This study applies a life history approach to analyzing the identities of 52 Maya individuals who lived between 2000 BC and AD 900 in and around the city of Holmul, within the Petén region of Guatemala. Primary goals were to: (1) identify migrant and local individuals within the urban population; (2) determine 87Sr/86Sr isotope ratio signatures for the sites of Holmul, Cival, La Sufricaya, K’o, and Hamontun; (3) compile osteobiographies, personal life histories revealed through skeletal remains, of the individuals in the sample; and (4) evaluate evidence bearing on the identities of inhabitants of the Holmul region and how they were represented within economic, political, and cultural landscapes of the ancient Maya. This work demonstrates how bioarchaeologists can implement osteobiographical analyses to advance the understanding of multifaceted social identities and individual experiences of life and death. By integrating osteological study, stable isotope analysis, and consideration of mortuary context, material culture, inscriptions, and monumental architecture, the individual, rather than the population, becomes the focus. This aggregate approach allows for an in-depth consideration of human remains as former social beings with complex identities. The findings of this research suggest that most elite inhabitants in this ancient Maya city were local to the Holmul region, with the few outliers having originated from elsewhere in the Maya lowlands. This conclusion aligns with Maya elite ideologies of establishing lineages and reinforcing power through ancestor veneration. The local 87Sr/86Sr ratio signature of the Holmul region is comparable to other archaeological sites in the southern Maya lowlands. The osteobiographies reveal life histories, which personalize prior interpretations that considered the population only as an aggregate. This project also elucidates identities of sacrificed children, elite/royal women, and the local Holmul elite. Results of the study support the use of the isotopic analysis of human remains as an essential tool for approaching complex archaeological questions and evaluating hypotheses previously addressed primarily using architectural, iconographic, and artifactual evidence. Further, this study demonstrates the benefit of the isotopic analysis of dental enamel, especially in the Maya region and other environments characterized by difficult excavation conditions and the poor preservation of human remains.

Há na literatura um grande número de publicações versando sobre métodos analíticos para a determinação de razões isotópicas através das mais diversas modalidades de espectrometria. Entretanto, praticamente todos esses métodos possuem umarestrição comum em relação à gama de íons moleculares que podem ser utilizados nessas determinações: eles devem ser, ou íons elementares, ou íons cujo único átomo poli-isotópicoé o elemento de interesse. Isto é obtido, ou mediante adestruição das moléculas da amostra, ou complexos tratamentosquímicos para a obtenção de espécies poli-atômicas adequadas.Neste trabalho, foi desenvolvido um método matemático capazde deconvolver o padrão isotopomérico de um íon molecular,isto é, calcular os padrões isotópicos dos átomos que ocompõem dados a sua fórmula elementar e o seu espectro .A principal contribuição de um método desse tipo é a ampliaçãoda variedade de espécies químicas e modalidades de espectrometria aceitáveis para análises isotópicas. O algoritmo desenvolvidofoi caracterizado através da sua aplicação a um grande númerode espectros simulados visando modelar a resposta do métodoquando submetido a algumas imperfeições experimentais típicasde espectrometria e relevantes para análises isotópicas,tais como ruído, discriminação instrumental de massas, nãolinearidade de detecção, falta de resolução e má compensaçãode espectral. Os resultados obtidos permitiram concluirque, ao contrário do que o senso comum às vezes possa sugerir,determinações isotópicas realizadas através de espéciespoli-atômicas podem, muitas vezes, ser mais exatas e precisasque as efetuadas pelas abordagens convencionais. Concluiu-seque, de maneira geral, os resultados tendem a ser tantomelhores quanto maior for o número de instâncias do elementode interesse na fórmula do íon molecular escolhido. Foiestudada experimentalmente a viabilidade de métodos analíticosde equilibração para determinações de razões isotópicashidrogênio/deutério em amostras aquosas utilizando polióiscomo sondas e espectrometria com ionização electrospray.Os polióis testados foram o manitol, o ácido glucônico,a glucosamina e a N-metilglucamina (através do seu complexocom o ácido bórico). Os resultados obtidos mostraram algunsdesvios sistemáticos que sugerem que haja troca parcialde hidrogênios não lábeis dos polióis na fase gasosa, oque impossibilitaria esta aplicação. Sondas aternativasaos polióis são propostas. / Several articles can be found in the literature describing methods forthe determination of isotopic ratios through the various modalities ofmass spectrometry. However, almost all of them have a commonrestriction on the type of molecular ion that can be employed in thesedeterminations: they must be either elemental ions, or polyatomic ionswhose sole polyisotopic element is the one being analysed. This isusually achieved through the destruction of the molecules, or throughcomplex synthetic procedures. In this work, a mathematical methodcapable of deconvolving the isotopomeric pattern of a molecular ion,i.e., calculating the isotopic pattern of its constituent atoms givenits formula and its mass spectrum, has been developed. The maincontribution of such a method to the field is the broadening of therange of acceptable chemical species for isotopic analyses. Thedeveloped algorithm was characterized by applying it to a large numberof simulated spectra with the objective of modelling its response tosome experimental imperfections common to mass spectrometry andrelevant for isotopic analyses, such as noise, instrumental massdiscrimination, detection non-linearity, lack of resolution and badbaseline compensation. The results allowed us to conclude that, inspite of whatever commonsense might suggest, isotopic analysescarried out through the polyatomic approaches can, in many cases, bemore exact and precise than those performed through conventionalapproaches. It could also be concluded that, in general, the largerthe number of instances of the element of interest in the formula ofthe chosen ion, the better the results become. Also as part of theproject, the viability of employing polyols as probes for thehydrogen/deuterium ratio in aquous samples in equilibration methodsand electrospray mass spectrometry has been studied. The studiedpolyols were: manitol, gluconic acid, glucosamine and N-metilglucamine(through its complex with boric acid). The obtained results showedsome systematic errors that suggest that there might be a partialexchange of non-labile hydrogen atoms during the electrosprayphenomenon. Alternative probes are proposed.

A partir de registros de dois testemunhos, KF-12 localizado na Bacia de Campos e KF-18 na Bacia de Santos, ambos na margem continental sudeste brasileira, realizou-se a caracterização do Último Interglacial s.l., de 60 a 130 ka atrás. Primeiramente, estabeleceu-se um Modelo de Idade para o KF-12 tendo como referência a curva do KF-18 que já possuía uma boa cronologia. Com a curva do plexo Menardii, determinou-se as biozonas de Ericson e Wollin (1968) e constatou-se a diferença existente entre os limites da Zona X e do estágio isotópico marinho 5. Os limites inferidos para a biozona X foram 135,6 ka AP (limite inferior), e 82,3 ka AP (limite superior) para o testemunho KF-18 e; para o KF-12, 133,5 ka AP (limite inferior) a 88,4 ka AP (limite superior). O estágio isotópico marinho (MIS) 5, na região de estudo, compreende o intervalo entre 129,5 e 71,1 ka AP, em ambos os testemunhos. Também foram utilizados outros dados, tais como, razão isotópica em foraminífero planctônico, fauna, teor de carbonato, razão Ti/Ca e Fe/Ca através dos quais pôde-se estimar paleotemperaturas da superfície do mar, aporte de material terrígeno de acordo com as condições úmidas/seca da região de estudo durante o intervalo de interesse. Por fim, verificou-se que tanto os dados isotópicos de oxigênio (δ18O) do testemunho de gelo da Groenlândia (NGRIP) quanto os da razão de deutério da Antártica variaram de forma semelhante aos δ18O de foraminíferos bentônicos do KF-12 e KF-18, confirmando o sincronismo de tais registros. / The Last Interglacial Cycle s.l. (between 60 and 130 ky ago) was characterized through registers of two different cores in the Brazilian continental shelf, KF-12, located in Campos Basin and KF-18, located in Santos Basin. First an \"age model\" was established for KF-12, from the KF-18 curve that already had a good cronology. Using Menardii group curve, the biozones from Ericson e Wollin (1968) were established and the difference between the X Zone and the marine isotope stage 5 edges was noticed. The inferred limits for X biozone were 35,6 ky BP (inferior limit) and 82,3 ky BP (superior limit) for KF-18 core and 133,5 and 88,4 ky BP for KF-12 core. In both cores the marine isotope stage (MIS) 5 was between 129,5 and 71,1 ky BP. Other data were also used in the study, such as isotope ratio in planktonic foraminifera, fauna, carbonate content, Ti/Ca and Fe/Ca ratios whereby humidity/dry conditions and continental runoff were inferred. Lastly, the study showed that both the oxygen isotope data from Greenland ice core (NGRIP) and the Antarctic deuterium ratio ranged in a similar way of the δ18O benthonic foraminifera from KF-12 and KF-18, confirming the data synchronism.

Vários complexos intrusivos de rochas alcalinas e carbonatitos ocorrem na região centro-oeste de Moçambique e estão intimamente relacionados ao Sistema do Rifte da África Oriental. Correspondem a atividades ígneas anorogênicas e cortam o embasamento pré-Cambriano da Cadeia Moçambicana. Destes, foram estudadas algumas amostras de seis complexos carbonatíticos (Xiluvo, Muambe, Muande, Fema, Rio Mufa e Evate) e três sieníticos (Chiperone, Tumbine e Salambidua). Os carbonatitos são caracterizados por uma grande predominância de carbonatos, mais apatita, flogopita e raramente anfibólio. O de Xiluvo apresenta, além disso, minerais típicos de terras raras e pirocloro. O sienito de Chiperone tem como constituinte principal nefelina, enquanto que os dois restantes são compostos essencialmente, de K-feldspatos pertíticos. Todos têm como componentes subordinados anfibólios, piroxênio, biotita e apatita. Idades K-Ar das rochas sieníticas, obtidas em anfibólio e biotita, por volta de 118 Ma, apontam o Cretáceo Inferior como período decolocação dos sienitos de Tumbine e Salambidua, enquanto que o sienito de Chiperone resultou muito mais antigo, com aproximadamente 450 Ma. Estes valores confirmam idades radiométricas anteriores, relacionadas com a Província de Chilwa em Malawi. Dados litogeoquímicos destacam dois grupos distintos entre as amostras dos carbonatitos estudadas. Xiluvo, Muambe e Evate situam-se no campo dos carbonatitos cálcicos, enquanto que Fema, Muande e Rio Mufa situam-se no campo dos carbonatitos ferromagnesianos. Os padrões de distribuição de elementos menores e de terras raras são similares àqueles definidos para diversas ocorrências congêneres. Foi analisada também, por comparação, uma amostra carbonática do mármore de Chíduè, tirando a amostra de Chíduè a qual mostrou-se quimicamente diferente, com concentrações muito baixas em praticamente todos elementos. Por outro lado as amostras do Xiluvo exibem os mais elevados teores na maior parte dos elementos. Quanto à geoquímica isotópica, os carbonatitos exibem uma correlação negativa no diagrama 87Sr/86Sr vs. Nd(0) e indicam a existência de pelo menos dois tipos de fontes. Uma delas, correspondendo aos complexos de Xiluvo e Muambe, com 87Sr/86Sr de cerca de 0.703 e Nd com valores positivos, poderia ser astenosférica. A outra fonte, relativa aos demais complexos, apresenta valores negativos de Nd entre (-4) e (-8), e valores moderadamente elevados de 87Sr/86Sr, entre 0.705 e 0.708. A interpretação dos dados geoquímicos isotópicos levou à hipótese de misturas de fontes mantélicas diferentes, bem como possibilidades de contaminação crustal. / Several Syenitic and carbonatitic alkaline complexes occur in central-western region of Mozambique and are related to the East African Rift System. They correspond to anorogenic igneous activities and intrude the Precambrian basement of the Mozambique belt. Of these, six carbonatites (Xiluvo, Muambe, Muande, Fema, Rio Mufa and Evate) and three syenites (Chiperone, Tumbine and Salambidua) were studied. The carbonatites exhibit a great predominance of carbonates, plus apatite, phlogopite and some amphibole. Xiluvo, Muambe and Rio Mufa in addition, include typical minerals of REE and pyrochlore. The Chiperone syenite exhibits nepheline as the main constituent, while the two other are mainly composed of perthitic K-feldspar. All them present amphibole, pyroxene, biotite and apatite as subordinate constituents. K-Ar ages for the Tumbine and Salambidua syenites, obtained in amphibole and biotite, with around 118 Ma, indicate the Lower Cretaceous as the period of placement. However, the Chiperone syenite yielded a much older age around 450 Ma. These values are compatible with earlier radiometric dates, related to the Chilwa Ineous Province of Malawi. On lithogeochemistry, two groups can be envisaged within the carbonatites. One of them includes the calcium carbonatites of Xiluvo, Muambe end Evate, and the other includes the ferromagnesian carbonatites of Fema, Muande and Rio Mufa. The distribution patherns of trace and REE elements are similar to those of normal carbonatites. A sample of the Chíduè marmor was also analyzed, for comparison, and yielded much lower concentrations for most elements. On the other hand, the Xiluvo samples yielded the highest contents for practically all trace and REE elements. The carbonatites exhibit a negative correlation in the 87Sr/86Sr vs. 143Nd/144Nd diagram, and indicate the existence of at least two different sources. One of them, corresponding to the Xiluvo and Muambe complexes, yielded 87Sr/86Sr values around 0.703 and positive Nd, indicating a possible astenospheric source. The second source, for the other complexes, presents negative values of Nd between (-4) e (-8) and moderately high values of 87Sr/86Sr between 0.705 and 0.708. The interpretation of the geochemical isotopic data leads to the hypothesis of mixtures of mantles sources, as well as some possibility of crustal contamination.

Proveniência por métodos isotópicos em duas unidades litodêmicas – o Complexo Metamórfico Porongos (CMP) no domínio central-oriental do Cinturão Dom Feliciano (CDF) e a Suíte Metamórfica Várzea do Capivarita (SMVC), localizada no domínio leste do CDF - apresentou áreas-fonte similares nos dois casos: Os metassedimentos do CMP, na região das Antiformes de Santana da Boa Vista e Serra dos Pedrosas, foram depositados entre 785 e 595 Ma (U-Pb em zircão detrítico por LA-ICP-MS). Apresentam registros de áreas-fonte com predominância de idades de ca. 2.2 – 2.0 Ga, mesmas idades do embasamento da região, o Complexo Encantadas. As assinaturas isotópicas de 207Pb/204Pb X 206Pb/204Pb mostraram pouca relação dos metassedimentos do CMP com áreas-fonte do cráton Rio de La Plata, e εNd variando entre -13 a -6.5, com valores menos negativos para amostras onde foram obtidos zircões com mesma idade do vulcanismo félsico do CMP. Outros registros incluem idades de 1.5-1.4 Ga, cujas assinaturas εHf indicam fontes juvenis, possivelmente relacionadas a um sistema de rifteamento registrado nos Anortositos Capivarita. Na Antiforme Capané, zircões datados em SHRIMP e LA-ICP-MS de rochas metavulcânicas intermediárias a félsicas indicaram idades de 663 ± 2.7 Ma, representando um vulcanismo mais jovem do que aquele encontrado anteriormente no CMP, vinculado à fusão parcial crustal. Novos dados U-Pb em zircão confirmam registro do metavulcanismo de 783.4 ± 3.9 Ma nos metassedimentos, comparáveis a idades obtidas nos Gnaisses Cerro Bori, interpretados como um arco continental de ca. 800 Ma. Zircões detríticos de rochas metassedimentares da SMVC apresentaram registros de ca. 2.2 – 2.0 Ga, além de idades de ca. 1.4 Ga e idade máxima de deposição de 714.3 ± 3.9 Ma, com pico metamórfico registrado em borda metamórfica de zircões com 618 ± 7.3 Ma εHf predominantemente negativas. Mármores apresentaram razões 87Sr/86Sr de 0.70609, o que permite deduzir uma idade de deposição mais antiga que 715 Ma, próximo dos valores encontrados em mármores na região de Arroio Grande. A comparação dos isótopos de Hf com rochas do Cinturão Damara nos crátons Kalahari e Congo, cuja amalgamento junto ao Rio de La Plata deu origem ao Gondwana Ocidental, mostram que existe pouca ou nenhuma relação com áreas-fonte dos metassedimentos do CMP e SMVC no Neoproterozóico. Estes dados levam a dedução de que acresção de terrenos ou microcontinentes com características de embasamento, nesse caso denominado aqui como Embasamento Encantadas, cuja evolução se dá com acresção de um arco continental de idades entre 780 e 660 Ma, é a origem de parte das áreas-fonte do CMP, e possivelmente foi um dos eventos tectônicos que controlaram evolução do terreno ao longo do CMP e SMVC. / Isotopic provenance realized in two lithodemic units – Porongos Metamorphic Complex (PMC), in the central-eastern domain of the Dom Feliciano Belt (DFB) and the Várzea do Capivarita Metamoprhic Suite (VCMS), in the eastern domain of the same belt – presented similar source-areas in both cases: The PMC metasediments, in Santana da Boa Vista and Serra dos Pedrosas Antiforms were deposited between 785 and 595 Ma (LA-ICP-MS detrital zircon U-Pb). Both PMC and VCMS displayed source-areas with ages varying from ca. 2.2 – 2.0 Ga, which is the same age presented in the regional basement, the Encantadas Complex. 207Pb/204Pb X 206Pb/204Pb isotopic signatures displayed little resemblance between CMP metasediments and possible source-areas in the Rio de La Plata Craton, and εNd varied between -13 to -6.5, with less negative values in samples were where obtained zircons with the same age of felsic volcanism in the PMC. Others records included ages from 1.5 to 1.4 Ga, with εHf signatures indicating juvenile sources, possibly related to a rifting system recorde in the Capivarita Anorthosite. In the Capané Antiform, SHRIMP and LA-ICP-MS U-Pb zircon ages from felsic to intermediary metavolcanic rocks displayed 663 ± 2.7 Ma, which is a younger record than the previously obtained in the PMC, and can be related to partial crustal fusion. Also new U-Pb detrital zircon ages confirm the record of the metavolcanics of 783.4 ± 3.9 Ma in the metasediments, comparable to the ages obtained in the Cerro Bori orthogneisses, interpreted as a continental arc of ca. 800 Ma. Metasedimentary rocks of VCMS displayed zircons with ca. 2.2-2.0 Ga, besides ages of ca. 1.4 Ga and maximum depositional age of 714.3 ± 3.9 Ma, with metamorpich peak recorded in metamorphic rims of 618 ± 7.3 Ma and negative εHf signatures. Marbles presented 87Sr/86Sr ratios of 0.70609, which can be deducted as an older than 715 Ma depositional age, near values obtained to Arroio Grande marbles. Comparison of Hf signatures with rocks from Damara Belt of Kalahari and Congo Cratons, whose assembly with Rio de La Plata to form West Gondwana in Neoproterozoic, displayed little to no relationship with the source-areas of PMC and VCMS metasediments I in the Neoproterozoic. This indicates that terrain or a microcontinent accretion with basement features, in this case the Encantadas Basement, whose evolution underwent accretion in a continental arc between 780 to 660 Ma, it’s the source to part of the PMC , and possible was one of the tectonic events that controlled terrain evolution in the PMC and VCMS.

Neodymium (Nd) isotopes have been increasingly used to trace the modern and past ocean circulation. This assumes that seawater Nd isotope ratios (εNd) effectively fingerprint different water masses and approximate expected values from water mass mixing. However, the decoupling of Nd isotopes and Nd concentration (the “Nd paradox”) in the water column, and the lack of understanding of sources and sinks of Nd, restrain our understanding of the “quasi-conservative” behavior of εNd in seawater. Nd is one of the lanthanide rare earth elements (REEs) with similar chemical characteristics that undergo some degree of fractionation. The shale-normalized REE patterns and REE ratios can be used to investigate potential sources/sinks of REEs. Combining REEs with εNd will provide additional information to study REE cycling in the ocean. To better understand the reliability of εNd as a water mass tracer, 17 high-resolution seawater profiles were sampled meridionally in the Southwest Atlantic (GEOTRACES GA02 Leg 3; RRS James Cook 057) and measured for εNd. This region involves the major water masses in the Atlantic Meridional Overturning Circulation: southward flowing North Atlantic Deep Water (NADW), northward flowing Antarctic Intermediate Water (AAIW) and Antarctic Bottom Water (AABW). Along the cruise track, there are potential sources (eolian dusts, marginal sediments, oceanic volcanism, and nepheloid layer) that could add external Nd to seawater and disturb the “quasi-conservative” behavior of εNd. Our results show strikingly that the Southwest Atlantic transect confirms “quasi-conservative” behavior of εNd in intermediate and deep water. Our evaluations of Nd isotopic deviations (ΔεNd) from conservative behavior show that out of 198 intermediate and deep samples, 49% of ΔεNd-values are within ± 0.25 εNd units (< analytical error: ± 0.30 εNd units) and 84% of ΔεNd-values are within ± 0.75 εNd units. Potential sources that could add external Nd to seawater from oceanic volcanism and the nepheloid layer do not show impact on seawater εNd. Terrigenous sources of Nd (e.g. eolian dusts from Africa and Patagonia, marginal sediments from South America) show influence on surface/subsurface water εNd but this εNd signature is not transferred to intermediate and deep water. To better understand the conservative vs. non-conservative behavior of REEs in the ocean, the dissolved REE concentrations were analyzed for the 17 seawater profiles in the Southwest Meridional Atlantic Transect (GEOTRACES GA02 Leg 3). The shale-normalized REE patterns are consistent with typical seawater patterns. To investigate whether and how much REE concentrations deviate from conservative water mass mixing, the REE concentration deviations were calculated for the intermediate and deep water. It is shown that within the SAMT, the intermediate and deep water REEs generally reflect water mass mixing and nearly conservative behavior. Along this transect, the potential sources that could add external REEs to seawater are dissolution of REEs from eolian dust to the surface/subsurface water, REEs released from dissolution of Fe-Mn oxides in the oxygen depleted zone, REEs from sediments near the continental margin, and dissolution of REEs from deep sea sediments. REEs and Nd isotopes of most intermediate and deep water masses passing the volcanic Rio Grande Rise (RGR) and Vitória-Trindade Ridge (VTR) do not show influence from RGR and VTR. REEs and Nd isotopes of the bottom water Lower Circumpolar Deep Water (LCDW) and AABW passing the RGR are influenced by dissolved REEs from the deep sea sediments. LCDW and AABW passing the VTR are influenced by dissolved REEs from the deep sea sediments as well as the volcanic VTR. In order to better understand the oceanic Nd cycling in the North Pacific, its sources and sinks in seawater must be better characterized. The high εNd of North Pacific Deep Water (NPDW, ~ −4) has been difficult to reconcile with the eolian inputs as reflected in surface waters (e.g. Jones et al., 2008), which have much lower εNd (~ −10), indicating potential addition of a component from Pacific volcanism. In order to constrain the REE sources in the North Pacific, we measured εNd and REEs of seawater from five stations across the subarctic North Pacific sampled by the Innovative North Pacific Experiment (INOPEX) Cruise SO202 (2009). In the surface water (~10 m), the highest εNd is observed at the station closest to the Aleutian-Kamchatka volcanic margin (Northwest station SO202-5), suggesting higher contribution of external REEs from volcanic ashes compared to the other stations. In the shallow water (100-400 m, depending on location), remineralization of REEs from volcanic ashes prevails over Asian dusts at Northwest station SO202-5 and near Japan stations SO202-44, 41, and 39, whereas remineralization of REEs from Asian dusts prevails over volcanic ashes at the Northeast station SO202-32 in the open ocean of the Alaska Peninsula. From the depths of North Pacific Intermediate Water (NPIW) to NPDW, seawater εNd and REEs show conservative water mass mixing of NPIW-NPDW. They also show conservative behavior along the water mass transport paths of NPIW and NPDW. Below the depths of NPDW, addition of external REEs is observed in the vertical profiles of εNd and REEs as well as along the transport path of LCDW. The potential sources that add external REEs to the bottom water are (1) sediments on the Kuril-Kamchatka-Aleutian volcanic margin along the LCDW transport path, and (2) sediments on the seafloor, both of which could interact with seawater and modify the seawater εNd and REE signatures.

A partir de registros de dois testemunhos, KF-12 localizado na Bacia de Campos e KF-18 na Bacia de Santos, ambos na margem continental sudeste brasileira, realizou-se a caracterização do Último Interglacial s.l., de 60 a 130 ka atrás. Primeiramente, estabeleceu-se um Modelo de Idade para o KF-12 tendo como referência a curva do KF-18 que já possuía uma boa cronologia. Com a curva do plexo Menardii, determinou-se as biozonas de Ericson e Wollin (1968) e constatou-se a diferença existente entre os limites da Zona X e do estágio isotópico marinho 5. Os limites inferidos para a biozona X foram 135,6 ka AP (limite inferior), e 82,3 ka AP (limite superior) para o testemunho KF-18 e; para o KF-12, 133,5 ka AP (limite inferior) a 88,4 ka AP (limite superior). O estágio isotópico marinho (MIS) 5, na região de estudo, compreende o intervalo entre 129,5 e 71,1 ka AP, em ambos os testemunhos. Também foram utilizados outros dados, tais como, razão isotópica em foraminífero planctônico, fauna, teor de carbonato, razão Ti/Ca e Fe/Ca através dos quais pôde-se estimar paleotemperaturas da superfície do mar, aporte de material terrígeno de acordo com as condições úmidas/seca da região de estudo durante o intervalo de interesse. Por fim, verificou-se que tanto os dados isotópicos de oxigênio (&#948;18O) do testemunho de gelo da Groenlândia (NGRIP) quanto os da razão de deutério da Antártica variaram de forma semelhante aos &#948;18O de foraminíferos bentônicos do KF-12 e KF-18, confirmando o sincronismo de tais registros. / The Last Interglacial Cycle s.l. (between 60 and 130 ky ago) was characterized through registers of two different cores in the Brazilian continental shelf, KF-12, located in Campos Basin and KF-18, located in Santos Basin. First an \"age model\" was established for KF-12, from the KF-18 curve that already had a good cronology. Using Menardii group curve, the biozones from Ericson e Wollin (1968) were established and the difference between the X Zone and the marine isotope stage 5 edges was noticed. The inferred limits for X biozone were 35,6 ky BP (inferior limit) and 82,3 ky BP (superior limit) for KF-18 core and 133,5 and 88,4 ky BP for KF-12 core. In both cores the marine isotope stage (MIS) 5 was between 129,5 and 71,1 ky BP. Other data were also used in the study, such as isotope ratio in planktonic foraminifera, fauna, carbonate content, Ti/Ca and Fe/Ca ratios whereby humidity/dry conditions and continental runoff were inferred. Lastly, the study showed that both the oxygen isotope data from Greenland ice core (NGRIP) and the Antarctic deuterium ratio ranged in a similar way of the &#948;18O benthonic foraminifera from KF-12 and KF-18, confirming the data synchronism.

This thesis provides a geochemical interpretation of natural gas resources in north eastern British Columbia (NEBC), Canada. The work is part of the three-year project, British Columbia Natural Gas Atlas (BC-NGA) to collect samples and compile data on molecular (C1 to C5) and stable isotope ratio (δ13C and δ2H) compositions of natural gases in NEBC. The primary objective of the BC-NGA project is to produce a comprehensive, public, web database with maps of the gas geochemical data from a variety of gas tests including mudgas collected during drilling, downhole flow tests, production gas, and gas collected from surface emissions. The area of study in NEBC is a large portion of the Western Canadian Sedimentary Basin (WCSB) with Paleozoic, Mesozoic, and Cenozoic strata of thousands of meters thickness. Within this stratigraphic package there are numerous depositional hiatus and regional aquitards complicating the generation of regional maps and profiles. This M.Sc. thesis utilizes the geochemical gas parameters to characterize the range of gases in the BC-NGA database. The thesis found that the petroleum sources and active generation processes are not uniform in the NEBC. In some cases, the original gas signatures have been overprinted by localized processes in specific strata. The results of this new data plus compilation of existing data in the BC-NGA dataset indicate that many classical interpretive diagrams, e.g., Bernard Diagram (C1/[C2+C3] vs. δ13C1) and CD Diagram (δ13C1 vs. δ2H-C1), confirm the microbial/ thermogenic nature of the gases, but lack the resolution for detailed stratigraphic interpretation of gas sources and migration. A particularly interesting finding is that δ13Ckerogen (-33 ‰) estimated from δ13C1 observed for most strata in NEBC is 13C depleted compared with conventional kerogens and the data supports new calibration of the methane isotopes. This δ13Ckerogen value is an unlikely value and therefore the offset observed compared with conventional natural gases requires a different explanation, including commingling of 13C depleted methane from microbial sources. Enhanced characterization is obtained by combinations of the gas parameter ratios: δ13C1, δ13C2, δ13C3, C2/C3, C2/iC4, (e.g., ‘Berner-Faber Diagram’, ‘Prinzhofer Diagram’, ‘Lorant Diagram’). In addition, a new plot of δ13C2-δ13C1 versus iC4/nC4 ratio was developed in this thesis. / Graduate

abstract: Variations of 238U/235U in sedimentary carbonate rocks are being explored as a tool for reconstructing oceanic anoxia through time. However, the fidelity of this novel paleoredox proxy relies on characterization of uranium isotope geochemistry via laboratory experimental studies and field work in modern analog environmental settings. This dissertation systematically examines the fidelity of 238U/235U in sedimentary carbonate rocks as a paleoredox proxy focusing on the following issues: (1) U isotope fractionation during U incorporation into primary abiotic and biogenic calcium carbonates; (2) diagenetic effects on U isotope fractionation in modern shallow-water carbonate sediments; (3) the effects of anoxic depositional environments on 238U/235U in carbonate sediments. Variable and positive shifts of 238U/235U were observed during U uptake by primary abiotic and biotic calcium carbonates, carbonate diagenesis, and anoxic deposition of carbonates. Previous CaCO3 coprecipitation experiments demonstrated a small but measurable U isotope fractionation of ~0.10 ‰ during U(VI) incorporation into abiotic calcium carbonates, with 238U preferentially incorporated into the precipitates (Chen et al., 2016). The magnitude of U isotope fractionation depended on aqueous U speciation, which is controlled by water chemistry, including pH, ionic strength, carbonate, and Ca2+ and Mg2+ concentrations. Based on this speciation-dependent isotope fractionation model, the estimated U isotope fractionation in abiotic calcium carbonates induced by secular changes in seawater chemistry through the Phanerozoic was predicted to be 0.11–0.23 ‰. A smaller and variable U isotope fractionation (0–0.09 ‰) was observed in primary biogenic calcium carbonates, which fractionated U isotopes in the same direction as abiotic calcium carbonates. Early diagenesis of modern shallow-water carbonate sediments from the Bahamas shifted δ238U values to be 0.270.14 ‰ (1 SD) higher than contemporaneous seawater. Also, carbonate sediments deposited under anoxic conditions in a redox-stratified lake—Fayetteville Green Lake, New York, USA— exhibited elevated δ238U values by 0.160.12 ‰ (1 SD) relative to surface water carbonates with significant enrichments in U. The significant U isotope fractionation observed in these studies suggests the need to correct for the U isotopic offset between carbonate sediments and coeval seawater when using δ238U variations in ancient carbonate rocks to reconstruct changes in ocean anoxia. The U isotope fractionation in abiotic and biogenic primary carbonate precipitates, during carbonate diagenesis, and under anoxic depositional environments provide a preliminary guideline to calibrate 238U/235U in sedimentary carbonate rocks as a paleoredox proxy. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2018

Food webs in aquatic ecosystems can be dramatically altered by invasive species. Quagga mussels are prevalent invaders that compete with existing species and disrupt nutrient cycling. In 2012, the Quagga Mussel (Dreissena rostriformus bugensis) was introduced into Lake Powell and is expected to move throughout the reservoir in the near future. Stable isotope analysis is a powerful tool for characterizing food webs and trophic interactions. To predict the long-term effects of Quagga Mussels, we used stable isotope analysis of primary producers, primary consumers, prey fish species, and predator fish species in Lake Powell to determine food web structure. Quagga Mussel are positioned to disrupt the pelagic arm of the food web by interfering with the link between phytoplankton and herbivorous zooplankton. This will likely have negative impacts on pelagic fish such as striped bass (Morone saxatilis) and threadfin shad (Dorosoma petenense). Quagga Mussel may also boost benthic productivity in the littoral zone by diverting nutrients from the water column to the benthos. This may have positive impacts on littoral fishes such as largemouth bass (Micropterus salmoides), smallmouth bass (Micropterus dolomieu), bluegill (Lepomis macrochirus), and green sunfish (Lepomis cyanellus).