Evidence Of Sulfate Reduction Research Articles

Sulfur Biogeochemical Cycling and Redox Dynamics in a Shale‐Dominated Mountainous Watershed

AbstractSulfur (S) is an essential macronutrient and important component of the earth’s crust, and its cycling has critical impacts on trace metal mobility, water quality, and human health. Pyrite weathering is the primary pathway by which sulfur enters surface waters. However, biogeochemical cycling of sulfur in soils and the river corridor mediates sulfate exports. In this study, we identified the major forms of sulfur across multiple compartments and scales in a pristine mountainous watershed, including shale bedrock weathering profiles, hillslope soils, and alluvial floodplain sediments, in order to provide insight into biogeochemical sulfur cycling in a hydrologically variable alpine system. X‐ray absorption near‐edge spectroscopy (XANES) analysis of shale weathering profiles showed clear evidence of pyrite oxidation to sulfate, with large accumulations of intermediate S(0) (20%–53%). Micro‐scale XANES showed evidence of reprecipitation of pyrite at fracture surfaces within the permanently saturated zone. Organic sulfur dominated S speciation in shallow hillslope soil and floodplain sediment, with little evidence of reduced inorganic S. However, mackinawite formation, representing active sulfate reduction, was observed in saturated oxbow sediments and saturated weathered shale underlying floodplain sediments. Further evidence of sulfate reduction from aqueous sulfur isotopic analysis was observed in shallow groundwater transects across an Fe‐reducing meander, whereas increases in pore water sulfate concentrations implied sulfur oxidation at other locations. The data present an integrated picture of sulfur cycling in a shale‐dominated watershed, where riverine sulfate exports are mediated by biological cycling, particularly in redox‐stratified and temporally dynamic hyporheic zone sediments.

An Assessment of xsBa Flux as a Paleoproductivity Indicator and Its Water‐Depth Dependence in the Easternmost Equatorial Pacific Ocean

AbstractWe present the first regional‐scale records of biogenic Barium (xsBa) fluxes in the Panama basin of the eastern‐equatorial margin of the Pacific Ocean in order to assess xsBa as a paleoproductivity proxy. Measurements of xsBa from 13 cores that range in water depths from about 700 to 3,000 m show an increase in 230Th‐normalized xsBa mass accumulation rates (MARs) with increasing water depth during both marine oxygen isotope stages (MIS) 1 and 2. The correlation of xsBa MARs with depth are strong despite differences in bulk sediment MARs and differing degrees of sediment redistribution. We interpret the increasing xsBa with water depth as likely due to the continued decomposition and remineralization of falling and/or resuspended biogenic particles. xsBa does not seem to be affected by diagenetic sulfate reduction in most of the cores. Calculated estimates of xsBa preservation in the sediment pile are high and fluctuate between 45% and 52% throughout the last 25 kyr. Although xsBa fluxes can be a robust indicator of paleoproductivity, caution is needed if (a) there is evidence of sulfate reduction in sediments being analyzed, and (b) one is trying to quantify differences in paleoproductivity among sites that are located at different depths in the water column.

The Formation of Authigenic Carbonates at a Methane Seep Site in the Northern Part of the Laptev Sea

Authigenic carbonates from cold seeps are unique archives for studying environmental conditions, including biogeochemical processes associated with methane-rich fluid migration through the sediment column. The aim of this research was to study major oxide, mineralogical, and stable isotopic compositions of cold-seep authigenic carbonates collected in the northern part of the Laptev Sea. These carbonates are represented by Mg-calcite with an Mg content of 2% to 8%. The δ13C values range from −27.5‰ to −28.2‰ Vienna Peedee belemnite (VPDB) and indicate that carbonates formed due to anaerobic oxidation of methane, most likely thermogenic in origin. The authigenic pyrite in Mg-calcite is evidence of sulfate reduction during carbonate precipitation. The δ18O values of carbonates vary from 3.5‰ to 3.8‰ VPDB. The calculated δ18Ofluid values show that pore water temperature for precipitated Mg-calcite was comparable to bottom seawater temperature. The presence of authigenic carbonate in the upper horizons of sediments suggests that the sulfate–methane transition zone is shallowly below the sediment–water interface.

Importance of microbial iron reduction in deep sediments of river-dominated continental-margins

Remineralization of organic carbon in deep-sea sediments is thought to proceed primarily via aerobic respiration and sulfate reduction because the supply of nitrate and metal oxides is not usually significant in deep-sea sediments. Dissimilatory metal reduction, on the other hand, may represent a dominant pathway in coastal and continental shelf sediments where delivery of terrigenous Fe(III) and Mn(IV/III) oxides is sufficiently high or where physical mixing processes near the sediment–water interface can result in the reoxidation of Fe2+ or Mn2+. Passive continental margin sediments receiving outflow from large rivers are well-known deposition centers for organic carbon and may also be hotspots for metal-reducing microbial activity, considering the simultaneous rapid deposition of unconsolidated metal oxides of terrigenous origin. Despite its potential, only a few studies have examined the role of microbial metal reduction in Corg remineralization in these environments. To investigate carbon remineralization processes in continental margin sediments, shallow cores across channels and levees in the Congo River fan (~5000m) and Louisiana slope (<1800m) were profiled for the main redox species involved in early diagenesis using a combination of voltammetric gold mercury (Au/Hg) microelectrodes and conventional analyses. Interestingly, metal reduction dominated carbon remineralization processes in the top ~20cm of sediment subject to high deposition, while evidence for sulfate reduction was lacking. These findings suggest that dissimilatory Fe(III) reduction may be more significant than previously thought in continental slope sediments, which may have important implications on carbon cycling in marine environments. In addition, these findings may have geological implications in controlling atmospheric oxygen levels over geological time and the evolution of microbial life on Earth.

Heterogeneous hyporheic zone dechlorination of a TCE groundwater plume discharging to an urban river reach

The typically elevated natural attenuation capacity of riverbed-hyporheic zones is expected to decrease chlorinated hydrocarbon (CHC) groundwater plume discharges to river receptors through dechlorination reactions. The aim of this study was to assess physico-chemical processes controlling field-scale variation in riverbed-hyporheic zone dechlorination of a TCE groundwater plume discharge to an urban river reach. The 50-m long pool–riffle–glide reach of the River Tame in Birmingham (UK) studied is a heterogeneous high energy river environment. The shallow riverbed was instrumented with a detailed network of multilevel samplers. Freeze coring revealed a geologically heterogeneous and poorly sorted riverbed. A chlorine number reduction approach provided a quantitative indicator of CHC dechlorination. Three sub-reaches of contrasting behaviour were identified. Greatest dechlorination occurred in the riffle sub-reach that was characterised by hyporheic zone flows, moderate sulphate concentrations and pH, anaerobic conditions, low iron, but elevated manganese concentrations with evidence of sulphate reduction. Transient hyporheic zone flows allowing input to varying riverbed depths of organic matter are anticipated to be a key control. The glide sub-reach displayed negligible dechlorination attributed to the predominant groundwater baseflow discharge condition, absence of hyporheic zone, transition to more oxic conditions and elevated sulphate concentrations expected to locally inhibit dechlorination. The tail-of-pool–riffle sub-reach exhibited patchy dechlorination that was attributed to sub-reach complexities including significant flow bypass of a low permeability, high organic matter, silty unit of high dechlorination potential. A process-based conceptual model of reach-scale dechlorination variability was developed. Key findings of practitioner relevance were: riverbed-hyporheic zone CHC dechlorination may provide only a partial, somewhat patchy barrier to CHC groundwater plume discharges to a surface water receptor; and, monitoring requirements to assess the variability in CHC attenuation within a reach are expected to be onerous. Further research on transient hyporheic zone dechlorination is recommended.

Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China

High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 µg/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 µg/L in the basin and from 3.1 to 44 µg/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals. The wide range of δ 34S [SO4] values (from − 2.5 to + 36.1‰) in the basin relative to the margins (from + 8‰ to + 15‰) indicate that sulfur is undergoing redox cycling. The highly enriched values point to sulfate reduction that was probably mediated by bacteria. The presence of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) is also evidence of microbial reactions. The depleted signatures indicate that some oxidation of depleted sulfide occurred in the basin. It must be noted that the samples with depleted sulfur isotope values have very low sulfate concentrations and therefore even a small amount of sulfide oxidation will bias the ratio. No significant correlation was observed between δ 34S [SO4] values and total arsenic contents when all the samples were considered. However, the wells in the central basin do appear to become enriched in δ 34S [SO4] as arsenic concentration increases. Although there is evidence for sulfate reduction, it is clear that sulfate reduction does not co-precipitate or sequester arsenic. The one sample with high arsenic that is oxidizing cannot be explained by oxidation of pyrite and is likely an indication that there are multiple redox zones that control arsenic speciation but not necessarily its mobilization and contradict the possibility that Fe-oxyhydroxides sorb appreciable amounts of arsenic in this study area. It is evident that this basin like other two young sedimentary basins (Huhhot and Hetao in Inner Mongolia) of northern China with high arsenic groundwater is transporting arsenic at a very slow rate. The data are consistent with the possibility that the traditional models of arsenic mobilization, namely reductive dissolution of Fe-oxyhydroxides, reduction of As(V) to more mobile As(III), and bacteria mediated reactions, are active to varying degrees. It is also likely that different processes control arsenic mobilization at different locations of the basin and more detailed studies along major flow paths upgradient of the high arsenic aquifers will shed more light on the mechanisms.

Enzymatic recovery of platinum (IV) from industrial wastewater using a biosulphidogenic hydrogenase

It has been established that dissolved heavy metals escaping into the environment pose a serious health hazard. As a result, there is an urgent need for controlling metal emissions into the environment. The aims of this study were to purify and biochemically characterise hydrogenase(s) from sulphate reducing consortium (SRB) and investigate the potential of the purified enzyme(s) in the recovery of platinum from wastewaters. A hydrogenase from sulphate reducing consortium was purified by a combination of PEG 20000 concentration, ion exchange (Toyopearl-Super Q 650 S) and size exclusion (Sephacryl S-200) chromatographies. SDS-PAGE analysis revealed a distinct protein band with a molecular mass of 58 kDa. The investigation of enzymatic platinum (IV) reduction in vitro, showed highest hydrogen-dependent platinum (IV) reducing activity in the presence of hydrogenase and its physiological electron carrier, cytochrome c3. When the purified hydrogenase enzyme (with and without cytochrome c3) was used with the industrial effluent, containing 7.9 mg.l-1 platinum, only 10 – 15% recovery was noted pointing to a suppression of enzyme activity due to the low pH (0.38) of the effluent. Bioremediation studies on industrial effluent using resting SRB cells showed a 34% platinum removal from the effluent while growing SRB cells, within a sulphidogenic reactor, gave a platinum removal of 78%, with the pH of the system fluctuating at around 5.6. Evidence of sulphate reduction and sulphide generation were not observed during this treatment process suggesting that platinum sulphide was not formed and supporting the argument that the increased amount (78%) of platinum removal from the industrial wastewater by the growing SRB cells was due to more hydrogenase/cytochrome c3 enzyme complex being available.

Redox patterns and trace-element behavior in the East Midlands Triassic Sandstone Aquifer, U.K.

Redox conditions exercise important controls on water chemistry in the red-bed Sherwood Sandstone Aquifer of the English East Midlands. A distinct redox boundary exists some 3 to 5 km downgradient of the onset of confined conditions, defined by a 300 mV drop in Eh and complete reaction of dissolved oxygen. The aerobic aquifer contains polluted water with high nitrate concentrations and organic carbon significantly above background concentrations (> 0.2 mg/L). Concentrations of Fe, Mn, and Mo are highest in reducing ground water. As, Sb, Se, and U show a residence-time-dependent increase in aerobic ground water, but are much lower under reducing conditions. Iron oxides are believed to play a key role in determining the spatial patterns in many of these trace elements as a result of Eh- and pH-controlled sorption/desorption reactions, as well as some reductive dissolution in the confined aquifer. Fresh ground water persists in the confined aquifer to approximately 30 km downgradient of the redox boundary. However, SO4 concentrations increase progressively along the flowline as a result of the dissolution of gypsum or anhydrite. Concentrations of available organic carbon are low in ground water (1 mg/L or less) and are also likely to be limited in the sediments; conditions are insufficiently reducing for significant sulphate reduction to have taken place. Only in the extreme down-gradient (eastern) part of the aquifer do conditions become sufficiently reducing with some evidence of sulphate reduction. In this part of the aquifer, ground water is more saline (TDS values up to 10 g/L) and is believed to be composed substantially of older formation water. This has distinctive concentrations of several redox-influenced trace elements, with relatively high Fe, Mn, As, and Sb, occasional high Cr, and low Mo relative to the confined fresh ground water upgradient.

Potential for anaerobic biodegradation of linear alkylbenzene cable oils: Literature review and preliminary investigation

Linear alkylbenzene (LAB) cable oils are used for the electrical insulation of high-voltage underground power cables. Due to thermal movement of the cables, leaks can occur at the joints, resulting in cable oil leaking into the surrounding environment. A review of the literature indicates that relatively little is known about the fate of LAB as a bulk pollutant in soil. To investigate this, a physical model of a cable joint bay was constructed and contaminated with cable oil. Fluorometry confirmed that the cable oil became localised to the upper regions of the saturated zone where dissolved oxygen, pH, and oxidation-reduction measurements indicated that conditions were predominately anaerobic, with evidence for sulphate reduction. Mathematical modelling indicates that these conditions were not due solely to the geochemistry of the system. Mesocosm experiments suggest that LAB may be degraded naturally under anaerobic conditions at rates high enough to justify the use of monitored natural attenuation as a remediation strategy. The mechanisms involved in anaerobic degradation are not currently well understood and more research is required to clarify these and identify the microorganisms involved.

Large‐scale Intrusion of shallow water into a vertical fracture zone in crystalline bedrock: Initial hydrochemical perturbation during tunnel construction at the Äspö Hard Rock Laboratory, southeastern Sweden

On March 13, 1991, construction of the entrance tunnel to the Äspö Hard Rock Laboratory opened a vertical fracture zone at a depth of 70 m. This provides an opportunity to study geochemical changes resulting from shallow water inflow into a crystalline bedrock aquifer as anticipated during construction and operation of a deep repository for spent nuclear fuel. Chloride ion is a natural conservative tracer for mixing between the dilute ([Cl−] &lt; 10 mg L−1) shallow groundwater and the saline ([Cl−] = 5000 mg L−1) native groundwater of the fracture zone. A sharp dilution front, corresponding to 80% dilution of the native groundwater, indicated arrival of shallow groundwater in the entrance tunnel after 3 weeks. In spite of this large input of shallow water, the fracture zone remains predominantly anoxic. Major element hydrochemistry and carbon and oxygen stable isotope data indicate large inputs of alkalinity and biogenic CO2(g). Input of organic carbon with shallow groundwater provides a possible energy and carbon source for anaerobic respiration. There is no evidence for sulfate reduction, and Fe(III) oxyhydroxide fracture minerals are the only other dominant electron acceptor observed.