This thesis describes a study in petroleum geochemistry and specifically of the application of Land-plant derived hydrocarbons to elucidating source matter type, depositional environment and thermal maturity of crude oils. Large volumes of petroleum have been generated from land-plant organic matter in many parts of the world, but especially in the Tertiary deltaic provinces of the USA, Canada, Africa, Southeast Asia, Australia and New Zealand. Compared to oils from other regions, these oils have a relatively complex pattern of biomarkers or molecular fossils, a feature reflecting the diversity of deltaic depositional environments and the advanced state of plant evolution during late Mesozoic and Tertiary time. The molecular and carbon isotopic composition of these oils is useful in identifying the character of their source beds and also in understanding the conditions that give rise to oil-prone sediments generally.Despite their widespread occurrence in oils and sediments, land-plant biomarkers have been used less frequently than compounds of algal origin as markers for source, depositional environment and thermal maturity. The present work sets out to extend the range of land-plant biomarker and isotope tools available to the petroleum geochemist and to provide a firmer foundation for some of the existing tools. A systematic study of the biomarker and n-alkane carbon-isotope composition of a set of late Mesozoic/Tertiary-age oils was carried out as a preamble to more focussed investigations. A comparison of the biomarker and n-alkane isotope data showed that parameters such as the oleanane/hopane ratio overestimate the higher plant contribution to marine deltaic oils. The abundance of bicadinane isomers was found to be much more variable than that of the oleananes, probably because of their close association with the highly resinous, dipterocarp hardwoods of ++ / Southeast Asia. However, small amounts of bicadinanes were found in an oil from outside the paleogeographic range of the dipterocarp family, indicating a more general source. Retention indices based on the regular hopane series were calculated for the main bicadinane and methyl bicadinane isomers and for a group of oleanoid triterpanes.Source rock depositional setting proved to be the primary control on the shape of the n-alkane isotope profile, with negatively sloping curves being characteristic of fluvio-deltaic and marginal lacustrine oils and flat or positively sloping curves typical of marine oils. The difference is probably related to the bacterial reworking of higher plant matter in the fluvio-deltaic environment. A slight isotopic anomaly at n-C(subscript)17 correlates with the abundance of algal-derived steranes and may indicate a minor marine contribution to the source of an fluvio-deltaic oil. A study of sediments from the South Sumatra Basin and New Zealand showed that the n-alkane isotope profile is determined mainly by source matter type and is little influenced by thermal maturity or depositional environment.Based on the results of the work described above, three aspects were chosen for further examination. These were: a) the factors controlling the carbon isotopic composition of n-alkanes and of resin-derived compounds in terrigenous oils; b) the influence of source, maturity and biodegradation on the abundance of bicadinanes, especially the effect of maturity on the isomer distribution, and c) the factors controlling the abundance of oleananes and rearranged oleananes in oils and Ancient sediments, especially the role of depositional environment.A preliminary study using sediments, from the Visayan Basin (Philippines) showed the bicadinane isomeric distribution to be sensitive to maturity. This suggested new maturity parameters which would be ++ / resistant to even severe biodegradation and largely immune to interference from diagenetic effects. A more detailed study of a marine-fluvio-deltaic depositional sequence from the South Sumatra Basin confirmed that the maturity indices based on bicadinanes and aromatic analogs were less subject to non-maturity influences than those based on the steranes and aromatic hydrocarbons. The values obtained for the bicadinane indices were compared with the maturity required for oil generation as estimated by kinetic modelling and with conventional maturity indicators such as sterane epimerisation and the methyl phenanthrene index. Values for several of the indices were also measured for 17 Tertiary-age oils from Southeast Asia, Papua New Guinea, New Zealand and Australia. The main bicadinane maturity indicator (BMI-1) continues to change into the oil window and hence is useful in ranking the relative maturity of oils as well as sediments. Values of BMI-1 for two oils having unusually low sterane maturities were found to be normal and, in the light of this observation, the conventional explanation for low sterane epimerisation of many Tertiary-age oils was critically evaluated.The oleananes, as markers for the angiosperms, provide valuable source and age information when present in an oil. Nevertheless, their abundance is not quantitatively related to the land plant input and indeed their presence results from a small "leak" in diagenetic processes leading primarily to aromatic oleanoids. Evidence is presented that contact of plant matter with seawater during early diagenesis enhances the expression of oleananes in a mature sediment or oil. Oleananes are absent or present at very low concentrations in samples from the base of an Eocene coal seam affected by post-depositional seawater intrusion. However, their abundance increases toward the top of the seam in correlation with ++ / % organic sulphur, dibenzothiophene/phenanthrene and the homohopane index. Similarly, in deltaic sediments from the South Sumatra Basin, oleanane/hopane is strongly correlated with indicators of marine influence such as C[subscript 27]/C[subscript 29] steranes and of oxic/anoxic conditions such as the homohopane index. In each case, increasing oleanane abundance is accompanied by a reduction in the extent of aromatisation and, for the South Sumatra Basin, the proportion of A-ring contracted oleananes. An angiosperm-derived Miocene coal from the Philippines, deposited under freshwater conditions, shows abundant aromatic oleanoids but no oleananes. These results show that oleananes need to be used with caution as age and source markers in fluvio- deltaic and lacustrine petroleum systems. On the other hand, their sensitivity to early diagenetic conditions may make them useful in locating effective source rocks in such systems.Compounds derived from plant resins are major components of some terrigenous oils. Although recent studies have elucidated the molecular structure of resinites, very little information was available on the carbon isotope composition of resinites prior to the present study. No carbon isotope studies of resin-derived compounds in oils had been performed. Hence, carbon stable isotope analyses were carried out on a set of modern and fossil resins of diverse origins and compound specific isotope analysis was used to characterise individual hydrocarbons in resin pyrolysates and oils derived from resinitic source matter. The results showed that "Class V' resinites derived from gymnosperms are enriched in the heavy carbon isotope compared with the angiosperm-derived "Class W' resinites. Furthermore, both the fossil resinites themselves and individual hydrocarbons derived from them are isotopically heavy compared with modern plant resins. The reasons for ++ / these differences and their implications for petroleum geochemical studies are discussed.

The isotopic composition of meteorite sulphur and sea water sulphates was investigated by means of a simultaneous collection mass spectrometer. It was found that sixteen samples of meteorite sulphur possessed identical isotope abundances within the precision of the instrument. The sulphates from various depths in the Atlantic, Pacific and Arctic Oceans, were found to be enriched in s34 compared to the meteorite base level. The overall variation in s32/s34 content was 0.39 percent for the sea water samples. / Thesis / Master of Science (MS)

This work deals with the issue of lead isotopic composition in reference materials. These reference materials were extracted by using method of sequential extraction analyses Isotopic composition of the lead was determined by ICP MS (Thermo scientific). The first part summarizes knowledge in the field of sequential extraction analyses; in the following section issue of using isotopic composition of lead in environmental sciences is discussed. Experimental part describes research methodology and presents results of the sequential extraction and the isotopic composition of lead contained in the analysed reference materials. Following reference materials were analysed: CRM BCR 483, CRM BCR 701, SRM NIST 2709a, SRM NIST 2710a, SRM NIST 2711a. Results of modified sequential extraction procedure BCR (three steps methodology created by Community Bureau of Reference, Belgium to harmonize technical procedure) measured in this work corresponds to the certified or indicative values. Isotopic composition expressed by isotopic ratios 206 Pb/207 Pb among fractions of BCR sequential extraction (fractions I - IV) was folloving: CRM BCR 483 (1,1168 - 1,1350); CRM BCR 701 (1,1583 - 1,1844); SRM NIST 2709a (1,1819 - 1,2118); SRM NIST 2710a (1,1583 - 1,1989); SRM NIST 2711a (1,1079 - 1,1284). Key words: lead isotopic...

Na região dos Andes Patagônicos entre os 41 a 44° S estão expostos amplos e contínuos afloramentos de rochas graníticas do segmento norte do Batólito Norte-Patagônico (BNP). Durante sua evolução a maior parte das rochas graníticas foram colocadas em rochas metamórficas, e outras partes foram colocadas em rochas vulcânicas do Jurássico-Berriasano, sedimentares e vulcânicas do Cretáceo Inferior, vulcânicas do Cretáceo Superior e sedimentares do Mioceno. Parte desta atividade magmática está associada à gênese de depósitos de minério. As rochas plutônicas expostas apresentam uma gradação desde dioritos até granitos e leucogranitos, apesar de que a área é largamente dominada por variedades intermediárias a ácidas. Determinações K-Ar permitiram identificar extensos e volumosos eventos plutônicos que descrevem duas faixas de orientação N-S durante o Cretáceo Inferior (ca. 120-100 Ma) e Mioceno (ca. 20-7 Ma), discretos durante o Jurássico Superior (ca. 155 Ma) e o Cretáceo Superior (ca. 95-70 Ma), restritos durante o Plioceno (ca. 5-3 Ma), e um provável evento plutônico no Eoceno (ca. 54-34 Ma), ao passo que experimentos Ar/Ar confirmam os eventos magmáticos do Cretáceo Inferior (ca. 126-100 Ma) e Mioceno (ca. 19-9 Ma). Determinações U-Pb convencionais indicam a provável perda e herança de Pb, apesar de confirmar os eventos magmáticos do Cretáceo Inferior (ca.129-114 Ma) e Mioceno (ca. 22-13 Ma). Além disso, as determinações U-Pb convencionais em zircões revelam a presença de rochas magmáticas pré-Andinas do Devoniano Inferior (ca. 400 Ma) provavelmente relacionadas com rochas do Maciço Norte-Patagônico. Determinações U-Pb SHRIMP em zircões indicam 110,0±9,6 Ma para um monzogranito e de 126,3±6,7 Ma para um piroxênio dioritio, 8,4±0,3 Ma para um tonalito e 13,26±0,19 Ma para um andesito porfirítico, e de 385,9±7,4 Ma para um corpo de microdiorito tectonizado. Estes dados indicam que o início da atividade plutônica é representada em ambos das faixas por pequenos corpos de colocação superficial, e a idade U-Pb SHRIMP do Devoniano confirma o evento magmático inferido das idades U-Pb convencionais. A distribuição de idades mostra um padrão complexo, mas, permite definir eventos magmáticos do Cretáceo, preferencialmente localizados, a E da Zona de Falha Liquiñe-Ofqui (ZFLO), do Mioceno no interior e a O desta estrutura, e do Plioceno no traço principal da ZFLO. A atividade plutônica do Mioceno, em direção a trincheira é diferente que o padrão definido para a região centro-norte dos Andes chilenos, onde é verificada a migração do arco magmático para a E com a conseqüente diminuição de idades neste sentido. Composições isotópicas de Sr e Nd mostram baixos e positivos teores de Nd com Sr entre -4 e +7 sugerindo que o BNP no segmento estudado, foi composto a partir de mistura de matérias do manto com fusão de crosta inferior, como é demonstrado pelos trabalhos anteriores, em áreas vizinhas. As composições isotópicas de Pb em feldspato, das mesmas amostras datadas por U-Pb convencional, variou com a idade, plútons com 206Pb/204Pb >18,62 são do Mioceno, enquanto que aqueles plútons com 206Pb/204Pb <18,57 são do Cretáceo, com uma relação inversa entre os plútons do Mioceno, o que é atribuído à variável interação com o embasamento metamórfico. Mineralizações de metais base com Au e Ag estão hospedadas em rochas vulcânicas do Cretáceo e limitadas à faixa magmática do Cretáceo Inferior e mineralizações de Au-As estão hospedadas no Microdiorito do Devoniano e em rochas metamórficas do Paleozóico e limitadas à faixa magmática do Mioceno. Além disso, em ambos as faixas, ocorrências de Cu-Mo são relatadas associadas com monzogranitos e tonalitios. Mineralizações de metais preciosos e de base no prospecto Las Juntas estão relacionados com alteração silíca-adularia e quartzo-sericita e deposição de pirita, esfalerita, galena com conteúdos de Ag e Bi, e calcopirita, e menor hematita, tetraedrite, arsenopirita, bornita e calcocita, em veios, vênulas, brechas e escassa disseminação. Os teores são variáveis, mas em veios mineralizados em Cu os teores podem atingir até 15% Cu, e em brechas mineralizadas em Cu-Pb-Zn os teores podem atingir até 32% Pb, 23% Zn e 0,28% Cu, com 1,4 para 1.300 ppm de Ag e 0,02 para 3,9 ppm de Au. Dados de inclusões fluidas indicam temperaturas de homogeneização variando entre 140 a 230º C, salinidades entre 3 a 6% em peso de NaCl equiv., e de deposição de metais base durante ebulição e mistura. Mineralizações de Au-As no prospecto Pichicolo estão relacionadas com alteração silíca e quartzo-sericita e deposição de arsenopirita e pirita, e menor pirrotita, calcopirita e bornita, em vênulas, stockwork e disseminação. Os teores variam entre 0,02 a 2,0 ppm de Au. Dados de inclusões fluidas indicam temperaturas de homogeneização entre 180 a 270º C, salinidades entre de 3 a 5% em peso de NaCl equiv., e deposição metálica durante ebulição e mistura. A mineralização, alteração e as características químicas e físicas de fluidos sugerem para ambos os prospectos características de epitermais de baixa sulfetação. O método Re-Os foi utilizado em molibdenitas hospedadas em plútons de monzogranito e tonalito para determinar a idade da mineralização de Cu-Mo. As idades obtidas (ca. 119 e 9,1 a 8,2 Ma) sugerem que a mineralização ocorreu em sistemas hidrotermais intimamente associada com os eventos magmáticos de Cretáceo Inferior e Mioceno, o que confirma a interpretação acerca da existência das faixas metalogéneticas polimetálicas do Cretáceo Inferior e aurífera do Mioceno propostas para a Cordilheira Norte-Patagônica. Biotita do monzogranito hospedeiro de mineralizaçao de Cu-Mo na aldeia Palena foi datada por Ar/Ar em 114,7 Ma, e outra datação, próxima da ocorrência, em 114,2 Ma. Biotita do tonalito hospedeiro da mineralização de Cu-Mo no estuário Reloncaví foi datada por Ar/Ar em 8,53 Ma, e outra datação, próxima da ocorrência, em 8,64 Ma. A proximidade e a superposição, dentro do erro analítico, entre as idades Ar/Ar em biotita, em ambas as áreas, sugerem que a alteração hidrotemal não foi estendida. Uma idade isocrônica Rb-Sr de 126±8 Ma obtida de rochas hidrotermalmente alteradas com mineralização polimetálica é interpretada como a idade do evento hidrotermal. Experimentos Ar/Ar em sericita hidrotemal de granulação muito fina com mineralização de Au-As mostra redistribuição de Ar por \'recoil\' e a idade integrada de 142±2 Ma sugere que a associação mineralização- magmatismo félsico do Jurássico não deve ser descartada. Composições isotópicas de Sr e Nd de rochas hospedeiras e ígneas associadas indicam que os magmas são principalmente derivados do manto com contaminação de crosta continental variável. Composições isotópicas de Pb em minerais de minério, rochas hospedeiras e ígneas associadas, em ambos os prospectos, se agrupam próximos da curva do orógeno no modelo da \'plumbotectonica\'. Em um diagrama 206Pb/204Pb-207Pb/204Pb, os minerais de minério e as rochas ígneas associados do prospecto Las Juntas são menos radiogênicos (206Pb/204Pb <18.6) que o prospecto Pichicolo (206Pb/204Pb >18.6). Este modelo é compatível com a idade absoluta cretácea da mineralização para Las Juntas e com a idade miocena assumida para Pichicolo. As tendências alongadas da composição de Pb nos minerais de minério indicam, principalmente, um modelo orogênico, sugerindo mistura variável de chumbo a partir de diferentes fontes, sobretudo de crosta superior. / In the Patagonian Andes region between 41 and 44° S extensive and continuous plutonic rocks of the North-Patagonian Batholith north segment are exposed. During their evolution most of the granitic rocks were emplaced in metamorphic rocks and other parts were emplaced in Late Jurassic-Berriasan volcanic rocks, Early Cretaceous sedimentary and volcanic rocks, Late Cretaceous volcanic rocks and Miocene sedimentary rocks. Part of this magmatic activity is associated with ore deposit genesis. The exposed plutonic rocks range mainly from diorites to granites and leucogranites, although the area is extensively dominated by intermediate to acid varieties. K-Ar determinations have allowed identification of extensive and voluminous plutonic events which describe two N-S oriented belts during the late Lower Cretaceous (ca. 120-100 Ma) and Miocene (ca. 20-7 Ma), discreet during the Upper Jurassic (ca. 155 Ma) and the Upper Cretaceous (ca. 95-70 Ma), restricted during the early Pliocene (ca. 5-3 Ma) and a probable plutonism in Eocene times (ca. 54-34 Ma), while Ar/Ar experiments confirm the late Lower Cretaceous (ca. 126-100 Ma) and Miocene (ca. 19-9 Ma) magmatic events. Conventional U-Pb determinations indicate the probable inheritance and loss of Pb, although they confirm the late Lower Cretaceous (ca. 129-114 Ma) and Miocene (ca. 22-13 Ma) magmatic events. In addition, the zircons conventional U-Pb determinations show the presence of pre-Andean Lower Devonian magmatic rocks (ca. 400 Ma) probably linked with rocks of the North- Patagonian Massif. Zircon U-Pb SHRIMP determinations indicate 110.0±9.6 Ma for a monzogranitic pluton and 126.3±6.7 Ma for a pyroxene dioritic stock, 8.4±0.3 Ma for a tonalitic pluton and 13.26±0.19 Ma for hornblende andesitic porphyry, and 385.9±7.4 Ma for a tectonized microdioritic body. These data indicate that the early plutonic activity is represented, in Mesozoic and Cenozoic belts, by basic to intermediate small bodies of shallow emplacement, and the SHRIMP U-Pb Devonian age confirms a magmatic event previously inferred by conventional U-Pb ages. The age distribution shows a complex pattern, which nevertheless allows, magmatic Cretaceous events to be located, preferably, to the E of the Liquiñe-Ofqui Fault Zone, magmatic Miocene events located in and to the W of this structure, and magmatic Pliocene events located in the main branch of the Liquiñe-Ofqui Fault Zone to be defined. The Miocene plutonic activity towards the trench is different to the defined pattern for the north-central Chilean Andes, where the magmatic arc migration to the E and the consequent age diminution in this same direction is verified. Nd and Sr isotopic compositions show low and positive Nd values together with Sr between -4 and +7 suggesting that the North-Patagonian Batholith in the studied segment, has been composed from mixing of mantle derived or mafic lithospheric material with melting of lower continental crust, as is shown by previous work in neighboring areas. The Pb isotopic compositions in feldspar, of the same dating samples by U-Pb conventional method, varied with the age, plutons with 206Pb/204Pb greater than 18.62 are Miocene, whereas those plutons with 206Pb/204Pb less than 18.57 are Cretaceous, with an inverse relation between Miocene plutons, which is attributed to varying interaction grade with the metamorphic basement. Metal base-mineralization with Au and Ag contains are hosted in Cretaceous volcanic rocks and restricted to the Lower Cretaceous magmatic belt and Au-As mineralization are hosted in Devonian microdiorite and Paleozoic metamorphic rocks and restricted to the Miocene magmatic belt. Also, in both belts Cu-Mo occurrences are reported in associated with monzogranites and tonalities, respectively. Metal base and precious mineralizations in the Las Juntas Prospect are related to silicicadularia and quartz-sericite alteration and deposition of pyrite, sphalerite, Ag-bearing and Bi-bearing galena, and chalcopyrite, and minor hematite, tetrahedrite, arsenopyrite, bornite and chalcocite, in vein, veinlets and minor breccia bodies, and scarce dissemination. Ore grades are variable, but in mineralized Cu-veins the values reach up 15% Cu, and in Pb-Zn-Cu breccias the values reach up 32% Pb, 23% Zn and 0.28% Cu, 1.4 to 1,300 ppm Ag and 0.02 to 3.9 ppm Au. Fluid inclusion data indicate homogenization temperatures varying between 140 to 230 ºC, salinities ranging from 3 to 6 weight % NaCl equivalent, and metal base deposition during boiling and mixing events. Asmineralizations with gold contain in the Pichicolo Prospect are related to silicic and quartz-sericite alterations and deposition of arsenopyrite and pyrite, and minor pyrrotite, chalcopyrite and bornite, in veinlets, stockwork and dissemination. Grades vary between 0.02 to 2.0 ppm Au. Fluid inclusion data indicate homogenization temperatures varying between 180 to 270 ºC, salinities ranging from 3 to 5 weight % NaCl equivalent, and metallic deposition during boiling and mixing events. The mineralization, alteration and the chemical and physical fluid characteristics suggest for both studied prospects epithermal low-sulphidation features. Re-Os method in molybdenites hosted in monzogranitic and tonalitic plutons have been used to determine timing of Cu-Mo mineralizations. The obtained ages (ca. 119 and 9.1 to 8.2 Ma) suggest that the mineralization occurred in hydrothermal systems closely associated with late Lower Cretaceous and Miocene plutonic events, which confirm the interpretation about the existence of Lower Cretaceous and Miocene metallogenic belts proposed for the North-Patagonian Cordillera. Biotite of the monzogranitic host rock directly related with the Palena village molybdenite mineralization was dated by Ar/Ar in 114.7 Ma, and near of the occurrence in 114.2 Ma. Biotite of the tonalite host rock directly related with the Reloncaví estuary molybdenite mineralization was dated by Ar/Ar in 8.53 Ma and near of the occurrence in 8.64 Ma. The proximity, and superposition within the analytical error, between the Ar/Ar biotite ages, in both areas, suggests non extended hydrothermal alteration. Rb-Sr isochron age of 126±8 Ma obtained from hydrothermally alterated rocks in a polymetallic prospect is interpreted as the age of the hydrothermal event. Ar/Ar step-heating experiments in hydrothermal very fine grain sericite from Au-As mineralization shown Ar-redistribution by recoil effect and the integrated age of 142±2 Ma suggest that the association mineralization-Jurassic volcanic felsic magmatism should not be discarded. Sr and Nd isotopic compositions of the host and igneous-related mineralization rocks indicate that magmas are mainly mantle derived with variable little crustal contamination. Pb isotopic compositions of the ore minerals, host and igneous-related mineralization rocks in both prospect clusters near of the orogene curve within a plumbotectonic model. On 206Pb/204 versus 207Pb/204Pb plot, the ore minerals and the associated igneous units of the Las Juntas prospect are less radiogenic (206Pb/204Pb <18.6) that the Pichicolo prospect (206Pb/204Pb >18.6). This model is compatible with the absolute Cretaceous mineralization-age determined for the Las Juntas prospect and with the constraint Miocene mineralization-age for the Pichicolo prospect. The elongate trends of the ore minerals in the general clusters indicate mainly an orogenic model fit, suggesting variable mixing of lead from different sources, mainly from upper crust.

Made available in DSpace on 2016-06-02T19:29:24Z (GMT). No. of bitstreams: 1 3085.pdf: 11800699 bytes, checksum: 71c066e8e0a2f17d9129aaf2bec7145c (MD5) Previous issue date: 2010-04-24 / Records of isotopic and elemental carbon and nitrogen and pollen in lake sediments and soils have been used for studies of Quaternary paleoecology worldwide, including in the Amazon at specific sites, such as the region of Carajas, Lake Pata and Region Porto Velho in Rondonia state making it necessary to register in the central southern region. We collected two cores in the Lagoa Jabuti site and a core on the Site Três Coqueiros in the floodplain of the Teles Pires river in northern Mato Grosso state. The cores were analyzed for elemental and isotopic nitrogen and carbon (% C, % N, 13C, 15N and C/N), and palynology and radiometric dating by 14C via AMS. Was also used samples of Quaternary megafauna and elements of material culture. From the analysis carried out it appears that southern Amazon in the Mato Grosso there were no significant ecological changes during the study period, which is around 5,500 years B.P., except for the registration of a relatively sharp change in carbon isotope values for about 2,700 years BP. The pollen analysis of the sediment of Jabuti showed the predominance of elements on forest herb/fern coinciding with data from botanical surveys conducted in the area in which stand families Fabaceae, Arecaceae, Euphorbiaceae, Malvaceae, Combretaceae, Melastomataceae, Annonaceae, among the trees; Cyperaceae , Asteraceae, Chenopodiaceae, Poaceae, Achantaceae and Amaranthaceae between herbs and Polygonaceae, Cyatheaceae and Asplenium among the ferns. The megafauna considered in the paper presented by ESR beyond the age covered by the project and analyzed the material culture (ceramics) revealed that from the earliest moments of occupation (about 1,300 years BP) the ecological conditions of the region have not changed, although they have been registered large gaps in regional occupation that can be interpreted as a crisis in the supply of natural resources necessary for survival in the region. / Registros de dados isotópicos e elementares de carbono e nitrogênio e palinológicos em sedimentos lacustres e solos têm sido utilizados para estudos da paleoecologia do Quaternário em todo mundo, inclusive na Amazônia em sítios específicos, a exemplo da região de Carajás, Lagoa da Pata e região de Porto Velho no estado de Rondônia fazendo-se necessário o registro na região centro meridional da região. Foram coletados dois testemunhos de sondagem na Lagoa Jabuti e um testemunho no Sítio Três Coqueiros na planície de inundação do rio Teles Pires no norte de Mato Grosso. Os testemunhos foram analisados elementar e isotopicamente para nitrogênio e carbono (%C, %N, 13C, 15N e C/N), além de palinologia e datação radiométrica pelo 14C via AMS. Foram ainda utilizadas amostras da megafauna quaternária e elementos da cultura material. A partir das análises executadas, especialmente &#948;13C (-222 a - ) verifica-se que na Amazônia Meridional matogrossense não ocorreram significativas mudanças ecológicas no período estudado, que está em torno dos 5.500 anos, exceto pelo registro de uma alteração relativamente acentuada nos valores isotópicos de carbono há cerca de 2.700 anos A.P. A análise palinológica dos sedimentos da Lagoa Jabuti evidenciaram a predominância de elementos florestais sobre ervas/pteridófita coincidindo com os dados de levantamentos botânicos efetuados na região em que sobressaem famílias Fabaceae, Arecaceae, Euphorbiaceae, Malvaceae, Combretaceae, Melastomataceae, Annonaceae, entre as arbóreas; Cyperaceae, Asteraceae, Chenopodiaceae, Poaceae, Achantaceae e Amaranthaceae entre as ervas e Polygonaceae, Asplenium e Cyatheaceae entre as pteridófitas. A megafauna considerada no trabalho apresentou pelo ESR idade além da abrangida pelo projeto e a cultura material analisada (cerâmica) revelou que desde os primeiros momentos de ocupação (cerca de 1.300 anos A.P.) as condições ecológicas da região não se alteraram, ainda que tenham sido registrados grandes hiatos na ocupação regional que podem ser interpretados como crises no fornecimento de recursos naturais fundamentais para a sobrevivência na região.

Na região dos Andes Patagônicos entre os 41 a 44° S estão expostos amplos e contínuos afloramentos de rochas graníticas do segmento norte do Batólito Norte-Patagônico (BNP). Durante sua evolução a maior parte das rochas graníticas foram colocadas em rochas metamórficas, e outras partes foram colocadas em rochas vulcânicas do Jurássico-Berriasano, sedimentares e vulcânicas do Cretáceo Inferior, vulcânicas do Cretáceo Superior e sedimentares do Mioceno. Parte desta atividade magmática está associada à gênese de depósitos de minério. As rochas plutônicas expostas apresentam uma gradação desde dioritos até granitos e leucogranitos, apesar de que a área é largamente dominada por variedades intermediárias a ácidas. Determinações K-Ar permitiram identificar extensos e volumosos eventos plutônicos que descrevem duas faixas de orientação N-S durante o Cretáceo Inferior (ca. 120-100 Ma) e Mioceno (ca. 20-7 Ma), discretos durante o Jurássico Superior (ca. 155 Ma) e o Cretáceo Superior (ca. 95-70 Ma), restritos durante o Plioceno (ca. 5-3 Ma), e um provável evento plutônico no Eoceno (ca. 54-34 Ma), ao passo que experimentos Ar/Ar confirmam os eventos magmáticos do Cretáceo Inferior (ca. 126-100 Ma) e Mioceno (ca. 19-9 Ma). Determinações U-Pb convencionais indicam a provável perda e herança de Pb, apesar de confirmar os eventos magmáticos do Cretáceo Inferior (ca.129-114 Ma) e Mioceno (ca. 22-13 Ma). Além disso, as determinações U-Pb convencionais em zircões revelam a presença de rochas magmáticas pré-Andinas do Devoniano Inferior (ca. 400 Ma) provavelmente relacionadas com rochas do Maciço Norte-Patagônico. Determinações U-Pb SHRIMP em zircões indicam 110,0±9,6 Ma para um monzogranito e de 126,3±6,7 Ma para um piroxênio dioritio, 8,4±0,3 Ma para um tonalito e 13,26±0,19 Ma para um andesito porfirítico, e de 385,9±7,4 Ma para um corpo de microdiorito tectonizado. Estes dados indicam que o início da atividade plutônica é representada em ambos das faixas por pequenos corpos de colocação superficial, e a idade U-Pb SHRIMP do Devoniano confirma o evento magmático inferido das idades U-Pb convencionais. A distribuição de idades mostra um padrão complexo, mas, permite definir eventos magmáticos do Cretáceo, preferencialmente localizados, a E da Zona de Falha Liquiñe-Ofqui (ZFLO), do Mioceno no interior e a O desta estrutura, e do Plioceno no traço principal da ZFLO. A atividade plutônica do Mioceno, em direção a trincheira é diferente que o padrão definido para a região centro-norte dos Andes chilenos, onde é verificada a migração do arco magmático para a E com a conseqüente diminuição de idades neste sentido. Composições isotópicas de Sr e Nd mostram baixos e positivos teores de Nd com Sr entre -4 e +7 sugerindo que o BNP no segmento estudado, foi composto a partir de mistura de matérias do manto com fusão de crosta inferior, como é demonstrado pelos trabalhos anteriores, em áreas vizinhas. As composições isotópicas de Pb em feldspato, das mesmas amostras datadas por U-Pb convencional, variou com a idade, plútons com 206Pb/204Pb >18,62 são do Mioceno, enquanto que aqueles plútons com 206Pb/204Pb <18,57 são do Cretáceo, com uma relação inversa entre os plútons do Mioceno, o que é atribuído à variável interação com o embasamento metamórfico. Mineralizações de metais base com Au e Ag estão hospedadas em rochas vulcânicas do Cretáceo e limitadas à faixa magmática do Cretáceo Inferior e mineralizações de Au-As estão hospedadas no Microdiorito do Devoniano e em rochas metamórficas do Paleozóico e limitadas à faixa magmática do Mioceno. Além disso, em ambos as faixas, ocorrências de Cu-Mo são relatadas associadas com monzogranitos e tonalitios. Mineralizações de metais preciosos e de base no prospecto Las Juntas estão relacionados com alteração silíca-adularia e quartzo-sericita e deposição de pirita, esfalerita, galena com conteúdos de Ag e Bi, e calcopirita, e menor hematita, tetraedrite, arsenopirita, bornita e calcocita, em veios, vênulas, brechas e escassa disseminação. Os teores são variáveis, mas em veios mineralizados em Cu os teores podem atingir até 15% Cu, e em brechas mineralizadas em Cu-Pb-Zn os teores podem atingir até 32% Pb, 23% Zn e 0,28% Cu, com 1,4 para 1.300 ppm de Ag e 0,02 para 3,9 ppm de Au. Dados de inclusões fluidas indicam temperaturas de homogeneização variando entre 140 a 230º C, salinidades entre 3 a 6% em peso de NaCl equiv., e de deposição de metais base durante ebulição e mistura. Mineralizações de Au-As no prospecto Pichicolo estão relacionadas com alteração silíca e quartzo-sericita e deposição de arsenopirita e pirita, e menor pirrotita, calcopirita e bornita, em vênulas, stockwork e disseminação. Os teores variam entre 0,02 a 2,0 ppm de Au. Dados de inclusões fluidas indicam temperaturas de homogeneização entre 180 a 270º C, salinidades entre de 3 a 5% em peso de NaCl equiv., e deposição metálica durante ebulição e mistura. A mineralização, alteração e as características químicas e físicas de fluidos sugerem para ambos os prospectos características de epitermais de baixa sulfetação. O método Re-Os foi utilizado em molibdenitas hospedadas em plútons de monzogranito e tonalito para determinar a idade da mineralização de Cu-Mo. As idades obtidas (ca. 119 e 9,1 a 8,2 Ma) sugerem que a mineralização ocorreu em sistemas hidrotermais intimamente associada com os eventos magmáticos de Cretáceo Inferior e Mioceno, o que confirma a interpretação acerca da existência das faixas metalogéneticas polimetálicas do Cretáceo Inferior e aurífera do Mioceno propostas para a Cordilheira Norte-Patagônica. Biotita do monzogranito hospedeiro de mineralizaçao de Cu-Mo na aldeia Palena foi datada por Ar/Ar em 114,7 Ma, e outra datação, próxima da ocorrência, em 114,2 Ma. Biotita do tonalito hospedeiro da mineralização de Cu-Mo no estuário Reloncaví foi datada por Ar/Ar em 8,53 Ma, e outra datação, próxima da ocorrência, em 8,64 Ma. A proximidade e a superposição, dentro do erro analítico, entre as idades Ar/Ar em biotita, em ambas as áreas, sugerem que a alteração hidrotemal não foi estendida. Uma idade isocrônica Rb-Sr de 126±8 Ma obtida de rochas hidrotermalmente alteradas com mineralização polimetálica é interpretada como a idade do evento hidrotermal. Experimentos Ar/Ar em sericita hidrotemal de granulação muito fina com mineralização de Au-As mostra redistribuição de Ar por \'recoil\' e a idade integrada de 142±2 Ma sugere que a associação mineralização- magmatismo félsico do Jurássico não deve ser descartada. Composições isotópicas de Sr e Nd de rochas hospedeiras e ígneas associadas indicam que os magmas são principalmente derivados do manto com contaminação de crosta continental variável. Composições isotópicas de Pb em minerais de minério, rochas hospedeiras e ígneas associadas, em ambos os prospectos, se agrupam próximos da curva do orógeno no modelo da \'plumbotectonica\'. Em um diagrama 206Pb/204Pb-207Pb/204Pb, os minerais de minério e as rochas ígneas associados do prospecto Las Juntas são menos radiogênicos (206Pb/204Pb <18.6) que o prospecto Pichicolo (206Pb/204Pb >18.6). Este modelo é compatível com a idade absoluta cretácea da mineralização para Las Juntas e com a idade miocena assumida para Pichicolo. As tendências alongadas da composição de Pb nos minerais de minério indicam, principalmente, um modelo orogênico, sugerindo mistura variável de chumbo a partir de diferentes fontes, sobretudo de crosta superior. / In the Patagonian Andes region between 41 and 44° S extensive and continuous plutonic rocks of the North-Patagonian Batholith north segment are exposed. During their evolution most of the granitic rocks were emplaced in metamorphic rocks and other parts were emplaced in Late Jurassic-Berriasan volcanic rocks, Early Cretaceous sedimentary and volcanic rocks, Late Cretaceous volcanic rocks and Miocene sedimentary rocks. Part of this magmatic activity is associated with ore deposit genesis. The exposed plutonic rocks range mainly from diorites to granites and leucogranites, although the area is extensively dominated by intermediate to acid varieties. K-Ar determinations have allowed identification of extensive and voluminous plutonic events which describe two N-S oriented belts during the late Lower Cretaceous (ca. 120-100 Ma) and Miocene (ca. 20-7 Ma), discreet during the Upper Jurassic (ca. 155 Ma) and the Upper Cretaceous (ca. 95-70 Ma), restricted during the early Pliocene (ca. 5-3 Ma) and a probable plutonism in Eocene times (ca. 54-34 Ma), while Ar/Ar experiments confirm the late Lower Cretaceous (ca. 126-100 Ma) and Miocene (ca. 19-9 Ma) magmatic events. Conventional U-Pb determinations indicate the probable inheritance and loss of Pb, although they confirm the late Lower Cretaceous (ca. 129-114 Ma) and Miocene (ca. 22-13 Ma) magmatic events. In addition, the zircons conventional U-Pb determinations show the presence of pre-Andean Lower Devonian magmatic rocks (ca. 400 Ma) probably linked with rocks of the North- Patagonian Massif. Zircon U-Pb SHRIMP determinations indicate 110.0±9.6 Ma for a monzogranitic pluton and 126.3±6.7 Ma for a pyroxene dioritic stock, 8.4±0.3 Ma for a tonalitic pluton and 13.26±0.19 Ma for hornblende andesitic porphyry, and 385.9±7.4 Ma for a tectonized microdioritic body. These data indicate that the early plutonic activity is represented, in Mesozoic and Cenozoic belts, by basic to intermediate small bodies of shallow emplacement, and the SHRIMP U-Pb Devonian age confirms a magmatic event previously inferred by conventional U-Pb ages. The age distribution shows a complex pattern, which nevertheless allows, magmatic Cretaceous events to be located, preferably, to the E of the Liquiñe-Ofqui Fault Zone, magmatic Miocene events located in and to the W of this structure, and magmatic Pliocene events located in the main branch of the Liquiñe-Ofqui Fault Zone to be defined. The Miocene plutonic activity towards the trench is different to the defined pattern for the north-central Chilean Andes, where the magmatic arc migration to the E and the consequent age diminution in this same direction is verified. Nd and Sr isotopic compositions show low and positive Nd values together with Sr between -4 and +7 suggesting that the North-Patagonian Batholith in the studied segment, has been composed from mixing of mantle derived or mafic lithospheric material with melting of lower continental crust, as is shown by previous work in neighboring areas. The Pb isotopic compositions in feldspar, of the same dating samples by U-Pb conventional method, varied with the age, plutons with 206Pb/204Pb greater than 18.62 are Miocene, whereas those plutons with 206Pb/204Pb less than 18.57 are Cretaceous, with an inverse relation between Miocene plutons, which is attributed to varying interaction grade with the metamorphic basement. Metal base-mineralization with Au and Ag contains are hosted in Cretaceous volcanic rocks and restricted to the Lower Cretaceous magmatic belt and Au-As mineralization are hosted in Devonian microdiorite and Paleozoic metamorphic rocks and restricted to the Miocene magmatic belt. Also, in both belts Cu-Mo occurrences are reported in associated with monzogranites and tonalities, respectively. Metal base and precious mineralizations in the Las Juntas Prospect are related to silicicadularia and quartz-sericite alteration and deposition of pyrite, sphalerite, Ag-bearing and Bi-bearing galena, and chalcopyrite, and minor hematite, tetrahedrite, arsenopyrite, bornite and chalcocite, in vein, veinlets and minor breccia bodies, and scarce dissemination. Ore grades are variable, but in mineralized Cu-veins the values reach up 15% Cu, and in Pb-Zn-Cu breccias the values reach up 32% Pb, 23% Zn and 0.28% Cu, 1.4 to 1,300 ppm Ag and 0.02 to 3.9 ppm Au. Fluid inclusion data indicate homogenization temperatures varying between 140 to 230 ºC, salinities ranging from 3 to 6 weight % NaCl equivalent, and metal base deposition during boiling and mixing events. Asmineralizations with gold contain in the Pichicolo Prospect are related to silicic and quartz-sericite alterations and deposition of arsenopyrite and pyrite, and minor pyrrotite, chalcopyrite and bornite, in veinlets, stockwork and dissemination. Grades vary between 0.02 to 2.0 ppm Au. Fluid inclusion data indicate homogenization temperatures varying between 180 to 270 ºC, salinities ranging from 3 to 5 weight % NaCl equivalent, and metallic deposition during boiling and mixing events. The mineralization, alteration and the chemical and physical fluid characteristics suggest for both studied prospects epithermal low-sulphidation features. Re-Os method in molybdenites hosted in monzogranitic and tonalitic plutons have been used to determine timing of Cu-Mo mineralizations. The obtained ages (ca. 119 and 9.1 to 8.2 Ma) suggest that the mineralization occurred in hydrothermal systems closely associated with late Lower Cretaceous and Miocene plutonic events, which confirm the interpretation about the existence of Lower Cretaceous and Miocene metallogenic belts proposed for the North-Patagonian Cordillera. Biotite of the monzogranitic host rock directly related with the Palena village molybdenite mineralization was dated by Ar/Ar in 114.7 Ma, and near of the occurrence in 114.2 Ma. Biotite of the tonalite host rock directly related with the Reloncaví estuary molybdenite mineralization was dated by Ar/Ar in 8.53 Ma and near of the occurrence in 8.64 Ma. The proximity, and superposition within the analytical error, between the Ar/Ar biotite ages, in both areas, suggests non extended hydrothermal alteration. Rb-Sr isochron age of 126±8 Ma obtained from hydrothermally alterated rocks in a polymetallic prospect is interpreted as the age of the hydrothermal event. Ar/Ar step-heating experiments in hydrothermal very fine grain sericite from Au-As mineralization shown Ar-redistribution by recoil effect and the integrated age of 142±2 Ma suggest that the association mineralization-Jurassic volcanic felsic magmatism should not be discarded. Sr and Nd isotopic compositions of the host and igneous-related mineralization rocks indicate that magmas are mainly mantle derived with variable little crustal contamination. Pb isotopic compositions of the ore minerals, host and igneous-related mineralization rocks in both prospect clusters near of the orogene curve within a plumbotectonic model. On 206Pb/204 versus 207Pb/204Pb plot, the ore minerals and the associated igneous units of the Las Juntas prospect are less radiogenic (206Pb/204Pb <18.6) that the Pichicolo prospect (206Pb/204Pb >18.6). This model is compatible with the absolute Cretaceous mineralization-age determined for the Las Juntas prospect and with the constraint Miocene mineralization-age for the Pichicolo prospect. The elongate trends of the ore minerals in the general clusters indicate mainly an orogenic model fit, suggesting variable mixing of lead from different sources, mainly from upper crust.

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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.