Geochemistry Commons^™

Utilizing Isotope Tracing To Assess Land Use Implications To Tap And Stream Water Chemistry, Katrina Alexis Mcfadden

Theses and Dissertations--Biosystems and Agricultural Engineering

Water quality is an issue that continues to be worsened by extreme flooding, specifically in Eastern Kentucky. The most recent 2022 flooding event in Eastern Kentucky resulted in loss of human life, over $23.3 billion in damaged infrastructure, and impaired human health. Infrastructure failures, such as leaky pipes, are a growing challenge in these regions as rebuilding has occurred. Therefore, the goal of this project was to evaluate water quality in two of the counties most impacted by the 2022 flood in Kentucky, Breathitt and Perry Counties, using sulfur isotopes as a novel tracer to identify potentially failures in distribution …

Identification Of The Causes And Extent Of Elevated Methane Concentrations In The Groundwater Of Eastern Kentucky, Cristopher Alvarez Villa

Theses and Dissertations--Earth and Environmental Sciences

Recent development of unconventional oil and gas (UOG) resources has prompted concerns about its potential impact on public health and the quality of water and air resources. Elevated dissolved methane concentrations (> 1 mg/L) have been associated with proximity to UOG development and stray gas, but also with natural microbial activity. Baseline gas data, local hydrogeology and geochemistry context can aid assessment of methane sources and interactions. Methane concentrations in eastern Kentucky groundwater are above the “immediate action” level in some private/domestic water wells, show wide variations over small distances, and have been hypothesized to have different relationships to mining. …

Evaluation Of Cryptic Sulfur Cycling In Marine Sediments, Michael Ngari Mathuri

Open Access Theses & Dissertations

Despite the importance of marine sediments as a carbon sink and many efforts to integrate microbiological with geochemical and geological data, the understanding of microbial organic carbon mineralization processes in marine sediments remains incomplete. There is growing evidence for the existence of an unrecognized oxidative sulfur cycling (cryptic sulfur cycling) above, within and below of the main sulfate reduction zone. For example, sulfate exists in supposedly sulfate-free methanogenic marine sediments from the Aarhus Bay and Black Sea. This implies that sulfur cycling is an ongoing process in the deep biosphere. Quantification of cryptic sulfur cycling is a major challenge because …

A New Method For Ultra-Low Sulfate Extraction And A Pilot Study In Arid Soils, Marisela Montelongo

Open Access Theses & Dissertations

Sulfur in soils is a crucial nutrient for all organisms including plants. Sulfate (SO42-), a water soluable anion, is a good source of this important element. Because of the importance of sulfur for agriculture, the use of sulfate has been well studied in temperate climate zones, and it is generally accepted that microbes play a critical role in controlling the availability of sulfate. Organically bound sulfur, such as sulfate esters and carbon-bonded sulfur, compounds that are generated and decomposed by microbes, are essential sulfur sources for plants under these conditions. For arid environments, knowledge of sulfate turnover in soils by …

Are 34s-Enriched Authigenic Sulfide Minerals A Proxy For Elevated Methane Flux And Gas Hydrates In The Geologic Record?, Walter S. Borowski, Nancy M. Rodriguez, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

The sulfate–methane transition (SMT) zone is a diagenetic transition within anoxic marine sediments created by the metabolic activity of a consortium of sulfate-reducing bacteria and methane-oxidizing Archaea. As interstitial dissolved sulfate is consumed by microbially mediated sulfate reduction of sedimentary organic matter (SOM) and anaerobic oxidation of methane (AOM) large enrichments of ³⁴S occur in the interstitial sulfate pool. These isotopic enrichments are transmitted to the dissolved sulfide pool (∑HS⁻) and subsequently into sulfide minerals (So, ∼FeS, FeS₂).

We investigate the sulfur isotopic composition of pore-water sulfate and sulfide minerals at three sites underlain …

Enrichments Of Heavy Sulfur (34s) In Sulfide Minerals: Gas Hydrates, Methane Delivery, And Anaerobic Methane Oxidation, Walter S. Borowski, Namcy M. Rodriguez, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

The sulfur isotopic composition of authigenic, sedimentary sulfide minerals is largely controlled by sulfate reduction and related processes within sedimentary environments. Histograms show that that d³⁴S values of sulfide minerals forming in depositional and diagenetic environments are most often negative (d³⁴S < 0^o/_oo CDT) reflecting the original isotopic composition of seawater sulfate (now ~21^o/_oo), microbially-mediated fractionations of ~-8 to -40^o/_oo (a = 1.029-1.059) during sulfate reduction, and more extreme fractionations caused by sulfur disproportionation. Enrichments of heavy sulfur (d³⁴S > 0^o/_oo) in sulfide …

A Preliminary Study Of Sulfide Mineral Formation In Methane-Rich, Marine Sediments Associated With Anaerobic Methane Oxidation, Cascadia Continental Margin, Offshore Oregon, David Deigert, Walter S. Borowski

EKU Faculty and Staff Scholarship

Within gas hydrate settings, sulfide mineralization in marine sediments is likely controlled by two microbially-mediated, sulfate-depleting processes: anaerobic methane oxidation (AMO) and sulfate reduction. If large amounts of methane are delivered to the sulfate-methane interface (SMI), predominantly by diffusion, larger amounts of solid sulfide sulfur should occur there as dissolved sulfide combines with iron, forming an authigenic precipitate. We measure the amount of diagenetic sulfide sulfur at three locations in the Hydrate Ridge vicinity by extracting the bulk sedimentary sulfide-phase minerals (S^o, FeS, and FeS₂) through chromium reduction, precipitating sulfide sulfur as silver sulfide, and gravimetrically …

Data Report: Dissolved Sulfide Concentration And Sulfur Isotopic Composition Of Sulfide And Sulfate In Pore Waters, Odp Leg 204, Hydrate Ridge And Vicinity, Cascadia Margin, Offshore Oregon, Walter S. Borowski

EKU Faculty and Staff Scholarship

We report dissolved sulfide sulfur concentrations and the sulfur isotopic composition of dissolved sulfate and sulfide in pore waters from sediments collected during Ocean Drilling Program Leg 204. Porewater sulfate is depleted rapidly as the depth to the sulfate/methane interface (SMI) occurs between 4.5 and 11 meters below seafloor at flank and basin locations. Dissolved sulfide concentration reaches values as high as 11.3 mM in Hole 1251E. Otherwise, peak sulfide concentrations lie between 3.2 and 6.1 mM and occur immediately above the SMI. The sulfur isotopic composition of interstitial sulfate generally becomes enriched in 34 S with increasing sediment depth. …

A Preliminary Comparison Of The Sulfur Geochemistry Between Two Gas Hydrate Terranes, Michael D. Spicer, Walter S. Borowski

EKU Faculty and Staff Scholarship

We compare the authigenic sulfide mineral geochemistry of two, different gas hydrate terranes: the accretionary wedge of the Cascadia continental margin (offshore Oregon) and the passive margin of the Blake Ridge region (offshore southeastern US). We expect diagenetic processes effecting sulfide mineral formation (elemental sulfur, iron monosulfides, and pyrite) within these sediments to respond to differing geologic conditions at each setting. In both settings, methane diffuses upward from gas hydrates to the methane-sulfate interface (SMI), where it is consumed by reaction with sulfate during anaerobic methane oxidation (AMO). This microbially-mediated, diagenetic process produces an interstitial environment conducive to authigenic sulfide …

Sulfide Mineralization In Deep-Water Marine Sediments Related To Methane Transport, Methane Consumption, And Methane Gas Hydrates, Matthew K. Thompson, Walter S. Borowski, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

Patterns of sulfide sulfur concentration and sulfur isotopic composition (d³⁴ S) are perhaps related to upward methane transport, especially in sediments underlain by methane gas hydrate deposits. Increased methane delivery augments the effect of anaerobic methane oxidation (AMO) occurring at the sulfate-methane interface (SMI). Sulfate and methane co-consumption results in production of dissolved sulfide at the interface that is eventually sequestered within sulfide minerals (elemental sulfur, iron monosulfide, pyrite).

We examine the sediments of two piston cores collected over the Blake Ridge gas hydrate deposits (offshore southeastern United States) by extracting total sedimentary sulfide using chromium reduction. We use …

Sulfide Mineralization Within Modern, Deep-Sea Marine Sediments And Oxygenation Of The Early Earth, Matthew K. Thompson, Walter S. Borowski

EKU Faculty and Staff Scholarship

The Earth’s atmosphere and oceans have not always been oxygenated. The exact pathway and timing of the oxygenation of the Earth’s early oceans is poorly constrained, although it appears that oxygenation was essentially complete by the beginning of the Cambrian (545 million years ago). Indeed, the appearance and diversification of the first animals may have been dependent on threshold levels of oxygen. Eventually we intend to use the sulfur isotopic composition of sulfide minerals (iron monosulfides and pyrite) present in sedimentary rocks to reconstruct the oxygenation of Proterozoic oceans, but first must strive to understand sulfide mineral formation in the …

Sulfide Mineralization In Deep-Water Marine Sediments Related To Methane Transport, Methane Consumption, And Methane Gas Hydrates, Matthew K. Thompson, Walter S. Borowski, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

Patterns of sulfide sulfur concentration and sulfur isotopic composition (d³⁴ S) are perhaps related to upward methane transport, especially in sediments underlain by methane gas hydrate deposits. Increased methane delivery augments the effect of anaerobic methane oxidation (AMO) occurring at the sulfate-methane interface (SMI). Sulfate and methane co-consumption results in production of dissolved sulfide at the interface that is eventually sequestered within sulfide minerals (elemental sulfur, iron monosulfide, pyrite).

We examine the sediments of two piston cores collected over the Blake Ridge gas hydrate deposits (offshore southeastern United States) by extracting total sedimentary sulfide using chromium reduction. We use …

Changes In Sulfur Concentration And Sulfur Isotopic Composition Within Authigenic Sulfide Minerals From Sediments Of Miocene Age To The Present, Odp Site 995, Blake Ridge, Offshore Southeastern United States, Kathryn G. Takacs, Walter S. Borowski

EKU Faculty and Staff Scholarship

The Blake Ridge area (offshore southeastern United States) consists of deep-water continental margin sediments overlying deposits of methane gas hydrate. Authigenic sulfide minerals (elemental sulfur, S˚; iron monosulfides, ~FeS; and pyrite, FeS₂) are actively deposited in these sediments due to sulfate reduction and focused anaerobic methane oxidation (AMO) at the sulfate-methane interface (SMI). Sulfide minerals at the present SMI are enriched in ³⁴S relative to those produced by sulfate reduction of organic matter higher in the sulfate reduction zone. ³⁴S enrichments preserved in the sediment column may identify relatively high amounts of AMO and thus record …

Sulfide Mineralization In Deep-Water Marine Sediments Related To Methane Transport, Methane Consumption, And Methane Gas Hydrates, Matthew K. Thompson, Walter S. Borowski, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

Patterns of sulfide sulfur concentration and sulfur isotopic composition (d³⁴S) are perhaps related to upward methane transport, especially in sediments underlain by methane gas hydrate deposits. Increased methane delivery augments the affect of anaerobic methane oxidation (AMO) occurring at the sulfate-methane interface (SMI). Sulfate and methane co-consumption results in production of dissolved sulfide at the interface that is eventually sequestered within sulfide minerals (elemental sulfur, iron monosulfide, pyrite).

We examine the sediments of two piston cores collected over the Blake Ridge gas hydrate deposits (offshore southeastern North America) by extracting total sedimentary sulfide using chromium reduction. We use …

Enrichments Of 34s In Sulfide Minerals Of Deep-Water Marine Sediments Of The Blake Ridge, Offshore Southeastern United States, Kathryn G. Takacs, Walter S. Borowski

EKU Faculty and Staff Scholarship

Past research shows that active sulfide mineralization occurs at the base of the sulfate reduction zone (SRZ) in modern, deep-water, continental-margin sediments that overlie methane gas hydrate. These sulfide minerals (elemental sulfur, Sº; iron monosulfides, ~FeS; and pyrite, FeS₂) are enriched in ³⁴S because of sulfate reduction and anaerobic methane oxidation (AMO) processes occurring above and near the sulfate-methane interface (SMI).

The data in this study show that 5 discrete zones of sulfide minerals are preserved in a 703.8-meter sediment column associated with methane gas hydrate. These zones of sulfide minerals are also enriched in ³⁴S. …

The Meeting Of Two Microbial Worlds: Geochemistry Of The Sulfate-Methane Interface, Walter S. Borowski, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

No abstract provided.

Significance Of Anaerobic Methane Oxidation In Methane-Rich Sediments Overlying The Blake Ridge Gas Hydrates, Walter S. Borowski, Tori M. Hoehler, Mark J. Alperin, Namcy M. Rodriguez, Charles K. Paull

EKU Faculty and Staff Scholarship

A unique set of geochemical pore-water data, characterizing the sulfate reduction and uppermost methanogenic zones, has been collected at the Blake Ridge (offshore southeastern North America) from Ocean Drilling Program (ODP) Leg 164 cores and piston cores. The δ13 C values of dissolved CO2(Σ CO2) are as 13 C-depleted as –37.7‰ PDB (Site 995) at the sulfate-methane interface, reflecting a substantial contribution of isotopically light carbon from methane. Although the geochemical system is complex and difficult to fully quantify, we use two methods to constrain and illustrate the intensity of anaerobic methane oxidation in Blake Ridge sediments. An estimate using …