was attributed to mixing of metals from difference sources.These results confirm the utility of heavy isotope analysis of archaeological materials for provenance determination. The combination of these data with elemental composition analyses further confirm the interpretive strength of combining independent but related sets of analytical data for exploring questions of archaeological provenance. With improvements in instrument technology and application in the past two decades, very high precision and high accuracy analyses can be made which eliminate some earlier concerns of heavy isotope applications in archaeology.

The paper examines lead isotope and trace element analysis in the context of a battlefield and their role in determining the course of the battle and categorizing the bullets within and to each participating side. It uses a theoretical framework with papers from both the archaeological and the forensic field. It concludes that trace element analysis has its criticism, especially from the forensic field, but can act as a complement to lead isotope analysis as it can give different answers from other parts of the bullet’s life cycle and should have a place in archaeology. The focus is on lead isotopes but concludes ICP-MS as a tool for examining bullets and other ammunition from archaeological battlefields is preferable. This is because of ICP-MS’s capability to analyse both lead isotope and trace elements. The paper also studies the ethical problems of using these methods and the answers they may give as a vessel for a discussion about what actions we are measuring with these methods.

This dissertation seeks to establish the possible provenance of copper and copper alloys used at Great Zimbabwe (1000-1700CE) to infer local and regional circulation circuits. It employs archaeological, archival, and geochemical methods to characterize samples of 26 wound wire bracelets, bangles, anklets, necklaces, and other forms of expressive and decorative wear excavated from the southern terrace, (Hill Complex) at Great Zimbabwe. The samples were macroscopically, microscopically, chemically and isotopically characterized to understand the technique of manufacture, chemical composition, lead isotopic ratios and the starting composition of uranium and thorium in relation the model ages. The Pb isotopic data calculated 238U/204Pb (μ), 232Th/ 238U(κ) ratios and estimated model ages (T) were compared with published lead isotopic ratios from various ore samples from central and southern Africa. Within opportunities afforded by the historical record and limitations imposed by small sample sizes especially of the comparative geology, indications are that the studied objects were produced using ores matching the Cu-Ni mineralization at Empress Mine (in Zimbabwe), Cu Ag and Cu Pb Zn Ag mineralization associated with the Kundelungu Plateau (bordering Zambia and Democratic Republic of Congo). This suggests that Great Zimbabwe participated directly and indirectly in the vibrant micro, regional and interregional circulation of copper and other resources. Future work, must however, add more trace element data from the objects and increase the number of samples from ancient mines and other sites to develop a fuller picture of the movement of copper in Iron Age southern Africa through space and time.

Metal played important role in the social and economic development of societies since its discovery. It is so important that the some part of humankind historical development were designated by the type of metal which was extensively used depending upon the level of technology of that period enabling the processing of metal like bronze age and iron age. In this frame, the rich metal deposits of Anatolia made this region a very important metal working and civilization center. K&uuml / ltepe where it was the center of the trade organization in Anatolia realized between Assur and Anatolia during 1945-1730 B.C called Assyrian Trade Colonies Period was one of the most important metal working center of Anatolia at that period. In this thesis, it is aimed to make a contribution to understand the metal working technology in K&uuml / ltepe by examining the uncovered metal artifacts dated to that period. For this purpose, the metal artifacts uncovered from K&uuml / ltepe Ancient Site belonging to Colonies Period which are exhibited in the Anatolian Civilization Museum were examined by portable XRF (PXRF) to obtain the quantity of elements that constituted the artifacts without giving any harm to the artifact. Besides the examination of exhibited artifacts in the Anatolian Civilization Museum, the uncovered metal artifact parts belonging to Colonies Period which are not suitable for exhibition and separated for studying were examined by energy dispersive X-ray unit of scanning electron microscope for elemental analysis and by X-ray diffraction for the analysis of minerals. The microstructures of artifacts were examined by scanning electron microscope and optical microscope for revealing the operations on metal applied by ancient metalsmith. In addition to analysis mentioned above, in order to make a contribution to understand the copper trade between K&uuml / ltepe and its environs lead isotope analysis of some samples from the separated metal artifacts for studying was also performed. As a result of all those analyses, it was concluded that K&uuml / ltepe ancient metalsmiths in Colonies Period had the knowledge to smelt the copper and to pour molten metal into a mold to produce an object of desired shape. Moreover, they also discovered that the addition of some elements to copper hardens the structure. In this frame the bronze to be obtained by deliberately adding of tin to copper was attained. In addition, they were aware of shaping the casted object by hammering. In the meantime, they had the knowledge of heat treatment that allows them forging the object many times till giving the desired shape without causing the fracture in the structure.

Submitted by (lucia.rodrigues@ufrpe.br) on 2016-08-17T12:29:29Z No. of bitstreams: 1 Nielson Machado dos Santos.pdf: 2159134 bytes, checksum: 0924bbce3bea148e3c14b840a9443026 (MD5) / Made available in DSpace on 2016-08-17T12:29:29Z (GMT). No. of bitstreams: 1 Nielson Machado dos Santos.pdf: 2159134 bytes, checksum: 0924bbce3bea148e3c14b840a9443026 (MD5) Previous issue date: 2015-07-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This work was carried out to investigate the possible influence of human activities on heavy metal concentrations, by enrichment factor and isotopic signature of Pb and determine the natural levels of heavy metals in the vicinity Todos os Santos Bay-BA (BTS). For this, two sampling design of the soil around the BTS were realized. The first sampling 114 topsoil samples (0.0 - 0.2 m depth) were collected from 38 samplings sites and the concentrations of Pb, Zn, As, Cd, and Hg were determined by ICP-OES or AA-FIAS after microwave sample digestion. Results showed that mean values for heavy metal concentrations in soils (mg kg-1) followed the order Pb (39.45) > Zn (12.52) > As (1.95) > Cd (0.23) > Hg (0.09). The mean natural concentrations of heavy metals found in the soils of an important economic region of Brazil’s were generally lower than those reported in the national and international literature, with exception Pb concentration that was higher than all compared soils.The quality reference values (QRvs) calculated for the TSB based on the 75th percentile, were as follows (mg kg−1): Pb (54.37); Cr (36.55); Zn (10.40); Cu (7.10); Ni (4.05); Co (0.38); Cd (0.30). The second sampling six soil profiles were collected, the samples were collected from different horizons, totaling 44 samples. Soil pits were dug until 2 m or until the parent material (C horizon) was reached.The soil samples were microwave digested in the mixture of HNO3, H2O2 using the method described by Sah and Miller (1992). Concentrations of Pb and the isotopes 204Pb, 206Pb, 207Pb and 208Pb were measured on an inductively coupled plasma (quadrupole) mass spectrometry. Pb concentrations varied from 3.2 to 44.1 mg kg−1 with an average concentration of 13.65 mg kg−1. In general the samples feature a wide range of Pb isotope ratios, ranging from 36.71 to 47.38 for 208Pb/204Pb, 16.86 to 20.59 for 206Pb/204Pb, 1.10 to 1.31 for 206Pb/207Pb and a ranged slightly from 15.00 to 15.65 for 207Pb/204Pb. The PCA performed identified that Pb, Zn, and Cd were associated with the same factor (F1) and had chiefly anthropogenic origin whereas Pb and Zn have also contributions from both sources (natural, lithogenic and anthropogenic). The As and Hg concentrations (F2) were related to the natural component; the parent material underlying the soils (igneous-metamorphic rocks) seemingly confirm this hypothesis. The natural concentrations of heavy metals in soils of TSB had the following decreasing order: Pb > Cr > Zn > Cu > Ni > Co > Cd. Pb concentration in all soil profiles not seem have been influenced by the abandoned lead smelter plant located in the municipality of Santo Amaro da Purificação-BA. The distinct Pb isotopic compositions were clearly related to the different exposure of the sampling sites in relation to atmospheric deposition and geological parent material. / Este trabalho foi realizado para investigar a possível influência das atividades humanas sobre as concentrações de metais pesados, por fator de enriquecimento e assinatura isotópica de Pb e determinar os níveis naturais de metais pesados ​​nas imediações Todos os Santos Bay-BA (BTS). Para isso, duas projecto de amostragem do solo ao redor da BTS foram realizados. A primeira amostragem de 114 amostras de solo superficial (0,0-0,2 m de profundidade) foram coletadas de 38 amostragens sites e as concentrações de Pb, Zn, As, Cd, Hg e foram determinados por ICP-OES ou AA-FIAS após digestão de amostras de microondas. Os resultados mostraram que os valores médios para as concentrações de metais pesados ​​em solos (mg kg-1) seguido a ordem Pb (39,45)> Zn (12,52)> Como (1,95)> Cd (0,23)> Hg (0,09). As concentrações médias naturais de metais pesados ​​encontrados nos solos de uma importante região econômica do Brasil de foram em geral menores que os relatados na literatura nacional e internacional, com exceção Pb concentração que era maior do que todos em comparação soils.The valores de referência de qualidade (QRvs) calculada para TSB a partir do percentil 75, foram as seguintes (mg kg-1): Pb (54,37); Cr (36,55); Zn (10,40); Cu (7,10); Ni (4,05); Co (0,38); Cd (0,30). A segunda amostragem seis perfis de solo foram coletadas, as amostras foram coletadas de horizontes diferentes, totalizando 44 amostras. Poços de solo foram escavadas até 2 m ou até que o material de origem (C horizonte) foi amostras de solo foram reached.The microondas digerido na mistura de HNO3, H2O2, utilizando o método descrito por Sah e Miller (1992). As concentrações de Pb e os isótopos 204Pb, 206Pb, 207Pb e 208Pb foram medidos em uma espectrometria de massa com plasma indutivamente acoplado (quadrupolo). Concentrações de Pb variou de 3.2 para 44,1 mg kg-1 com uma concentração média de 13,65 mg kg-1. Em geral, as amostras apresentam uma vasta gama de relações isotópicas Pb, variando 36,71-47,38 para 208Pb / 204Pb, 16,86-20,59 para 206Pb / 204Pb, 1,10-1,31 para 206Pb / 207Pb e uma variou ligeiramente 15,00-15,65 para 207Pb / 204Pb . O PCA realizada identificou que Pb, Zn e Cd foram associados com o mesmo fator (F1) e teve origem principalmente antropogénica Considerando Pb e Zn também tem contribuições de ambas as fontes (naturais, litogênicos e antropogênicos). As concentrações de Hg e Como (F2) estavam relacionados com a componente natural; o material de origem subjacentes aos solos (ígnea-rochas metamórficas) aparentemente confirmar esta hipótese. As concentrações naturais de metais pesados ​​em solos de TSB teve a seguinte ordem decrescente: Pb> Cr> Zn> Cu> Ni> Co> Cd. Concentração de Pb em todos os perfis de solo não parecem ter sido influenciados pela planta fundição de chumbo abandonada localizada no município de Santo Amaro da Purificação-BA. As composições isotópicas de Pb distintas foram claramente relacionadas com a diferente exposição dos pontos de amostragem em relação à deposição atmosférica e material de origem geológica.

The aim of this thesis was to define and evaluate the load of sediments by exposure of mercury and lead on the upper flow of the Vltava river and in the Lipno lake. To evaluate possible influence of the glass factory in Lenora for pollution of this area by toxic metals mentioned above. The literature survey refers about problems of mercury and lead content in fresh water and reservoirs sediments, the structure of toxic heavy metals and risks of their release in the enviroment, then in chemical composition of water reservoirs. It also engages in glass manufacturing problems in the glass factory in Lenora, especially the raw materials, which where obviously used for its manufacture. Experimental part describes profile of sampling points, working methods, used chemicals and results of individual analyses. Sediments of the Lipno reservoir and the upper flow of the Vltava river aren{\crq}t seriously loaded with mercury or lead, but in the sediments below Lenora was shown multiple increase of lead and mercury content in comparison with the background. Forest soils has higher mercury content in all localities in comparison with the sediments. On the contrary, the content of EDTA-extractable lead in soils is lower. Detected isotopic ratio of lead 206/207 and 208/206 in sediments of the Vltava river below the glass factory in Lenora have different signature in comparison with the signature of sediments from the Vltava river above the glass factory. On the contrary the signature of lead in all sediments of the Lipno reservoir showed values relevant to natural background of this locality. The structure which corresponds to the lead from the glass factory was also surprisingly detected in humic horizont of the forest soils in Lenora{\crq}s surroundings. The thesis was extended with fish samples from Lipno reservoir and their liver{\crq}s load by lead and mercury content. There were determined isotop ratio (signature) of lead in the fish, the izotop ratio of lead not corresponds to the lead signature from the glass factory in Lenora.

La investigació que es presenta en aquesta tesi es centra en l'aplicació i millora de metodologies analítiques existents i el desenvolupament de nous procediments que poden ser utilitzats per a l'estudi dels efectes ambientals de la dispersió dels metalls entorn a les zones mineres abandonades.En primer lloc, es van aplicar diferents procediments d'extracció simple i seqüencial per a estudiar la mobilitat, perillositat i bio-disponibilitat dels metalls continguts en residus miners de característiques diferents. Per altra banda, per a estudiar les fonts potencials de Pb en la vegetació de les zones mineres d'estudi, una metodologia basada en la utilització de les relacions isotòpiques de Pb determinades mitjançant ICP-MS va ser avaluada. Finalment, tenint en compte l'elevat nombre de mostres analitzades per a avaluar l'impacte de les activitats mineres, es va considerar apropiat el desenvolupament de mètodes analítics d'elevada productivitat. En aquest sentit la implementació d'estratègies quantitatives així com l'aplicació de les millores instrumentals en els equips de XRF han estat avaluades per a aconseguir resultats analítics fiables en l'anàlisi de plantes. A més, alguns paràmetres de qualitat com la precisió, l'exactitud i els límits de detecció han estat curosament determinats en les diverses configuracions de espectròmetres de XRF utilitzats en el decurs d'aquest treball (EDXRF, WDXRF i EDPXRF) per a establir la capacitat de la tècnica de XRF com a tècnica alternativa a les clàssiques comunament aplicades en la determinació d'elements en mostres vegetals. / The research presented in this thesis is based on the application and improvement of analytical existing methodologies and the development of novel procedures that can be used to assess the environmental effects on metal dispersal around abandoned mining activities. On the one hand, single and sequential extraction procedures were properly applied in order to study the potential mobility, risk and bioavailability of the metals contained in several mining wastes of different features. On the other hand, in an attempt to study the potential sources of the anomalous lead content in vegetation specimens growing on the waste and soils of abandoned mining areas, a methodology based on the use of stable lead isotope ratios using ICP-MS instrumentation was evaluated.Finally, in view of the considerable number of vegetation specimen analysis necessary to assess the impact of mining activities, the study of high productivity analytical methods for metal determination in this kind of matrices was considered appropriate. In this sense, the implementation of suitable quantitative strategies and the recent improvements in the XRF instrumentation have been evaluated to achieve reliable analytical results for plant analysis. Besides, analytical figures of merit such as precision, accuracy and limits of detection have been carefully determined in the diverse configurations of XRF spectrometers employed in the course of this work (EDXRF, WDXRF, EDPXRF) using different excitation sources in order to assess the capability of XRF as an alternative analytical tool to classical destructive methodologies, commonly applied for the determination of elements in vegetation matrices.