Bottom water hypoxia and its influence on the environment have been topics of increasing concern for many coastal regions. This research addresses both spatial and temporal variability in sediment biogeochemistry at the southeastern region of Corpus Christi Bay, TX, where seasonal (summer) hypoxia occurs. Traditional techniques for determination of a variety of dissolved and solid components, benthic oxygen demand, and sulfate reduction rates were augmented by measurements using solid state microelectrodes to simultaneously determine concentrations of dissolved O2, Mn2+, Fe2+, and [sigma]H2S in multiple small - interval (1 mm) depth profiles of sediment microcosms. Oxygen concentrations in the overlying water were manipulated in the sediment microcosms and electrode depth profile measurements were made over ~ 500 hours of experimentation. Laboratory and field microelectrode results were in good agreement for both norm - oxic and anoxic time periods. Results indicated that iron (Fe2+) and sulfide ([sigma]H2S) were the redox reactive species in these sediments. During hypoxic conditions an upward migration of dissolved Fe2+and [sigma]H2S through the sediment column and, at times, into the overlying water was observed as the dissolved oxygen concentrations decreased. A corresponding decline in the vertical extent of these redox species occurred when the overlying water was re-oxidized. When both dissolved iron and sulfide coexisted, FeS minerals were formed in the sediment, preventing sulfide diffusion into the overlying water. However, after a long duration of hypoxia (> 200 hours) this buffering capacity was exceeded and both iron and sulfide penetrated into the overlying waters. Results indicated that iron may have a greater influence on hypoxia than sulfide because its concentration in the overlying waters during induced hypoxia was an order of magnitude greater than those of sulfide. Moreover, in the southeastern region of the Bay, where mixing was minimal and the water column was shallow, the sediments alone may have caused the onset of the hypoxic event in a relatively short time period (< 5.5 days). These results demonstrated that in shallow marine environments where seasonal hypoxia occurs, such as Corpus Christi Bay, the associated major changes that take place in the sediment biogeochemistry must be included in benthic - pelagic models for overlying water hypoxia.

Bottom water hypoxia and its influence on the environment have been topics of increasing concern for many coastal regions. This research addresses both spatial and temporal variability in sediment biogeochemistry at the southeastern region of Corpus Christi Bay, TX, where seasonal (summer) hypoxia occurs. Traditional techniques for determination of a variety of dissolved and solid components, benthic oxygen demand, and sulfate reduction rates were augmented by measurements using solid state microelectrodes to simultaneously determine concentrations of dissolved O2, Mn2+, Fe2+, and [sigma]H2S in multiple small - interval (1 mm) depth profiles of sediment microcosms. Oxygen concentrations in the overlying water were manipulated in the sediment microcosms and electrode depth profile measurements were made over ~ 500 hours of experimentation. Laboratory and field microelectrode results were in good agreement for both norm - oxic and anoxic time periods. Results indicated that iron (Fe2+) and sulfide ([sigma]H2S) were the redox reactive species in these sediments. During hypoxic conditions an upward migration of dissolved Fe2+and [sigma]H2S through the sediment column and, at times, into the overlying water was observed as the dissolved oxygen concentrations decreased. A corresponding decline in the vertical extent of these redox species occurred when the overlying water was re-oxidized. When both dissolved iron and sulfide coexisted, FeS minerals were formed in the sediment, preventing sulfide diffusion into the overlying water. However, after a long duration of hypoxia (> 200 hours) this buffering capacity was exceeded and both iron and sulfide penetrated into the overlying waters. Results indicated that iron may have a greater influence on hypoxia than sulfide because its concentration in the overlying waters during induced hypoxia was an order of magnitude greater than those of sulfide. Moreover, in the southeastern region of the Bay, where mixing was minimal and the water column was shallow, the sediments alone may have caused the onset of the hypoxic event in a relatively short time period (< 5.5 days). These results demonstrated that in shallow marine environments where seasonal hypoxia occurs, such as Corpus Christi Bay, the associated major changes that take place in the sediment biogeochemistry must be included in benthic - pelagic models for overlying water hypoxia.

Specific conductivity (SC) and total dissolved solids (TDS) are increasingly being used as a parameter used to judge the aquatic health of streams that are impacted by coal mining operations in the Appalachian region of the United States. Due to this, government environmental regulatory bodies have been considering issuing a regulation on SC for all mining operation outfalls. Sulfate typically has the greatest dissolved ion presence in coal mine waters. In literature examining the treatment of mine waters, SC and TDS analysis is typically not reported. The technologies examined in this study were nanofiltration membrane technology and biological sulfate reducing bioreactors. In the nanofiltration study, three different nanofiltration membranes were evaluated for SC reduction: NF270, DK, and NFX. The DK and NFX nanofilters were able to reduce SC levels by an average of 84 percent for both mine waters tested and were able to reach SC levels below the proposed limit of 500 S/cm. The SC levels achieved by the NF270 nanofilters were observed to have much higher variability. The inclusion of microfiltration and simulated-sand filtration were also introduced as a pre-treatment stage in order to determine whether or not nanofiltration performance would improve in terms of SC reduction. In the biological sulfate reducing bioreactor study, multiple bioreactors were established to identify the optimal organic mixture to foster both SC and sulfate reduction. Sulfate reduction began to occur approximately 20 days after the establishment of each bioreactor. SC levels were greater than 13,000 S/cm in each of the bioreactors sampled by the fortieth day of sampling. The probable cause of the increase SC was identified to be the manure/compost used in the study. Future testing should incorporate more sampling in the early phases of experimentation in order to ensure the ability to monitor changes in water quality. / MS

Extensive research has been conducted in numerous coalbed methane (CBM) basins; however, the Williston Basin (WB) remains largely unexamined due to the absence of CBM production despite large coal reserves. CBM in WB coalbeds has been reported, but there has been no systematic study on gas origin and distribution, or hydrogeochemical controls on gas generation to date. This study aims to determine differences in chemistry between groundwaters with and without the presence of CH₄ to better understand factors affecting CBM generation. Results reveal that shallow gas accumulations in WB coalbeds are microbial in origin and formed via CO₂ reduction. CBM is associated with Na-HCO₃ type groundwater with SO₄ concentrations<1 mmole/L due to cation exchange and sulfate reduction, respectively. These groundwaters occur in deeper units of the Fort Union Formation, underlying multiple coalbeds, suggesting that CH₄ is present in waters that have reacted extensively with formations containing low-rank (lignite) coals.

Our ability to understand and predict the fate and transport of contaminants in natural systems is vital if we are to be successful in protecting our water resources. One important aspect of understanding chemical fate and transport in natural systems is identifying key kinetic controls on important redox reactions such as sulfate reduction. Anaerobic microbial activities like sulfate reduction are of particular interest because of the important role they play in the degradation of contaminants in the subsurface. However, current rate estimates for sulfate reduction have a wide range in the literature making it difficult to determine representative rates for a given system. These differences in rate data may be explained by varying kinetic controls on reactions. Push-pull tests were used to evaluate sulfate reduction rates at the wetland-aquifer interface. Anaerobic aquifer water containing abundant sulfate was injected into sulfate-depleted wetland porewater. The injected water was subsequently withdrawn and analyzed for geochemical indicators of sulfate reduction. Complexities in rate data, such as presence of a lag phase, changing rate order and spatial variability, were observed and are hypothesized to be linked to activities of the native microbial population. Subsequent experiments explored the response of native microorganisms to geochemical perturbations using a novel approach to measure directly the effects of a geochemical perturbation on an in situ microbial population and measure rates of resulting reactions. In situ experiments involved colonization of a substrate by microorganisms native to the wetland sediments followed by introductions of native water amended with sulfate and tracer. Experimental results showed that higher sulfate concentrations and warmer seasonal temperatures result in faster sulfate reduction rates and corresponding increases in sulfate reducing bacteria. Findings from this research provide quantitative evidence of how geochemical and microbiological processes are linked in a system not at equilibrium.

At hydrothermal vents, thermal and chemical gradients generated by the mixing of hydrothermal fluids with seawater provide diverse niches for prokaryotic communities. To date, our knowledge of environmental factors that shape bacterial and archaeal community composition and metabolic activities across these gradients within the active sulfide structures is limited. While many studies have laid the foundation for our understanding of the extent of diversity in relation to varying hydrothermal settings, few studies exists regarding the detailed spatial relationships between vent geochemistry and the abundance, distribution, and metabolic characteristics of the endolithic hosted communities. Even fewer data have been generated on the magnitude of metabolic rates and factors controlling the kinetics of these reactions have not been well constrained.

Upon request of the VPR and the thesis advisor this item has been made administrative access only until further notice. / Biodegradation of petroleum has been observed to be one of the most important factors that can alter reservoir chemistry. Biodegradation of petroleum has been connected to the generation of heavy oil at the expense of light hydrocarbon components. Generally, heavy oil is associated with the increasing in metal and sulfur content as well as viscosity. In addition, petroleum biodegradation will result in the production of certain metabolites that are implicated in forming emulsions and corrosion problems in the producing and refining facilities. However, identifying the microrganisms that catalyse this biodegradation is crucial to understanding their role in the hydrocarbons alteration. In this thesis, I addressed the connection between the petroleum biodegradation and the formation of light hydrocarbon components at the expense of heavy hydrocarbon components, and the increase in gas/oil ratio. A comparison between light, extra light, and medium sour crudes lends support to the hypothesis of light hydrocarbons formation through biodegradation of long chain oil components. The results suggested that there was no direct relationship between the relative density of oil and the level of biodegradation, but, there was a positive correlation between the level of biodegradation, the formation of light hydrocarbons, and an increase in the gas/oil ratio. As a first step in investigating this correlation, a metagenomics approach was used to identify and characterize the biodiversity in a European oil field. Extrapolation of the oilfield microbiome data based on an analysis of 200 species generated a hypothetical metabolic map that suggests a new model for petroleum formation and degradation that challenges the accepted dogma in which aerobic and anaerobic petroleum degradation is taking place in the hydrocarbons reservoir, as it is a matter of rate; where the aerobic petroleum degradation targets the short-chain hydrocarbons specifically methane and result in heavy oil generation; whereas the anaerobic petroleum degradation leads to form the gaseous components such as methane, carbon dioxide and hydrogen sulfide. Hence, the gaseous components have a direct impact on the oil density when they represent the majority of the oil field composition by making it more gaseous than liquid.

This study utilizes new geochemical analyses of fluids (formation water and gas) collected predominately from Devonian organic-rich shales and reservoir sandstones from the northern Appalachian Basin margin to investigate basin scale hydrologic processes, water-rock reactions, microbial activity, and natural gas generation. Elemental and isotopic composition of co-produced formation waters and natural gas show that the majority of methane in Devonian organic-rich shales and reservoir sandstones is thermogenic in origin with localized accumulations of microbial gas. Microbial methanogenesis appears to be primarily limited by redox buffered conditions favoring microbial sulfate reduction. Thermal maturity (bioavailability) of shale organic matter and the paucity of formation waters may also explain the lack of extensive microbial methane accumulations. Iodine and strontium isotopes, coupled to elemental chemistry demonstrate basin scale fluid flow and clay mineral diagenesis. Evidence for this is based on anomalously high ¹²⁹I/I values sourced from uranium deposits (fissiogenic production of ¹²⁹I) at the structural front of the Appalachian Basin. Radiogenic ⁸⁷Sr/⁸⁶Sr (up to 0.7220), and depleted boron and potassium concentrations support smectite clay diagenesis at temperatures greater than 120 °C. The development of fissiogenic ¹²⁹I as a tracer of basin scale fluid flow is a novel application of iodine isotopes provided that the sources of cosmogenic and anthropogenic ¹²⁹I are reasonably well constrained. The anomalously high ¹²⁹I/I in Appalachian Basin brines may be alternatively explained by microbial fractionation based on a correlation with decreasing δ¹³C-DIC values and decreasing sulfate concentrations in the range of sulfate reduction. These results demonstrate that the microbial fractionation of iodine isotopes may be possible and an important consideration when interpreting ¹²⁹I/I, regardless of the source of ¹²⁹I. Results from this study have important implications for understanding the controls on and origins of natural gas production in sedimentary basins; tectonically and topographically driven basin scale fluid flow, including diagenetically induced waterrock reactions and mineral ore deposition related to orogenesis; and an improvement of the use of iodine isotopes for understanding large scale fluid flow, and possibly its use as a tracer of organic matter diagenesis and the distribution of radionuclides in the environment.

No description available.

No description available.