Biogeochemistry Commons^™

Using Ammonium Pore Water Profiles To Assess Stoichiometry Of Deep Remineralization Processes In Methanogenic Continental Margin Sediments, David J. Burdige, Tomoko Komada

OES Faculty Publications

In many continental margin Sediments, a deep reaction zone exists which is separated from remineralization processes near the sediment surface. Here, methane diffuses upward to a depth where it is oxidized by downwardly diffusing sulfate. However, the methane sources that drive this anaerobic oxidation of methane (AOM) in the sulfate-methane transition zone (SMT) may vary among sites. In particular, these sources can be thought of as either (i) "internal" sources from in situ methanogenesis (regardless of where it occurs in the sediment column) that are ultimately coupled to organic matter deposition and burial, or (ii) "external" sources such as hydrocarbon …

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 …

Sulfur Geochemistry And Diagenesis In A Gas Hydrate Terrane, Cascadia Margin, Offshore Oregon: Role Of Anaerobic Methane Oxidation, David Deigert, Walter S. Borowski

EKU Faculty and Staff Scholarship

We present sulfide mineral data from south Hydrate Ridge located in a gas hydrate terrane, offshore Oregon. Sulfide sulfur concentration and the isotopic composition of sulfur (d³⁴S) in authigenic sulfide minerals are analyzed from sediment samples collected on Ocean Drilling Project (ODP) Leg 204. Shallow sediment samples (<25 >mbsf) assess the relative importance of anaerobic methane oxidation (AMO) as a biogeochemical process, both here and at the Blake Ridge, another well known gas hydrate terrane offshore southeastern United States. Deep samples (>25 mbsf) are used to evaluate sulfur diagenesis and its controls from early Pleistocene to the …

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 …

A Geologic Record Of Competing Sulfate-Depletion Processes Within Continental-Rise Sediments Overlying Methane Gas Hydrates Of The Blake Ridge Region (Continental Rise, Offshore Southeastern United States), Walter S. Borowski, Kathryn G. Takacs, Matthew K. Thompson

EKU Faculty and Staff Scholarship

Geochemical signals locked within sediments and sedimentary rocks record geochemical processes through geologic time. Sulfide minerals (elemental sulfur, iron monosulfides, and pyrite) are formed within marine sediments as dissolved sulfide is produced by various geochemical processes, which include sulfate reduction and anaerobic methane oxidation (AMO). The concentration and sulfur isotopic composition (d³⁴S) of sulfide minerals gives clues about the relative importance of these competing geochemical processes, and consequently about sedimentation rates and upward methane transport.

Marine sediments of the Blake Ridge(offshore South Carolina and Georgia) contain sulfide minerals that point to AMO as an important diagenetic process both …

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 …

A Geologic Record Of Methane Consumption Associated With Methane Gas Hydrates At Blake Ridge Region (Continental Rise, Offshore Southeastern United States), Walter S. Borowski, Kathryn G. Takacs, Matthew K. Thompson

EKU Faculty and Staff Scholarship

Geochemical signals locked within sedimentary rocks are a record of earth processes. Sulfide minerals (elemental sulfur, iron monosulfides, and pyrite) are formed within marine sediments by several different geochemical processes mediated by microbes. Investigating the concentration and sulfur isotopic composition (d³⁴S) of sulfide minerals gives clues about the relative importance of these competing geochemical processes.

Marine sediments of the Blake Ridge(offshore South Carolina and Georgia) contain sulfide minerals that point to anaerobic methane oxidation (AMO) as an important diagenetic process both today and in the recent geological past (Miocene). At the present-day methane-sulfate interface, upward-diffusing methane is consumed …

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 …

Relative Concentration Of Solid-Phase Sulfide Species In Marine Sediments Overlying Gas Hydrate Deposits: Recognition Of The Role Of Anaerobic Methane Oxidation In Authigenic Sulfide Formation, Matthew K. Thompson, Walter S. Borowski, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

Sulfide mineralization in marine sediments occurs when dissolved sulfide, produced by sulfate reduction processes, combines with dissolved iron to form iron sulfide minerals. Sulfide can be produced by oxidation of organic matter or by anaerobic methane oxidation (AMO), which involves the co-consumption of sulfate and methane. The latter process seems especially important within gas hydrate terrains like that of theBlakeRidge(offshore southeasternUnited States), where appreciable amounts of methane diffuse upward to the base of the sulfate reduction zone, or sulfate-methane interface (SMI).

We examine the sediments of two piston cores collected over the Blake Ridge gas hydrate deposits by sequentially extracting …

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. …

Data Report: Carbon Isotopic Composition Of Dissolved Co2, Co2 Gas, And Methane, Blake-Bahama Ridge And Northeast Bermuda Rise, Odp Leg 172, Walter S. Borowski, Namik Cagatay, Y Tournois, Charles K. Paull

EKU Faculty and Staff Scholarship

Carbon isotopic data of interstitial dissolved CO2 (ΣCO2), CO2 gas, and methane show that a variety of microbial diagenetic processes produce the observed isotopic trends. Anaerobic methane oxidation (AMO) is an important process near the sulfate-methane interface (SMI) that strongly influences the isotopic composition of ΣCO2 in the sulfate reduction and upper methanogenic zones, which in turn impacts methane isotopic composition. Dissolved CO2 and methane are maximally depleted in 3C near the SMI, where C values are as light as –31.8‰ and –101‰ PDB for ΣCO2 and methane, respectively. CO2 reduction links the CO2 and methane pools in the methanogenic …

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 …

New Technique Detects Gas Hydrates, Walter S. Borowski, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

As exploration and development moves into deep waters, the possibility of encountering gas hydrates within seafloor sediments becomes increasingly likely. The ability to accurately detect gas hydrates is key to producing deepwater fields, allowing operators to safely design and place offshore drilling and production platforms, subsea production equipment and flow lines, as well as pipelines.