Made available in DSpace on 2014-10-09T12:36:27Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:26Z (GMT). No. of bitstreams: 1 03875.pdf: 1641198 bytes, checksum: aa054234bd30c0adc370774ed47847d3 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

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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

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Rice grows in saturated soil water condition and its requirement for water is highest amongst other cereal crops. In India, the southwest monsoon wind regime brings rainfall that provides a favourable environment for rice cultivation. Thus, there is significant dependency ofrice production on the southwest monsoon rainfall. Being a crop that grows across diverse climatic regions in India ranging from the humid to semi-arid, it offers possibility to explore therelationship between stable isotopic compositions in the grain organic matter with the climaticfactors relevant for its growth. In this thesis, we measured the isotopic compositions of oxygen, hydrogen and carbon of several rice genotypes that were cultivated during the southwest monsoon in diverse climatic regions across the Indian landmass. These isotopic values were then compared with the seasonalaverage values of climate factors such as relative humidity and temperature. Together with thiswe also studied the dependency of the oxygen isotope composition of the grain OM (δ18OOM) onthat of the source water (δ18OSW). Upon removal of δ18OSW effect from δ18OOM, we obtained astrong and significant relationship between the 18O enrichment in grain organic matter (definedas 18OOM) with relative humidity. The gradient recorded was 0.45‰ shift in 18OOM with 1%change in the relative humidity level. This relationship can potentially be used to estimate thepast variations in relative humidity (and by extension, can provide a measure of monsoon rainfallvariations). We further validated this relationship based on experiments carried out in aglasshouse where all the physical factors were well-monitored. Together with this, carbonisotopic composition measured in the rice grain organic matter were used to infer the water useefficiency of rice grown in different climatic settings. The stable isotope approach was furtherimplemented for studying the archaeological rice grains recovered from archaeological sites. Analysis of carbon isotopic composition of archaeological rice grains from seven archaeologicalsites (Balu, Kanmer, Ojiyana, Lahuradewa, JognaKhera, Hulas and Kunal), belonging to theHarappan civilization and other contemporary cultures provided a new suit of data on quantitativeestimate of the hydroclimatic condition (specifically relative humidity) and water availabilityduring the existence of this civilization.

Rice grows in saturated soil water condition and its requirement for water is highest amongst other cereal crops. In India, the southwest monsoon wind regime brings rainfall that provides a favourable environment for rice cultivation. Thus, there is significant dependency ofrice production on the southwest monsoon rainfall. Being a crop that grows across diverse climatic regions in India ranging from the humid to semi-arid, it offers possibility to explore therelationship between stable isotopic compositions in the grain organic matter with the climaticfactors relevant for its growth. In this thesis, we measured the isotopic compositions of oxygen, hydrogen and carbon of several rice genotypes that were cultivated during the southwest monsoon in diverse climatic regions across the Indian landmass. These isotopic values were then compared with the seasonalaverage values of climate factors such as relative humidity and temperature. Together with thiswe also studied the dependency of the oxygen isotope composition of the grain OM (δ18OOM) onthat of the source water (δ18OSW). Upon removal of δ18OSW effect from δ18OOM, we obtained astrong and significant relationship between the 18O enrichment in grain organic matter (definedas 18OOM) with relative humidity. The gradient recorded was 0.45‰ shift in 18OOM with 1%change in the relative humidity level. This relationship can potentially be used to estimate thepast variations in relative humidity (and by extension, can provide a measure of monsoon rainfallvariations). We further validated this relationship based on experiments carried out in aglasshouse where all the physical factors were well-monitored. Together with this, carbonisotopic composition measured in the rice grain organic matter were used to infer the water useefficiency of rice grown in different climatic settings. The stable isotope approach was furtherimplemented for studying the archaeological rice grains recovered from archaeological sites. Analysis of carbon isotopic composition of archaeological rice grains from seven archaeologicalsites (Balu, Kanmer, Ojiyana, Lahuradewa, JognaKhera, Hulas and Kunal), belonging to theHarappan civilization and other contemporary cultures provided a new suit of data on quantitativeestimate of the hydroclimatic condition (specifically relative humidity) and water availabilityduring the existence of this civilization

Rice grows in saturated soil water condition and its requirement for water is highest amongst other cereal crops. In India, the southwest monsoon wind regime brings rainfall that provides a favourable environment for rice cultivation. Thus, there is significant dependency ofrice production on the southwest monsoon rainfall. Being a crop that grows across diverse climatic regions in India ranging from the humid to semi-arid, it offers possibility to explore therelationship between stable isotopic compositions in the grain organic matter with the climaticfactors relevant for its growth. In this thesis, we measured the isotopic compositions of oxygen, hydrogen and carbon of several rice genotypes that were cultivated during the southwest monsoon in diverse climatic regions across the Indian landmass. These isotopic values were then compared with the seasonalaverage values of climate factors such as relative humidity and temperature. Together with thiswe also studied the dependency of the oxygen isotope composition of the grain OM (δ18OOM) onthat of the source water (δ18OSW). Upon removal of δ18OSW effect from δ18OOM, we obtained astrong and significant relationship between the 18O enrichment in grain organic matter (definedas 18OOM) with relative humidity. The gradient recorded was 0.45‰ shift in 18OOM with 1%change in the relative humidity level. This relationship can potentially be used to estimate thepast variations in relative humidity (and by extension, can provide a measure of monsoon rainfallvariations). We further validated this relationship based on experiments carried out in aglasshouse where all the physical factors were well-monitored. Together with this, carbonisotopic composition measured in the rice grain organic matter were used to infer the water useefficiency of rice grown in different climatic settings. The stable isotope approach was furtherimplemented for studying the archaeological rice grains recovered from archaeological sites. Analysis of carbon isotopic composition of archaeological rice grains from seven archaeologicalsites (Balu, Kanmer, Ojiyana, Lahuradewa, JognaKhera, Hulas and Kunal), belonging to theHarappan civilization and other contemporary cultures provided a new suit of data on quantitativeestimate of the hydroclimatic condition (specifically relative humidity) and water availabilityduring the existence of this civilization.

Artifacts made of durable materials, such as stone, can provide valuable clues to reconstruct the past. Marble sourcing, in particular,provides information about contact, trade, and other activities in the greater Mediterranean area. The Worcester Art Museum of Massachusetts (WAM) initiated a provenance study by requesting that an analysis of several marble artifacts occur at the University of South Florida's Archaeological Science Laboratory. The 55 marble samples used in this study are from the Worcester Art Museum's collection of Antioch mosaics. Positive results might reveal: 1) preferred sources of tesserae, 2) information about trade of specialized stone, 3) changes in preferred sources during different chronological periods, and 4) workshop preferences. The requested analysis had two objectives. First, once the provenance of the materials is determined, then the results could reveal meaning behind the images contained within the mosaic floor. Second, the results could reveal new trade routes in the Mediterranean. The first step in this analysis was X-ray diffraction (XRD),which differentiates dolomite and calcite marbles. The second step used stable isotope ratio analysis (SIRA), which measures carbon-13 and oxygen-18 isotopic ratios. These two steps have helped to identify Mediterranean marble sources in previous studies. Most of the ancient Mediterranean marble sources have been identified. They have different isotopic values and other characteristics that allow for differentiation. Only one source of dolomite marble exists, which is located in the eastern Mediterranean. It has been identified through XRD in previous studies. Many of the calcite marble sources have different carbon and oxygen isotopic values, which were provided from the SIRA. Those marble artifacts with overlapping carbon and oxygen values can be further analyzed using archaeological, historical, and other information and by using other scientific techniques including cathodoluminescence, electron paramagnetic resonance, and strontium isotope analysis. This thesis discusses the methods used to prepare the samples and analysis conduction; it also discusses the results of the analyses, and presents interpretations regarding the provenance and trade of the marble used for mosaics at Antioch. The results of the SIRA and XRD analysis showed that the materials used for mosaic tesserae come from a variety of sources. Although no definitive matches were found, the results provide the basis for the collection of a colored marble database of sources and artifacts.

Early research into the stable hydrogen isotopic compositions (δD) of petroleum involved bulk deuterium/hydrogen (D/H) measurements which, while providing some useful information, had to contend with the analysis of complex mixtures of hydrocarbons, and alteration resulting from the rapid exchange of nitrogen-, oxygen- and sulphur-bound hydrogen. The use of gas chromatography-isotope ratio mass spectrometry (GC-irMS) overcomes these problems by allowing the analysis of individual compounds containing only the most isotopically conservative aliphatic carbon-bound (C-bound) hydrogen. This project investigates the geochemical utility and reliability of compound-specific δD values, with the aim to better understand and exploit this analytical capability. To demonstrate the source diagnostic potential of compound-specific δD values, normal and branched alkanes extracted from series of immature bog-head coals (torbanites) were analysed. The torbanites contain immature organic matter predominantly from a single, freshwater algal source, i.e. Botryococcus braunii (B. braunii). The δD values of n-alkanes reflect the climate regime at the time of deposition of the torbanites, and vary mainly in response to the δD values of the source meteoric waters in their depositional environments. n-Alkanes from torbanites deposited at high latitude in a glacial climate are depleted in D by up to 70% relative to those from a torbanite deposited at low latitude under a tropical climate regime. Torbanites deposited in a mid-latitude region under cool-temperate conditions contain n-alkanes with δD values falling in between those of n-alkanes from tropical and glacial torbanites. / The δD values of the n-alkanes also reflect their multiple source inputs. For example, a saw-toothed profile of n-alkane δD values in Australian torbanites is attributed to a dual-source system: a predominant B. braunii input, with a minor terrestrial plant input to odd-carbon-numbered n-alkanes in the range n-C20 [subscript] to n-C29 [subscript]. The δD values of n-alkanes and isoprenoids (pristane and phytane) differ significantly in two Permian torbanites from Australia, thought to be reflective of the offset between the δD values of their precursors in extant organisms. The torbanite data indicate that a biological δD signal has been preserved for at least 260–280 million years, extending the utility of δD values for palaeoclimate studies. To elucidate the effect of sedimentary processes on the δD values of petroleum hydrocarbons, three sedimentary sequences have been studied. These comprise one from the Perth Basin (Western Australia) and two from the Vulcan Sub-basin (northern Australia) covering a wide range of maturities, i.e. 0.53–1.6% vitrinite reflectance (Ro). The δD values of n-alkanes extracted from immature-early mature sediments (marine shales/siltstones and mudstones) are consistent with that expected of marine-derived n-alkyl lipids. The hydrocarbons become enriched in D with increasing maturity. The large (ca. 115%) biologically-derived offset between the δD values of n-alkanes and acyclic isoprenoids from immature sediments gradually decreases with increasing maturity, as the isoprenoids become enriched in D more rapidly than the n-alkanes. The D-enrichment in isoprenoids correlates strongly with Ro and traditional molecular maturity parameters. / This suggests that H/D exchange during maturation occurs via a mechanism involving carbocation-like intermediates, which proceeds more rapidly with compounds containing tertiary carbon centres. Significant epimerisation of pristane and phytane coincides with their D-enrichment, suggesting that hydrogen exchange occurs at their tertiary carbons. A mechanism is proposed which can account for both H/D exchange and the epimerisation of pristane and phytane in the sedimentary environment. Pristane and phytane extracted from a post-mature sediment from the Paqualin-1 sequence are significantly enriched in D (ca. 40%) relative to the n-alkanes, indicating that D-enrichment persists at very high maturity, and is more pronounced for the regular isoprenoids than the n-alkanes. This supports the notion that H/D exchange causes the observed shift in δD values, rather than free-radical hydrogen transfer. The differences between the δD values of pristane and phytane show opposite trends in the Perth Basin and Vulcan Sub-basin sediments. In the Perth Basin, phytane is enriched in D relative to pristane, likely due to a dominant algal source. In the Vulcan Sub-basin, pristane is enriched in D relative to phytane, and thus is attributed to a lower relative input of algal organic matter. The variance of the δD values of pristane and phytane is generally consistent throughout the maturity range and provides evidence that pristane and phytane exchange hydrogen at similar rates. δD analysis of crude oils and condensates reservoired in the Perth Basin and Vulcan Sub-basin has been carried out to evaluate potential applications in oil-source correlation. / The n-alkanes from crude oils and condensates are often more enriched in D than n-alkanes extracted from their supposed source rocks, and the oils also show relatively small differences between the δD values of n-alkanes and isoprenoids. These results suggest significant H/D exchange has occurred, implying that the liquids were generated from mature source rocks. A Perth Basin crude oil (Gage Roads-1) thought to be derived from a lacustrine/terrestrial source contains hydrocarbons that are significantly depleted in D relative to Perth Basin oils derived from a marine source, attributed to variability in the isotopic composition of marine and terrestrial source waters. δD values of n-alkanes from Vulcan Sub-basin crude oils and condensates are largely consistent with their prior classification into two groups: Group A, having a marine source affinity; and Group B, having a terrigenous source affinity. Some oils and condensates are suggested to be mixtures of Group A and Group B hydrocarbons, or Group A hydrocarbons and other as yet unknown sources. An exception is a former Group A oil (Tenacious-1) containing n-alkanes that are enriched in D relative to those from other Group A oils and condensates, attributed to mixing with another source of more mature hydrocarbons. The n-alkane δD profile appears to be indicative of source and sedimentary processes. One Perth Basin crude oil (Dongara-14) contains lower-molecular-weight n-alkanes that are depleted in D relative to higher-molecular-weight n-alkanes, attributed to a mixed marine/terrestrial source. / Group A crude oils and condensates from the Vulcan Sub-basin display a ‘bowl-shaped’ profile of n-alkane δD values. An upward inflection in the n-alkane δD profile from n-C11 [subscript] to n-C15 [subscript] is suggested to represent the addition of D-enriched lower-molecular-weight n-alkanes from a more mature wet gas/condensate to an initial charge of lower maturity oil. Ultimately, this project has demonstrated that the δD values of individual petroleum hydrocarbons can be used to elucidate the nature of source organic matter and depositional environments. The preservation potential of lipid δD values is greater than previously thought, although it is clear that H/D exchange accompanying maturation can have a significant effect on the δD values of certain hydrocarbons. Thus, great care must be taken when interpreting δD values of individual hydrocarbons, particularly those derived from sediments of high thermal maturity.