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

The depth of the sulfate-methane transition (SMT) above gas hydrate systems is a direct proxy to interpret upward methane flux and hydrate saturation. However, two competing reaction pathways can potentially form the SMT. Moreover, the pore water profiles across the SMT in shallow sediment show broad variability leading to different interpretations for how carbon, including CH4, cycles within gas-charged sediment sequences over time. The amount and distribution of marine gas hydrate impacts the chemistry of several other dissolved pore water species such as the dissolved inorganic carbon (DIC). A one-dimensional (1-D) numerical model is developed to account for downhole changes in pore water constituents, and transient and steady-state profiles are generated for three distinct hydrate settings. The model explains how an upward flux of CH4 consumes most SO42- at a shallow SMT implying that anaerobic oxidation of methane (AOM) is the dominant SO42- reduction pathway, and how a large flux of 13C-enriched DIC enters the SMT from depth impacting chemical changes across the SMT. Crucially, neither the concentration nor the d13C of DIC can be used to interpret the chemical reaction causing the SMT. The overall thesis objective is to develop generalized models building on this 1-D framework to understand the primary controls on gas hydrate occurrence. Existing 1-D models can provide first-order insights on hydrate occurrence, but do not capture the complexity and heterogeneity observed in natural gas hydrate systems. In this study, a two-dimensional (2-D) model is developed to simulate multiphase flow through porous media to account for heterogeneous lithologic structures (e.g., fractures, sand layers) and to show how focused fluid flow within these structures governs local hydrate accumulation. These simulations emphasize the importance of local, vertical, fluid flux on local hydrate accumulation and distribution. Through analysis of the fluid fluxes in 2-D systems, it is shown that a local Peclet number characterizes the local hydrate and free gas saturations, just as the Peclet number characterizes hydrate saturations in 1-D, homogeneous systems. Effects of salinity on phase equilibrium and co-existence of hydrate and gas phases can also be investigated using these models. Finally, infinite slope stability analysis assesses the model to identify for potential subsea slope failure and associated risks due to hydrate formation and free gas accumulation. These generalized models can be adapted to specific field examples to evaluate the amount and distribution of hydrate and free gas and to identify conditions favorable for economic gas production.