Authigenic clays are potential proxies for paleoclimate change when formed under saline conditions. Between 1.9 -1.7 mya, Olduvai was a closed-hydrologic basin into which Al- and Fe- rich detrital clays were transported from surrounding soils. Authigenic Mg-rich smectite formed within the basin due to chemical alteration in alkaline and saline conditions. 40 samples were chosen from a stratigraphic section in the center of the paleolake and analyzed to characterize the geochemical facies of the material using XRD, EMPA, and FTIR. ~70% of samples were Mg-rich with clay d060 XRD peaks between 1.506-1.523Å. EMPA indicated (Al2O3 + Fe2O3)/MgO ratios ranged from 0.2-4.8, 21 had ratios >1.0, indicating higher (Al2O3 + Fe2O3) content. These clay data correlated with bulk XRF data, indicating diagenetic controls on bulk composition. Therefore, bulk geochemistry can potentially indicate paleoclimate change when influenced by Mg-rich phyllosilicate formation.

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Grain assemblages in organic-rich mudrocks of the Eagle Ford Formation of South Texas are assessed to determine the relative contributions of intra- and extrabasinal sediment sources, with the ultimate goal of producing data of relevance to prediction of diagenetic pathways. Integrated light microscopy, BSE imaging, and X-ray mapping reveal a mixed grain assemblage of calcareous allochems, biosiliceous grains (radiolaria), quartz, feldspar, lithics, and clay minerals. Dominant fossils are pelagic and benthic foraminifers and thin-walled and prismatic mollusks; echinoderms, calcispheres, and oysters are present. Early-formed authigenic minerals, including calcite, kaolinite, dolomite, albite, pyrite, quartz, and Ca-phosphate, some reworked, add to the overall lithologic heterogeneity. Point counting of images produced using energy-dispersive X-ray mapping in the SEM provides observations at a scale appropriate to classifying the mudrocks based on the composition of the grain assemblage, although grains and other crystals of clay-size cannot be fully characterized even with the SEM. Each sample is plotted on a triangle, whose vertices correspond to terrigenous and volcanic grains (extrabasinal components), calcareous allochems, and biosiliceous grains. As a subequal mix of grains of intrabasinal and extrabasinal origins the detrital grain assemblage of the Eagle Ford, presents a formidable challenge to the task of lithologic classification of this unit, as neither conventional limestone nor sandstone classifications can be readily applied. The abundant marine skeletal debris in the Eagle Ford is accompanied by abundant calcite cementation and the dissolution and replacement of biosiliceous debris is accompanied by authigenic quartz, suggesting that mudrock grain classification has potential for yielding diagenetic predictions. / text

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.

Mineralogical and isotopic analysis of authigenic carbonates from different gas hydrate-bearing seepage structures in the Derugin Basin (Sea of Okhotsk) are presented. The analysis showed the existence of four morphological types of carbonates, with all of them mainly of Mg-calcite.13C values of carbonates generally light owing to the inheritance of carbon from microbial methane. 13C-enriched samples at the VNIIOkeangeologia structure with 13C values of up to +9.3‰ represent carbonate precipitation due to methanogenesis. The calculated equilibrium 18O values of carbonates in general correspond to measured values.

In order to understand the response of authigenic minerals to the gas hydrate geo-system, various authigenic pyrites were picked out under Zeiss Microscope and their S isotopes were analyzed later from 652 sediments samples at intervals of about 1.5m recovered from all 5 sites of Integrated Ocean Drilling Program (IODP) Expedition 311 on Cascadia Margin, northeastern Pacific. SEM photos of picked pyrites exhibit various aggregation features mainly in forms of strawberry, pillar/rod and dumbbell in sizes from 200 m to 1000m. Typical cubic pyrite crystals could be seen under smaller scale SEM photos. Most δ34S values in Site U1325 at the west deeper water location of IODP 311 show negative values low to -33.964‰ CDT, distinctly contrasted to the δ34S in Site U1329 at the east shallower location having much more positive values up to 28.29‰ CDT. At the cold venting position assigned as Site U1328 the δ34S values show strong negative values in the upper part of sediments column above 135 mbsf (meter below sea floor), increasing gradually with the depth from -35.83‰ CDT to -1.32‰ CDT, and then display many positive excursions up to 32.49‰ CDT below 135 mbsf, which is significantly distinguished from the values in nearby non-cold venting Site U1327 having much less positive excursions in the lower part of column below 110 mbsf. In all sites a general negative δ34S excursion occur in the upper part of sediments columns above 30~35 mbsf except in Site U1328 having more depth, indicating the potential current sulfate methane interface (SMI) activity zones. Distinct positive δ34S excursions up to the highest δ34S value 53.65‰ CDT from strawberry pyrites aggregations might indicate that sulfide products by AOM probably inherit completely the sulfate having high δ34S value and no sulfate was left after AOM at a high methane flux under gas hydrate geological background.

Magister Scientiae - MSc / Commercial hydrocarbon production relies on porosity and permeability that defines the storage capacity and flow capacity of the resevoir. To assess these parameters, petrographic and petrophysical log analyses has been found as one of the most powerful approach. The approach has become ideal in determining reservoir quality of uncored reservoirs following regression technique. It is upon this background that a need arises to integrate petrographic and petrophysical well data from the study area. Thus, this project gives first hand information about the reservoir quality for hydrocarbon producibility. Five wells (A-J1, A-D1, A-H1, A-K1 and K-A2) were studied within the Orange Basin, Offshore South Africa and thirty five (35) reservoirs were defined on gamma ray log where sandstone thickness is greater than 10m. Eighty three (83) sandstone samples were gathered from these reservoirs for petrographic analyses within Hauterevian to Cenomanian sequences. Thin section analyses of these sediments revealed pore restriction by quartz and feldspar overgrowths and pore filling by siderite, pyrite, kaolinite, illite, chlorite and calcite. These diagenetic minerals occurrence has distructed intergranular pore space to almost no point count porosity in well K-A2 whilst in A-J1, A-D1, A-H1 and A-K1 wells porosity increases at some zones due to secondary porosity. Volume of clay, porosity, permeability, water saturation, storage capacity, flow capacity and hydrocarbon volume were calculated within the pay sand interval. The average volume of clay ranged from 6% to 70.5%. The estimated average effective porosity ranged from 10% to 20%. The average water saturation ranged from 21.7% to 53.4%. Permeability ranged from a negligible value to 411.05mD. Storage capacity ranged from 6.56 scf to 2228.17 scf. Flow capacity ranged from 1.70 mD-ft to 31615.82 mD-ft. Hydrocarbon volume varied from 2397.7 cubic feet to 6215.4 cubic feet. Good to very good reservoir qualities were observed in some zones of well A-J1, A-K1 and A-H1 whereas well A-D1 and K-A2 presented poor qualities.

It has been hypothesized that authigenic carbonate minerals, formed within the pore spaces of marine siliciclastic formations during early diagenesis, may have had a substantial influence on the global carbon cycle, particularly in times of low oxygen in Earth history. According to this idea, alkalinity is generated via anaerobic organic matter degradation, resulting in carbonate oversaturation and the precipitation of low δ13C carbonate cements. If a substantial amount of 13C-depleted carbonate was sequestered in this authigenic sink, the δ13C of dissolved inorganic carbon (DIC) in the global ocean would be driven to more positive values without significant organic carbon burial - a signal which would be recorded in marine carbonates. Research presented herein tests this hypothesis from newly acquired lithostratigraphic and coupled stable carbon and oxygen isotope data of Upper Devonian limestone and black shale formations preserved within the Western Canada Sedimentary Basin. The Late Devonian includes a mass-extinction event, and is characterized by pervasive ocean anoxia and a dramatic reduction in platformal carbonate sediment deposition. As such, it has been hypothesized to represent an ideal time for the emergence of an active authigenic carbonate sink. Results show that both basinal shale (Besa River and Exshaw formations) and platform carbonates (Wabamun Group and its equivalents), record a δ13C signal that is within the expected range of Devonian seawater (3‰ to -2‰), signifying that precipitated authigenic carbonate had no influence on the isotopic composition of DIC. It was observed, however, that evaporitic depositional settings can accumulate carbonate sediment with low δ13C values (down to -8.4‰), potentially caused by local water column organic matter respiration during prolonged water-mass residence in a restricted marginal marine setting. If such depositional environments were globally pervasive, such as during during global sea-level lows, it is plausible that the carbon isotope mass balance would be affected. / Graduate / 2021-06-18

<p> Examination of subsurface cores of the Middle-Lower Silurian Thorold Sandstone from Consumers' Gas Silver Creek 004 Grimsby Pool indicate the presence of a single laminated sandstone facies deposited in a lower shoreface environment. Subsurface thin sections show greater development of quartz cement in the form of quartz overgrowths when compared to thin sections from surface outcrop leading to a porosity decrease of 20%. Petrographic and cathodoluminescence studies reveal that concavo-convex and sutured grain contacts, responsible for 80% of the grain contacts within the Thorold Sandstone, are generally between authigenic overgrowths and not detrital grains indicating that pressure solution is not the major source of silica within the Thorold Sandstone. Studies of detrital and authigenic clays utilizing a combination of thin section, scanning electron microscope and X-ray diffraction techniques show that illite (both detrital and authigenic) is the dominant clay mineral within the Thorold Sandstone in the 004 Pool, followed by approximately one half as much detrital kaolinite and minor authigenic chlorite. Shallow maximum depth of burial ( 786 to 1160m) and low diagenetic temperatures (30°c) suggest that clay minerals are unlikely to have undergone extensive diagenetic transformation. Consequently, detrital minerals represent the clay minerals present at the time of deposition while authigenic clays form by direct precipitation from pore fluids. During eodiagenesis mechanical compaction has reduced sandstone porosity from 40% to 28 to 29% while during mesodiagenesis the progressive paragenetic assemblage of authigenic quartz overgrowths, authigenic chlorite and authigenic illite have reduced porosity to its present value of 4 to 10%.</p> / Thesis / Bachelor of Science (BSc)

Cold seep-carbonates are the microbially mediated by-products of the anaerobic oxidation of methane (AOM) at seafloor cold seeps, and are widespread about modern continental margins and in the geologic record. Some modern and Miocene examples of cold seep-carbonates from the East Coast Basin, North Island, New Zealand have been analysed in this study, to characterise and determine their carbonate fabrics, elemental and mineralogical composition, and stable δ18O and δ13C isotope signatures, so as to provide insights into the diagenetic changes associated with the lithification and burial of seep-carbonates. The ancient samples were collected from the onshore middle Miocene Tauwhareparae (TWP) seep deposit, while the modern samples were obtained from the National Institute of Water and Atmosphere (NIWA) Cruise TAN0616 (November 2006) from Ritchie Ridge, offshore Hikurangi Margin. A paragenetic sequence of diagenetic events involving early aragonitic phases, followed by late calcitic phases is defined for the seep-carbonates. This sequence likely has relevance for understanding the fluid-cement histories of seep-carbonates more widely. Two main carbonate mineralogies occur in each of the sample groups - modern samples are aragonitic or dolomitic, while the ancient ones consist dominantly of either aragonite or calcite. Thus, aragonite common to both sample groups, and is interpreted to represent the initial primary carbonate precipitate in hydrocarbon seep provinces under specific fluid flux and local pore-water chemistry conditions. Aragonite morphologies range from microcrystalline carbonate ('micarb'), to acicular aragonites that may form botryoids or spherulites. Dolomite occurs in those modern samples which appear to constitute exhumed remnants of a former subsurface 'seep plumbing system', and so are strictly not true seabed 'seep-carbonates', but instead are part of the larger hydrocarbon seep province. Calcite in the ancient samples is either a product of alteration and neomorphic transformation of aragonite, or derives from late stage cementation from burial fluids. As a result of their formation processes, the calcites are generally recrystallised and have equant or 'cellular' textures. Stable δ13C and δ18O isotope cross-plots reveal a large spread of values for the sample groups. Ancient samples range from δ13C -8 to -50 PDB and δ18O -5.5 to +2 PDB. Modern samples have δ13C values from -6 to -41 PDB and δ18O values ranging from +2.6 to +6.7 PDB. The δ13C values suggest the majority of the methane that formed these seep-carbonates is of thermogenic origin, although some mixing from other carbon sources may have occurred. The positive δ18O signatures are suggestive of carbonate formation during dissociation of gas hydrates, while the negative values possibly indicate that some of the formation fluids were warmer than normal in the 17 - 30 C range.