Authigenic carbonate rock (ACR) is derived from microbial oxidation of methane, biodegradation of crude oil, and oxidation of sedimentary organic matter. The precipitation of ACR was characterized petrographically, mineralogically, and geochemically. ACR collected from the seafloor in the Gulf of Mexico (GOM) and ACR recovered from drilled cores in the Krishna-Godawari (KG) basin offshore India were used. All study sites are associated with hydrocarbon gas venting, seepage, free gas, or gas hydrate. ACR from the GOM is densely cemented and extremely irregular in shape, whereas ACR from offshore India is generally an oval-shaped smooth nodule and also densely cemented. The dominant mineral in ACR is authigenic calcite. ACR contains carbon derived from sedimentary organic carbon oxidation that geologically sequesters much fossil carbon. Bulk carbon and oxygen isotopes of ACR were measured. ACR from the GOM is strongly depleted in 13C with ?13C of ?42.5? and enriched in 18O with ?18O of 4.67?. The ?13C of hydrocarbon is typically more depleted in 13C than in the associated ACR. The reason is that authigenic carbonate cements from hydrocarbon oxidation generally enclose skeletal material characterized by normal marine carbonate. Three groups that represent different hydrocarbon sources to ACR were classified in this study: primary carbon sources to ACR from (1) methane plus biodegraded oil, (2) methane, or (3) biodegraded oil. Wide ranges in ?13C (?49.12 to 14.06?) and ?18O ( 1.27 to 14.06?) were observed in ACR from offshore India. In sediments, the ?13C may be affected by differences in the rate of organic carbon oxidation, which generate varying ?13C with depth during methanogenesis. Based on the wide range in ?13C, ACR from offshore India was classified: (1) ?13C may reflect high rates of organic carbon oxidation, (2) ACR may be derived primarily from methane oxidation, and (3) ?13C may reflect low rates of organic carbon oxidation. ?18O values are heavier than those of normal marine carbonates. The ?18O may be caused by reaction with deep-sourced water that was isotopically heavier than ambient seawater. Some samples may reflect heavy ?18O from gas hydrate decomposition, but it would not cause significant heavy oxygen isotopes.

The Sierra Mojada district consists of multiple types of mineral concentrations ranging from polymetallic sulfide deposits, "non-sulfide Zn" (NSZ) deposits, and a Pb carbonate deposit hosted by Upper Jurassic to Lower Cretaceous carbonates. This study focuses on the two non-sulfide Zn deposits, the Smithsonite Manto and the Iron Oxide Manto, that occur south of the San Marcos fault. The Smithsonite Manto shows karst features, including internal sediments interbanded with smithsonite (ZnCO₃). The Iron Oxide Manto consists of strata-bound zones dominantly of hemimorphite (Zn₄Si₂O₇ (OH)₂·H₂O) that fills pores in Fe-oxides. The mineralogy of the NSZ mineralization consists of smithsonite, hemimorphite and Zn clays (sauconite) associated mainly with calcite and Mn-Fe-oxides. Zn clays are abundant in the Smithsonite Manto, but no Zn clays have been found in the Iron Oxide Manto. This project attempts to constrain the origin of the NSZ concentrations through petrographic and mineralogical study of major Zn-bearing minerals, and their carbon and oxygen stable isotopes and Pb isotope geochemistry. Smithsonite in the Smithsonite Manto occurs as botryoidal aggregates consisting of scalenohedral or rhombohedral microcrystals and banded colloform or massive smithsonite in open spaces, whereas smithsonite in the Iron Oxide Manto occurs as rhombic microcrystals grown in pore spaces or finely intergrown with Fe-oxides. Both Fe-poor and Fe-rich smithsonite are found in the Iron Oxide Manto. Under optical-CL, smithsonite displays complex growth zoning that can be related to variable trace element content. Trace elements semiquantitatively analyzed using LA-ICP-MS show that most blue luminescent smithsonite has lower Mn contents than pink to bright red luminescent zones in smithsonite. Preliminary fluid inclusion petrography in hemimorphite and calcite suggests that fluid composition can be related to precipitation of NSZ minerals from freshwater to slightly saline waters. Calculated salinities for two phase (liquid +vapor) and single phase (liquid) inclusions in hemimorphite range between 0.0 and 1.6 wt. % NaCl equivalent, and salinities of inclusions in calcite were between 0.0 and 1.1 wt. % NaCl equivalent. The oxygen isotope values for smithsonite are relatively constant (avg. [delta]¹⁸O[subscriptVSMOW] = 21.9 ± 0.5[per mille]), whereas [delta]¹³C[subscriptVPDB] values range from -8.4 to -1.1 [per mille]. The oxygen isotope values in late calcite are within the same range of smithsonite, whereas the average values of the carbon isotope are lower by 5 [per mille]. Formational temperature of smithsonite is calculated to be between 26 ~ 40 °C using the modern groundwater composition at Cuatro Ciénegas. Similar Pb isotopic compositions of smithsonite and cerussite to galena suggest the source of metals in the NSZ deposits presumably originate from the sulfide deposits. / text

Submitted by William Justo Figueiro (williamjf) on 2015-07-15T20:29:02Z No. of bitstreams: 1 14c.pdf: 18447268 bytes, checksum: cb27bcfcdf1b467b658d2ece3ae7777b (MD5) / Made available in DSpace on 2015-07-15T20:29:02Z (GMT). No. of bitstreams: 1 14c.pdf: 18447268 bytes, checksum: cb27bcfcdf1b467b658d2ece3ae7777b (MD5) Previous issue date: 2012-11-12 / Nenhuma / O presente estudo apresenta a taxonomia, bioestratigrafia e paleoecologia dos foraminíferos planctônicos e bentônicos recuperados no intervalo Aptiano superiorAlbiano da sucessão dominantemente carbonática do Deep Sea Drilling Project (DSDP) Site 364, localizado na bacia de Kwanza (costa afora de Angola). Foram identificadas 30 espécies de foraminíferos planctônicos e 42 espécies de foraminíferos bentônicos. Com base nas assembleias de foraminíferos planctônicos, a seção sedimentar estudada foi subdividida em diversas biozonas, abrangendo as idades Aptiano tardio ao Albiano, da Zona Hedbergella trocoidea a Zona Pseudothalmanninella ticinensis. Uma conspícua discordância foi identificada no core 31, compreendendo do topo do Albiano inferior à base do Albiano superior. A composição específica das assembleias de foraminíferos planctônicos as caracteriza como assembleias marinhas de águas rasas e permite a inferência do domínio de condições mesotróficas a eutróficas ao longo do intervalo estudado. As associações aptianas de foraminíferos planctônicos apresentam afinidade paleobiogeográfica tetiana, suportando um influxo de água superficial tetiana no setor restrito (ao norte da Cadeia de Walvis-Elevação do Rio Grande) do Oceano Atlântico Sul setentrional já no Aptiano tardio. Tendências nos valores isotópicos de 13C, que devem ser cuidadosamente interpretadas devido a uma possível alteração diagenética, sugerem uma idade aptiana tardia (Zona Globigerinelloides algerianus) para o intervalo estratigráfico do core 42 ao core 37, no qual fósseis-guia tetianos estão ausentes, além de sugerir que os folhelhos negros da base do testemunho estudado (cores 42-39) podem ser correlatos ao evento anóxico do Aptiano tardio. Entre os foraminíferos planctônicos ocorre uma profunda mudança faunística na passagem Aptiano-Albiano, caracterizada por altas taxas de extinção seguidas por elevadas taxas de surgimento de espécies, além de uma significativa mudança no padrão arquitetural das testas. Foram identificadas três associações de foraminíferos bentônicos, que parecem ser principalmente controladas por variações paleobatimétricas. A fauna de foraminíferos bentônicos pode ser classificada como uma Associação do tipo Marssonella, provavelmente relacionada a paleoprofundidades neríticas a batiais superiores, e também exibindo uma marcada afinidade paleobiogeográfica tetiana. / This work presents a taxonomic, biostratigraphic and paleoecologic study on the planktic and benthic foraminiferal faunas recovered from the late Aptian-late Albian carbonatedominated succession of Deep Sea Drilling Project (DSDP) Site 364, located in the Kwanza Basin (offshore Angola). Thirty planktic and 42 benthic foraminiferal species were identified herein. Based on planktic foraminiferal assemblages, the studied section was subdivided in a series of biozones, late Aptian to late Albian in age, from the Hedbergella trocoidea Zone to the Pseudothalmanninella ticinensis Zone. A remarkable unconformity was identified in core 31, spanning the latest early to earliest late Albian. The specific composition of the recovered planktic foraminiferal assemblages characterizes them as open marine epipelagic dwellers, and permits the suggestion of predominant mesotrophic to eutrophic environmental conditions throughout the studied stratigraphic succession. Aptian planktic foraminiferal assemblages present a significant Tethyan paleobiogeographic affinity, supporting a Tethyan surface-water influx into this restricted southeastern sector of the northern South Atlantic Ocean (north to the Walvis Ridge-Rio Grande Rise) back in the late Aptian. 13C trends, which have to be carefully interpreted due to possible diagenetic overprint, suggest a late Aptian age (Globigerinelloides algerianus Zone) for the stratigraphic interval from core 42 to about core 37, where Tethyan age-diagnostic foraminiferal species are missing, as well as that the black shale levels in cores 42-39 could be correlated to the “late Aptian anoxic event”. Among planktic foraminifera, a conspicuous faunal turnover occurs at the Aptian/Albian transition, characterized by high rates of extinctions followed by increasing rates of species originations and changes in tests’ architecture. Three benthic foraminiferal associations were identified, which seem to be mainly controlled by changes in paleobathymetry. Also, the studied benthic foraminiferal fauna could be classified as a Marssonella Association, probably related to neritic and upper bathyal paleodepths, also exhibiting a Tethyan paleobiogeographic affinity.

The biostratigraphy and isotope stratigraphy of the upper Aptian to lower Cenomanian interval including oceanic anoxic events OAE1b, 1c and 1d are investigated in ODP Site 763, drilled on the Exmouth Plateau offshore northwest Australia. Benthic foraminifera suggest that Site 763 was situated in outer neritic to upper bathyal water depths (~150-600 m). OAEs of the Atlantic basin and Tethys are typically associated with organic carbon-rich black shales and δ13C excursions. However, OAEs at this high latitude site correlate with ocean acidification and/or pyrite formation under anoxic conditions rather than black shales. Ocean acidification maybe responsible for sporadic low abundances of planktic foraminifera compared to radiolarians and benthic foraminifera associated with increased volcanogenic CO2 production during the formation of the Southern and Central Kerguelen Plateaus. Sea surface temperature may have cooled to 11°C in the late Aptian but increased gradually during the Albian. The Aptian/Albian boundary is placed at a negative carbon isotope excursion associated with the lowest occurrence of Microhedbergella renilaevis, typically found within the Niveau Kilian black shale of OAE1b. Third-order sea level cycles, particularly in the middle Albian, produced cyclic changes in the abundance of inoceramid prisms that increased during inferred times of falling sea level. The late Albian OAE1c and OAE1d coincide with horizons of intense pyritization and the absence of all biocomponents suggesting the development of euxinia. Warm Tethyan waters reached the Exmouth Plateau during the latest Albian based on the presence of thermocline dwelling keeled planktic foraminifera including Planomalina buxtorfi.

Cette étude transdisciplinaire incluant sédimentologie, stratigraphie séquentielle, chimiostratigraphie, et géochimie organique et inorganique, examine la série carbonatée du Jurassique moyen-supérieur dans la chaîne du sud-ouest Gissar. Cette série représente l’affleurement le plus complet de la marge nord du Bassin d’Amu-Darya, une province gazière majeure d’Asie Centrale. La production de carbonates commence au début du Callovien, lors d’un ralentissement de la subsidence tectonique régionale associé à un réchauffement climatique. Un changement majeur dans la production carbonatée et la configuration de la plate-forme est enregistré à la fin du Callovien. Ce changement se caractérise par le passage (i) d’une rampe carbonatée avec un gradient proximal-distal bien contrasté du Callovien à (ii) un lagon à faciès péritidaux probablement protégé par des récifs de grande dimension à l’Oxfordien. La surface stratigraphique séparant ces deux séquences est interprétée comme une surface d'émersion régionale, enregistrant une chute du niveau marin entraînée par la tectonique et le climat. Durant la partie terminale de l’Oxfordien moyen, un ou plusieurs bassins intrashelfs sont localisés au sud-ouest de la plate-forme carbonatée. Des carbonates fins nodulaires ou laminés se déposent dans des eaux stratifiées, légèrement hypersalées et anoxiques à dysoxiques, où des tapis microbiens produisent de la matière organique et des carbonates. Ces faciès enregistrent l’initiation de la restriction du Bassin d’Amu Darya, qui se poursuit avec la progradation d’une sabkha et le dépôt de séries anhydritiques et salifères. La comparaison des séries sédimentaires met en évidence des évènements stratigraphiques communs entre le sud-ouest Gissar et les autres bassins des marges nord téthysienne et sud téthysienne : initiation de la plate-forme carbonatée, excursions isotopiques du carbone, âge et mode de formation des roches mères organiques (etc.), impliquant des contrôles climatiques et/ou tectoniques à grande échelle. L’étude pétrographique et géochimique de la diagenèse des carbonates révèle une paragenèse complexe. Certains faciès sont influencés par la fabrique sédimentaire lors de la diagenèse précoce. La succession des phases diagénétiques est reliée à la stratigraphie et à la subsidence des carbonates. Après leur dépôt, les sédiments de la série du Kugitang ont été enfouis à plus de 2 km de profondeur. Des phases liées à des fluides chauds et possiblement à la réduction thermochimique des sulfates se mettent en place durant la Mésogenèse. Finalement, les données stratigraphiques à haute résolution obtenues sur les affleurements du sud-ouest Gissar sont utilisées pour aider à la prédiction de la répartition des réservoirs d’hydrocarbures en subsurface du Bassin d’Amu-Darya. / This transdisciplinary study including sedimentology, sequence stratigraphy, chemostratigraphy, and organic and inorganic geochemistry examines the Middle-Upper Jurassic carbonates series located in the southwestern Gissar range. These carbonates, also known as the Kugitang series, represent the most complete outcrop of the northern margin of the Amu-Darya Basin, a gas-producing province of Central Asia. Carbonate production begins in the late Early Callovian during a regional slowing of the tectonic subsidence, coeval with a climate warming. A major change in the carbonate production and platform configuration is recorded at the end of the Callovian: (i) a carbonate ramp with a well-contrasted proximal-distal gradient develops during the Lower to Middle or Upper Callovian. It is overlain by (ii) a vast low energy lagoon dominated by peritidal facies, probably protected by large reefs, during the Lower and Middle Oxfordian. The stratigraphic surface separating the two depositional sequences is associated with a hiatus (Upper Callovian-Lower Oxfordian) and interpreted as a regional exposure surface recording a sea-level drop caused by tectonics and/or climate. During the Middle Oxfordian, one or several intrashelf basins develop southwestwards of the studied carbonate platform. Laminated and nodular carbonates rich in organic matter predominate in these basins. They are interpreted to have formed through the mineralization of microbial mats colonizing the stratified, slightly hypersaline, anoxic to dysoxic basin floor. Large scale reefs may have favored the isolation of these basins. These deposits record the initiation of the tectonic isolation of the Amu Darya Basin, which culminates with the progradation of a large-scale sabkha and the deposition of a thick anhydrite and salt series. The comparison of stratigraphic series highlights common events in several basins of the northern Tethyan margin, but also with the Arabian Plate: initiation of the carbonate platform, carbon isotope excursions, age and depositional conditions of organic-matter rich rocks, etc. The petrography and geochemistry of carbonates reveal a complex diagenetic history. Some facies are strongly controlled by the sedimentary fabric. The diagenetic succession is tentatively linked with the stratigraphy and the subsidence history. Following deposition, the Kugitang series was buried at more than 2 km. Some cements are interpreted to have formed through the circulation of hot fluids in the rocks during the mesogenesis and possibly due to thermochemical sulfate reduction, especially in the Callovian Sequence. Finally, the high-resolution stratigraphy established in this study is used to help improving the prediction of carbonate reservoirs in the subsurface Amu Darya Basin.