Sulfur transformations in pilot-scale constructed wetland treating high sulfate-containing contaminated groundwater: a stable isotope assessment.

PubMed

Wu, Shubiao; Jeschke, Christina; Dong, Renjie; Paschke, Heidrun; Kuschk, Peter; Knöller, Kay

2011-12-15

Current understanding of the dynamics of sulfur compounds inside constructed wetlands is still insufficient to allow a full description of processes involved in sulfur cycling. Experiments in a pilot-scale horizontal subsurface flow constructed wetland treating high sulfate-containing contaminated groundwater were carried out. Application of stable isotope approach combined with hydro-chemical investigations was performed to evaluate the sulfur transformations. In general, under inflow concentration of about 283 mg/L sulfate sulfur, sulfate removal was found to be about 21% with a specific removal rate of 1.75 g/m(2)·d. The presence of sulfide and elemental sulfur in pore water about 17.3 mg/L and 8.5 mg/L, respectively, indicated simultaneously bacterial sulfate reduction and re-oxidation. 70% of the removed sulfate was calculated to be immobilized inside the wetland bed. The significant enrichment of (34)S and (18)O in dissolved sulfate (δ(34)S up to 16‰, compared to average of 5.9‰ in the inflow, and δ(18)O up to 13‰, compared to average of 6.9‰ in the inflow) was observed clearly correlated to the decrease of sulfate loads along the flow path through experimental wetland bed. This enrichment also demonstrated the occurrence of bacterial sulfate reduction as well as demonstrated by the presence of sulfide in the pore water. Moreover, the integral approach shows that bacterial sulfate reduction is not the sole process controlling the isotopic composition of dissolved sulfate in the pore water. The calculated apparent enrichment factor (ɛ = -22‰) for sulfur isotopes from the δ(34)S vs. sulfate mass loss was significantly smaller than required to produce the observed difference in δ(34)S between sulfate and sulfide. It indicated some potential processes superimposing bacterial sulfate reduction, such as direct re-oxidation of sulfide to sulfate by oxygen released from plant roots and/or bacterial disproportionation of elemental sulfur. Furthermore, 41% of residual sulfate was calculated to be from sulfide re-oxidation, which demonstrated that the application of stable isotope approach combined with the common hydro-chemical investigations is not only necessary for a general qualitative evaluation of sulfur transformations in constructed wetlands, but also leads to a quantitative description of intermediate processes. Copyright © 2011 Elsevier Ltd. All rights reserved.

A comprehensive sulfur and oxygen isotope study of sulfur cycling in a shallow, hyper-euxinic meromictic lake

NASA Astrophysics Data System (ADS)

Gilhooly, William P.; Reinhard, Christopher T.; Lyons, Timothy W.

2016-09-01

Mahoney Lake is a permanently anoxic and sulfidic (euxinic) lake that has a dense plate of purple sulfur bacteria positioned at mid-water depth (∼7 m) where free sulfide intercepts the photic zone. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and the water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within an aquatic environment with extremely high sulfide concentrations (>30 mM). Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S > 50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake, sulfur disproportionation is likely inoperable or limited to a very narrow zone in the chemocline, and therefore the large instantaneous fractionations are best explained by the microbial process of sulfate reduction. Pyrite extracted from the sediments reflects the isotopic composition of water column sulfide, suggesting that pyrite buried in the euxinic depocenter of the lake formed in the water column. The offset between sulfate and dissolved sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by elevated sulfate reduction rates and inconsistent with appreciable disproportionation within this interval. Water column sulfate exhibits a linear response in δ18OSO4-δ34SSO4 and the slope of this relationship suggests relatively high sulfate reduction rates that appear to respond to seasonal changes in the productivity of purple sulfur bacteria. Although photosynthetic activity within the microbial plate influences the δ18OSO4-δ34SSO4 relationship, the biosignature for photosynthetic sulfur bacteria is restricted to the oxic/anoxic transition zone and is apparently minor relative to the more prevalent process of sulfate reduction operative throughout the light-deprived deeper anoxic water column and sediment pore waters.

SULFATE REDUCTION IN GROUNDWATER: CHARACTERIZATION AND APPLICATIONS FOR REMEDIATION

PubMed Central

Miao, Z.; Brusseau, M. L.; Carroll, K. C.; Carreón-Diazconti, C.; Johnson, B.

2013-01-01

Sulfate is ubiquitous in groundwater, with both natural and anthropogenic sources. Sulfate reduction reactions play a significant role in mediating redox conditions and biogeochemical processes for subsurface systems. They also serve as the basis for innovative in-situ methods for groundwater remediation. An overview of sulfate reduction in subsurface environments is provided, along with a brief discussion of characterization methods and applications for addressing acid mine drainage. We then focus on two innovative, in-situ methods for remediating sulfate-contaminated groundwater, the use of zero-valent iron (ZVI) and the addition of electron-donor substrates. The advantages and limitations associated with the methods are discussed, with examples of prior applications. PMID:21947714

TREATMENT OF HEXAVALENT CHROMIUM IN CHROMITE ORE PROCESSING SOLID WASTE USING A MIXED REDUCTANT SOLUTION OF FERROUS SULFATE AND SODIUM DITHIONITE

EPA Science Inventory

We developed a method for disseminating ferrous iron in the subsurface to enhance chemical reduction of hexavalent chromium (Cr(VI)) in a chromite ore processing solid waste derived from the production of ferrochrome alloy. The method utilizes ferrous sulfate (FeSO4) in combinati...

Impacts of shallow geothermal energy production on redox processes and microbial communities.

PubMed

Bonte, Matthijs; Röling, Wilfred F M; Zaura, Egija; van der Wielen, Paul W J J; Stuyfzand, Pieter J; van Breukelen, Boris M

2013-12-17

Shallow geothermal systems are increasingly being used to store or harvest thermal energy for heating or cooling purposes. This technology causes temperature perturbations exceeding the natural variations in aquifers, which may impact groundwater quality. Here, we report the results of laboratory experiments on the effect of temperature variations (5-80 °C) on redox processes and associated microbial communities in anoxic unconsolidated subsurface sediments. Both hydrochemical and microbiological data showed that a temperature increase from 11 °C (in situ) to 25 °C caused a shift from iron-reducing to sulfate-reducing and methanogenic conditions. Bioenergetic calculations could explain this shift. A further temperature increase (>45 °C) resulted in the emergence of a thermophilic microbial community specialized in fermentation and sulfate reduction. Two distinct maxima in sulfate reduction rates, of similar orders of magnitude (5 × 10(-10) M s(-1)), were observed at 40 and 70 °C. Thermophilic sulfate reduction, however, had a higher activation energy (100-160 kJ mol(-1)) than mesophilic sulfate reduction (30-60 kJ mol(-1)), which might be due to a trade-off between enzyme stability and activity with thermostable enzymes being less efficient catalysts that require higher activation energies. These results reveal that while sulfate-reducing functionality can withstand a substantial temperature rise, other key biochemical processes appear more temperature sensitive.

Comparison of Eh and H2 measurements for delineating redox processes in a contaminated aquifer

USGS Publications Warehouse

Chapelle, Francis H.; Haack, Sheridan K.; Adriaens, Peter; Henry, Mark A.; Bradley, Paul M.

1996-01-01

Measurements of oxidation-reduction potential (Eh) and concentrations of dissolved hydrogen (H2) were made in a shallow groundwater system contaminated with solvents and jet fuel to delineate the zonation of redox processes. Eh measurements ranged from +69 to -158 mV in a cross section of the contaminated plume and accurately delineated oxic from anoxic groundwater. Plotting measured Eh and pH values on an equilibrium stability diagram indicated that Fe(III) reduction was the predominant redox process in the anoxic zone and did not indicate the presence of methanogenesis and sulfate reduction. In contrast, measurements of H2concentrations indicated that methanogenesis predominated in heavily contaminated sediments near the water table surface (H2 ∼ 7.0 nM) and that the methanogenic zone was surrounded by distinct sulfate-reducing (H2 ∼ 1-4 nM) and Fe(III)-reducing (H2 ∼ 0.1-0.8 nM) zones. The presence of methanogenesis, sulfate reduction, and Fe(III) reduction was confirmed by the distribution of dissolved oxygen, sulfate, Fe(II), and methane in groundwater. These results show that H2 concentrations were more useful for identifying anoxic redox processes than Ehmeasurements in this groundwater system. However, H2-based redox zone delineations are more reliable when H2 concentrations are interpreted in the context of electron-acceptor (oxygen, nitrate, sulfate) availability and the presence of final products [Fe(II), sulfide, methane] of microbial metabolism.

The anaerobic degradation of organic matter in Danish coastal sediments - Iron reduction, manganese reduction, and sulfate reduction

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Thamdrup, BO; Hansen, Jens W.

1993-01-01

A combination of porewater and solid phase analysis as well as a series of sediment incubations are used to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark). Solid phase data are integrated with incubation results to define the zones of the various oxidation processes. At S(9), surface Mn enrichments of up to 3.5 wt pct were found, and with such a ready source of Mn, dissimilatory Mn reduction was the only significant anaerobic process of carbon oxidation in the surface 10 cm of the sediment. At S(4) and S(6), active Mn reduction occurred; however, most of the Mn reduction may have resulted from the oxidation of acid volatile sulfides and Fe(2+) rather than by a dissimilatory sulfate. Dissolved Mn(2+) was found to completely adsorb onto sediment containing fully oxidized Mn oxides.

[Bio-electrochemical effect on hydrogenotrophic sulfate reduction stimulated by electrical field in the presence of H2 under atmospheric pressure].

PubMed

Xu, Hui-Wei; Zhang, Xu; Yang, Shan-Shan; Li, Guang-He

2009-07-15

Microbial sulfate reduction rate is limited with H2 as electron donor. In order to improve hydrogenotrophic sulfate reduction under normal atmospheric H2 pressure, a bio-electrochemical system with direct current was designed and performed in this study. Results indicates that sulfate reduction rate (SRR) increases with the augment of current intensity under lower current intensity (I < or = 1.50 mA). When optimum current intensity of 1.50 mA is applied, the SRR is 1.7 to 2.1 times higher than that of the control reactor. The synergistic effect of electrochemistry and microbiology on sulfate reduction varies at different current intensity. Under the condition of I < or = 1.50 mA, the most probable mechanism of SRR increase is that electric or magnetic field stimulates the proliferation of sulfate-reducing bacteria (SRB) and the activity of the enzymes. When I is higher than 1.50 mA, the activity of SRB is inhibited, resulting in lower reduction rate compared with that at lower current. If controlling the cathode potential lower than -0.69 V and H2 partial pressure 1.01 x 10(5) Pa, electro-catalytic sulfate reduction process takes place with H2 as reductant in this bio-electrochemical system. However, the overall reduction rate is still lower than that when I = 1.50 mA is applied, and additionally the energy consumption is much higher. Therefore, electric field of low intensity can enhance hydrogenotrophic sulfate reduction in the presence of H2 under atmospheric pressure.

Realizing high-rate sulfur reduction under sulfate-rich conditions in a biological sulfide production system to treat metal-laden wastewater deficient in organic matter.

PubMed

Sun, Rongrong; Zhang, Liang; Zhang, Zefeng; Chen, Guang-Hao; Jiang, Feng

2017-12-22

Biological sulfur reduction can theoretically produce sufficient sulfide to effectively remove and recover heavy metals in the treatment of organics-deficient sulfate-rich metal-laden wastewater such as acid mine drainage and metallurgic wastewater, using 75% less organics than biological sulfate reduction. However, it is still unknown whether sulfur reduction can indeed compete with sulfate reduction, particularly under high-strength sulfate conditions. The aim of this study was to investigate the long-term feasibility of biological sulfur reduction under high sulfate conditions in a lab-scale sulfur-reducing biological sulfide production (BSP) system with sublimed sulfur added. In the 169-day trial, an average sulfide production rate (SPR) as high as 47 ± 9 mg S/L-h was achieved in the absence of sulfate, and the average SPR under sulfate-rich conditions was similar (53 ± 10 mg S/L-h) when 1300 mg S/L sulfate were fed with the influent. Interestingly, sulfate was barely reduced even at such a high strength and contributed to only 1.5% of total sulfide production. Desulfomicrobium was identified as the predominant sulfidogenic bacterium in the bioreactor. Batch tests further revealed that this sulfidogenic bacteria used elemental sulfur as the electron acceptor instead of the highly bioavailable sulfate, during which polysulfide acted as an intermediate, leading to an even higher bioavailability of sulfur than sulfate. The pathway of sulfur to sulfide conversion via polysulfide in the presence of both sulfur and sulfate was discussed. Collectively, when conditions favor polysulfide formation, sulfur reduction can be a promising and attractive technology to realize a high-rate and low-cost BSP process for treating sulfate-rich metal-laden wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interpreting isotopic analyses of microbial sulfate reduction in oil reservoirs

NASA Astrophysics Data System (ADS)

Hubbard, C. G.; Engelbrektson, A. L.; Druhan, J. L.; Cheng, Y.; Li, L.; Ajo Franklin, J. B.; Coates, J. D.; Conrad, M. E.

2013-12-01

Microbial sulfate reduction in oil reservoirs is often associated with secondary production of oil where seawater (28 mM sulfate) is commonly injected to maintain reservoir pressure and displace oil. The hydrogen sulfide produced can cause a suite of operating problems including corrosion of infrastructure, health exposure risks and additional processing costs. We propose that monitoring of the sulfur and oxygen isotopes of sulfate can be used as early indicators that microbial sulfate reduction is occurring, as this process is well known to cause substantial isotopic fractionation. This approach relies on the idea that reactions with reservoir (iron) minerals can remove dissolved sulfide, thereby delaying the transport of the sulfide through the reservoir relative to the sulfate in the injected water. Changes in the sulfate isotopes due to microbial sulfate reduction may therefore be measurable in the produced water before sulfide is detected. However, turning this approach into a predictive tool requires (i) an understanding of appropriate fractionation factors for oil reservoirs, (ii) incorporation of isotopic data into reservoir flow and reactive transport models. We present here the results of preliminary batch experiments aimed at determining fractionation factors using relevant electron donors (e.g. crude oil and volatile fatty acids), reservoir microbial communities and reservoir environmental conditions (pressure, temperature). We further explore modeling options for integrating isotope data and discuss whether single fractionation factors are appropriate to model complex environments with dynamic hydrology, geochemistry, temperature and microbiology gradients.

Use of Acetate, Propionate, and Butyrate for Reduction of Nitrate and Sulfate and Methanogenesis in Microcosms and Bioreactors Simulating an Oil Reservoir

PubMed Central

Shen, Yin; An, Dongshan; Voordouw, Gerrit

2017-01-01

ABSTRACT Acetate, propionate, and butyrate (volatile fatty acids [VFA]) occur in oil field waters and are frequently used for microbial growth of oil field consortia. We determined the kinetics of use of these VFA components (3 mM each) by an anaerobic oil field consortium in microcosms containing 2 mM sulfate and 0, 4, 6, 8, or 13 mM nitrate. Nitrate was reduced first, with a preference for acetate and propionate. Sulfate reduction then proceeded with propionate (but not butyrate) as the electron donor, whereas the fermentation of butyrate (but not propionate) was associated with methanogenesis. Microbial community analyses indicated that Paracoccus and Thauera (Paracoccus-Thauera), Desulfobulbus, and Syntrophomonas-Methanobacterium were the dominant taxa whose members catalyzed these three processes. Most-probable-number assays showed the presence of up to 107/ml of propionate-oxidizing sulfate-reducing bacteria (SRB) in waters from the Medicine Hat Glauconitic C field. Bioreactors with the same concentrations of sulfate and VFA responded similarly to increasing concentrations of injected nitrate as observed in the microcosms: sulfide formation was prevented by adding approximately 80% of the nitrate dose needed to completely oxidize VFA to CO2 in both. Thus, this work has demonstrated that simple time-dependent observations of the use of acetate, propionate, and butyrate for nitrate reduction, sulfate reduction, and methanogenesis in microcosms are a good proxy for these processes in bioreactors, monitoring of which is more complex. IMPORTANCE Oil field volatile fatty acids acetate, propionate, and butyrate were specifically used for nitrate reduction, sulfate reduction, and methanogenic fermentation. Time-dependent analyses of microcosms served as a good proxy for these processes in a bioreactor, mimicking a sulfide-producing (souring) oil reservoir: 80% of the nitrate dose required to oxidize volatile fatty acids to CO2 was needed to prevent souring in both. Our data also suggest that propionate is a good substrate to enumerate oil field SRB. PMID:28130297

Geochemical evidence for cryptic sulfur cycling in salt marsh sediments

NASA Astrophysics Data System (ADS)

Mills, Jennifer V.; Antler, Gilad; Turchyn, Alexandra V.

2016-11-01

Cryptic sulfur cycling is an enigmatic process in which sulfate is reduced to some lower-valence state sulfur species and subsequently quantitatively reoxidized; the rate and microbial energetics of this process and how prevalent it may be in the environment remain controversial. Here we investigate sulfur cycling in salt marsh sediments from Norfolk, England where we observe high ferrous iron concentrations with no depletion of sulfate or change in the sulfur isotope ratio of that sulfate, but a 5‰ increase in the oxygen isotope ratio in sulfate, indicating that sulfate has been through a reductive cycle replacing its oxygen atoms. This cryptic sulfur cycle was replicated in laboratory incubations using 18O-enriched water, demonstrating that the field results do not solely result from mixing processes in the natural environment. Numerical modeling of the laboratory incubations scaled to represent the salt marsh sediments suggests that the uptake rate of sulfate during this cryptic sulfur cycling is similar to the uptake rate of sulfate during the fastest microbial sulfate reduction that has been measured in the natural environment. The difference is that during cryptic sulfur cycling, all of the sulfur is subsequently reoxidized to sulfate. We discuss mechanisms for this pathway of sulfur cycling including the possible link to the subsurface iron cycle.

Anaerobic microbial redox processes in a landfill leachate contaminated aquifer (Grindsted, Denmark)

NASA Astrophysics Data System (ADS)

Ludvigsen, L.; Albrechtsen, H.-J.; Heron, G.; Bjerg, P. L.; Christensen, T. H.

1998-10-01

The distribution of anaerobic microbial redox processes was investigated along a 305 m long transect of a shallow landfill-leachate polluted aquifer. By unamended bioassays containing sediment and groundwater, 37 samples were investigated with respect to methane production, sulfate, iron, and manganese reduction, and denitrification. Methane production was restricted to the most reduced part of the plume with rates of 0.003-0.055 nmol CH 4/g dry weight/day. Sulfate reduction was observed at rates of maximum 1.8 nmol SO 42-/g dry weight/day along with methane production in the plume, but sulfate reduction was also observed further downgradient of the landfill. Iron reduction at rates of 5-19 nmol Fe(II)/g dry weight/day was observed in only a few samples, but this may be related to a high detection limit for the iron reducing bioassay. Manganese reduction at rates of maximum 2.4 nmol Mn(II)/g dry weight/day and denitrification at rates of 0.2-37 nmol N 2O-N/g dry weight/day were observed in the less reduced part of the plume. All the redox processes were microbial processes. In many cases, several redox processes took place simultaneously, but in all samples one process dominated accounting for more than 70% of the equivalent carbon conversion. The bioassays showed that the redox zones in the plume identified from the groundwater composition (e.g. as methanogenic and sulfate reducing) locally hosted also other redox processes (e.g. iron reduction). This may have implications for the potential of the redox zone to degrade trace amounts of organic chemicals and suggests that unamended bioassays may be an important supplement to other approaches in characterizing the redox processes in an anaerobic plume.

Volatile fatty acids as substrates for iron and sulfate reduction in Arctic marine sediments, Svalbard

NASA Astrophysics Data System (ADS)

Finke, N.; Vandieken, V.; Jorgensen, B. B.

2006-12-01

Anaerobic degradation of complex organic material in aquatic systems is a multi-step process. The metabolic products of fermentative bacteria serve as electron donors for the terminal oxidizing bacteria. In marine sediments, iron reduction and sulfate reduction are generally the most important terminal oxidation processes in the upper anoxic zone [1]. Microorganisms that reduce iron and sulfate may use a broad range of electron donors, yet the list of potential substrates provides little information about the substrates used in situ by these organisms. Investigations on the electron donors for sulfate reducers in marine sediments have shown that volatile fatty acids (VFA), and in particular acetate, together with hydrogen are the major substrates (e.g. [2-4]). Similar investigations for iron reduction or simultaneous iron and sulfate reduction are lacking for marine sediments. Furthermore, most of these studies were made in temperate sediments and little is known about the substrates for sulfate reducers in permanently cold sediments, which account for >90% of the ocean floor [5]. We investigated the relative contributions of iron reduction and sulfate reduction to the terminal oxidation of organic carbon and the importance of acetate, lactate, propionate, and isobutyrate as electron donors for iron and sulfate reduction in permanently cold, Arctic sediments from Svalbard. In the surface layer (0-2 cm) sulfate reduction accounted for 2/3 of the organic carbon oxidation (determined as DIC production), the remaining 1/3 were attributed to iron reduction. In the 5-9 cm layer sulfate reduction was the sole important terminal oxidation step. The contribution of acetate to terminal oxidation was determined by radiotracer incubation as well as from the accumulation after the inhibition of sulfate reduction by selenate. The rates determined with the two methods varied by less than 20%. Acetate turnover, determined with the tracer incubations, accounted for 10 and 40% of the sulfate reduction in the 0-2 cm and 5-9 cm layer, respectively. Together acetate, lactate, propionate and isobutyrate accounted for 21 and 52% of the sulfate reduction, in the 0-2 cm and 5-9 cm layer, respectively. Assigning all acetate and lactate turnover in the selenate inhibited samples, these two VFA account for less than 10 and 2%, respectively, of the iron reduction in the 0-2 cm layer. Thus, 67 and 48% of the terminal oxidation in the 0-2cm and 5-9 cm layer must be driven by electron donors other than the investigated VFA. The sulfate reduction rates as well as the VFA turnover rates were at the lower end of reported rates from similar studies, mostly measured in temperate sites (e.g. [2-4, 6, 7]). Comparing a series of studies with different in situ temperatures shows, parameters other than in situ temperature seem to be more important in determining the sulfate reduction and VFA turnover rates. [1] Thamdrup, B. (2000) Bacterial manganese and iron reduction in aquatic sediments, 41-84 pp. Kluwer Academic / Plenum Publ., New York. [2] Parkes, R.J., Gibson, G.R., Mueller-Harvey, I., Buckingham, W.J. and Herbert, R.A. (1989) J. Gen. Microbiol. 135, 175-187. [3] Christensen, D. (1984) Limnol. Oceanogr. 29, 189-192. [4] Shaw, D.G. and McIntosh, D.J. (1990) Estuarine Coastal & Shelf Science 31, 775-788. [5] Levitus, S. and Boyer, T. (1994) World Ocean Atlas, pp. US Department of Commerce, Washington, DC. [6] Kristensen, E., King, G.M., Holmer, M., Banta, G.T., Jensen, M.H., Hansen, K. and Bussarawit, N. (1994) Mar. Ecol.-Prog. Ser. 109, 245-255. [7] Wellsbury, P. and Parkes, R.J. (1995) FEMS Microbiol. Ecol. 17, 85-94.

The impact of biostimulation on the fate of sulfate and associated sulfur dynamics in groundwater

NASA Astrophysics Data System (ADS)

Miao, Ziheng; Carreón-Diazconti, Concepcion; Carroll, Kenneth C.; Brusseau, Mark L.

2014-08-01

The impact of electron-donor addition on sulfur dynamics for a groundwater system with low levels of metal contaminants was evaluated with a pilot-scale biostimulation test conducted at a former uranium mining site. Geochemical and stable-isotope data collected before, during, and after the test were analyzed to evaluate the sustainability of sulfate reducing conditions induced by the test, the fate of hydrogen sulfide, and the impact on aqueous geochemical conditions. The results of site characterization activities conducted prior to the test indicated the absence of measurable bacterial sulfate reduction. The injection of an electron donor (ethanol) induced bacterial sulfate reduction, as confirmed by an exponential decrease of sulfate concentration in concert with changes in oxidation-reduction potential, redox species, alkalinity, production of hydrogen sulfide, and fractionation of δ34S-sulfate. High, stoichiometrically-equivalent hydrogen sulfide concentrations were not observed until several months after the start of the test. It is hypothesized that hydrogen sulfide produced from sulfate reduction was initially sequestered in the form of iron sulfides until the exhaustion of readily reducible iron oxides within the sediment. The fractionation of δ34S for sulfate was atypical, wherein the enrichment declined in the latter half of the experiment. It was conjectured that mixing effects associated with the release of sulfate from sulfate minerals associated with the sediments, along with possible sulfide re-oxidation contributed to this behavior. The results of this study illustrate the biogeochemical complexity that is associated with in-situ biostimulation processes involving bacterial sulfate reduction.

THE IMPACT OF BIOSTIMULATION ON THE FATE OF SULFATE AND ASSOCIATED SULFUR DYNAMICS IN GROUNDWATER

PubMed Central

Miao, Ziheng; Carreón-Diazconti, Concepcion; Carroll, Kenneth C.; Brusseau, Mark L.

2014-01-01

The impact of electron-donor addition on sulfur dynamics for a groundwater system with low levels of metal contaminants was evaluated with a pilot-scale biostimulation test conducted at a former uranium mining site. Geochemical and stable-isotope data collected before, during, and after the test were analyzed to evaluate the sustainability of sulfate reducing conditions induced by the test, the fate of hydrogen sulfide, and the impact on aqueous geochemical conditions. The results of site characterization activities conducted prior to the test indicated the absence of measurable bacterial sulfate reduction. The injection of an electron donor (ethanol) induced bacterial sulfate reduction, as confirmed by an exponential decrease of sulfate concentration in concert with changes in oxidation-reduction potential, redox species, alkalinity, production of hydrogen sulfide, and fractionation of δ34S-sulfate. High, stoichiometrically-equivalent hydrogen sulfide concentrations were not observed until several months after the start of the test. It is hypothesized that hydrogen sulfide produced from sulfate reduction was initially sequestered in the form of iron sulfides until the exhaustion of readily reducible iron oxides associated with the sediment. The fractionation of δ34S for sulfate was atypical, wherein the enrichment declined in the latter half of the experiment. It was conjectured that mixing effects associated with the release of sulfate from sulfate minerals associated with the sediments, along with possible sulfide re-oxidation contributed to this behavior. The results of this study illustrate the biogeochemical complexity that is associated with in-situ biostimulation processes involving bacterial sulfate reduction. PMID:25016586

Practical applications of sulfate-reducing bacteria to control acid mine drainage at the Lilly/Orphan Boy Mine near Elliston, Montana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Canty, M.

The overall purpose of this document is to provide a detailed technical description of a technology, biological sulfate reduction, which is being demonstrated under the Mine Waste Technology Pilot Program, and provide the technology evaluation process undertaken to select this technology for demonstration. In addition, this document will link the use of the selected technology to an application at a specific site. The purpose of this project is to develop technical information on the ability of biological sulfate reduction to slow the process of acid generation and, thus, improve water quality at a remote mine site. Several technologies are screenedmore » for their potential to treat acid mine water and to function as a source control for a specific acid-generating situation: a mine shaft and associated underground workings flooded with acid mine water and discharging a small flow from a mine opening. The preferred technology is the use of biological sulfate reduction. Sulfate-reducing bacteria are capable of reducing sulfate to sulfide, as well as increasing the pH and alkalinity of water affected by acid generation. Soluble sulfide reacts with the soluble metals in solution to form insoluble metal sulfides. The environment needed for efficient sulfate-reducing bacteria growth decreases acid production by reducing the dissolved oxygen in water and increasing pH. A detailed technical description of the sulfate-reducing bacteria technology, based on an extensive review of the technical literature, is presented. The field demonstration of this technology to be performed at the Lilly/Orphan Boy Mine is also described. Finally, additional in situ applications of biological sulfate reduction are presented.« less

Characterization of two subsurface H2-utilizing bacteria, Desulfomicrobium hypogeium sp. nov. and Acetobacterium psammolithicum sp. nov., and their ecological roles.

PubMed

Krumholz, L R; Harris, S H; Tay, S T; Suflita, J M

1999-06-01

We examined the relative roles of acetogenic and sulfate-reducing bacteria in H2 consumption in a previously characterized subsurface sandstone ecosystem. Enrichment cultures originally inoculated with ground sandstone material obtained from a Cretaceous formation in central New Mexico were grown with hydrogen in a mineral medium supplemented with 0.02% yeast extract. Sulfate reduction and acetogenesis occurred in these cultures, and the two most abundant organisms carrying out the reactions were isolated. Based on 16S rRNA analysis data and on substrate utilization patterns, these organisms were named Desulfomicrobium hypogeium sp. nov. and Acetobacterium psammolithicum sp. nov. The steady-state H2 concentrations measured in sandstone-sediment slurries (threshold concentration, 5 nM), in pure cultures of sulfate reducers (threshold concentration, 2 nM), and in pure cultures of acetogens (threshold concentrations 195 to 414 nM) suggest that sulfate reduction is the dominant terminal electron-accepting process in the ecosystem examined. In an experiment in which direct competition for H2 between D. hypogeium and A. psammolithicum was examined, sulfate reduction was the dominant process.

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

NASA Astrophysics Data System (ADS)

Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

2016-09-01

The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and provide important mechanistic details about the overall TSR process.

Tracking photosynthetic sulfide oxidation in a meromictic lake using sulfate δ34S and δ18O

NASA Astrophysics Data System (ADS)

Gilhooly, W. P.; Reinhard, C.; Lyons, T. W.; Glass, J. B.

2012-12-01

Phototrophic sulfur bacteria oxidize sulfide and fix carbon dioxide in the presence of sunlight without producing oxygen. Environmental conditions in the Paleo- and Mesoproterozoic, when atmospheric oxygen concentrations were at low levels and portions of the oceans were anoxic and sulfidic (euxinic), were conducive to widespread carbon fixation by anoxygenic photosynthesis. This pathway may have helped sustain euxinic conditions in the Proterozoic water column. With limited organic biomarker and geochemical evidence for widespread production of anoxygenic phototrophs, however, additional proxies are needed to fingerprint paleoecological and biogeochemical signals associated with photic zone euxinia. Paired δ34S and δ18O from ancient sulfates (gypsum, barite, or CAS) may offer an added constraint on the history and ecological dominance of photosynthetic S-oxidation. Sulfate-oxygen can fractionate during sulfate reduction, but the extent of isotopic enrichment is controlled either by kinetic isotope effects imparted during intracellular enzymatic steps or equilibrium oxygen exchange with ambient water. An improved understanding of these processes can be gained from modern natural environments. Mahoney Lake is a density-stratified lake located within the White Lake Basin of British Columbia. The euxinic water column supports a dense plate of purple sulfur bacteria (Amoebobacter purpureus) that thrives where free sulfide intercepts the photic zone at ~7 m water depth. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within this meromictic lake. Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S >50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake ([H2S] = 30 mM), sulfur disproportionation is likely inoperable, and so the large instantaneous fractionations are best explained by single-step sulfate reduction. The offset between sulfate and sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by sulfide oxidation or decreasing sulfate reduction rates. Sulfate exhibits a curvilinear response in δ18OSO4/δ34SSO4 that approaches δ18OSO4 values (~24-33‰) in equilibrium with ambient water (δ18OH2O = -2.2‰). Although an inverse relationship between δ18OSO4/δ18OH2O is inconsistent with chemical sulfide oxidation (typically a positive relationship), fine-scale variations in δ34SSO4 and δ18OSO4 at the chemocline imply sulfate reduction coupled with near quantitative reoxidation by A. purpureus. Although observed within the microbial plate, this photosynthetic S-bacteria biosignature is restricted to the oxic/anoxic transition zone and is apparently swamped by the more prevalent process of sulfate reduction operative throughout the anoxic water column and sediment pore waters.

Theoretical study on the reactivity of sulfate species with hydrocarbons

USGS Publications Warehouse

Ma, Q.; Ellis, G.S.; Amrani, A.; Zhang, T.; Tang, Y.

2008-01-01

The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions SO42 - are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of SO42 - is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions (HSO4-) and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive. Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of HSO4- relative to SO42 -. However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO4- is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as SO42 -, aqueous calcium sulfate ([CaSO4](aq)), and aqueous magnesium sulfate ([MgSO4](aq)). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions (HSO4-) and/or magnesium sulfate contact ion-pairs ([MgSO4]CIP) rather than 'free' sulfate ions (SO42 -) or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR. ?? 2008 Elsevier Ltd. All rights reserved.

Theoretical study on the reactivity of sulfate species with hydrocarbons

NASA Astrophysics Data System (ADS)

Ma, Qisheng; Ellis, Geoffrey S.; Amrani, Alon; Zhang, Tongwei; Tang, Yongchun

2008-09-01

The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions SO42- are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of SO42- is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions ( HSO4-) and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive. Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of HSO4- relative to SO42-. However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO4- is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as SO42-, aqueous calcium sulfate ([CaSO 4] (aq)), and aqueous magnesium sulfate ([MgSO 4] (aq)). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions ( HSO4-) and/or magnesium sulfate contact ion-pairs ([MgSO 4] CIP) rather than 'free' sulfate ions ( SO42-) or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR.

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate.

PubMed

Thorup, Casper; Schramm, Andreas; Findlay, Alyssa J; Finster, Kai W; Schreiber, Lars

2017-07-18

This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. IMPORTANCE Sulfide oxidation and sulfate reduction, the two major branches of the sulfur cycle, are usually ascribed to distinct sets of microbes with distinct diagnostic genes. Here we show a more complex picture, as D. alkaliphilus , with the genomic setup of a sulfate reducer, grows by sulfide oxidation. The high expression of genes typically involved in the sulfate reduction pathway suggests that these genes, including the reductive-type dissimilatory bisulfite reductases, are also involved in as-yet-unresolved sulfide oxidation pathways. Finally, D. alkaliphilus is closely related to cable bacteria, which grow by electrogenic sulfide oxidation. Since there are no pure cultures of cable bacteria, D. alkaliphilus may represent an exciting model organism in which to study the physiology of this process. Copyright © 2017 Thorup et al.

Modeling the anaerobic digestion of cane-molasses vinasse: extension of the Anaerobic Digestion Model No. 1 (ADM1) with sulfate reduction for a very high strength and sulfate rich wastewater.

PubMed

Barrera, Ernesto L; Spanjers, Henri; Solon, Kimberly; Amerlinck, Youri; Nopens, Ingmar; Dewulf, Jo

2015-03-15

This research presents the modeling of the anaerobic digestion of cane-molasses vinasse, hereby extending the Anaerobic Digestion Model No. 1 with sulfate reduction for a very high strength and sulfate rich wastewater. Based on a sensitivity analysis, four parameters of the original ADM1 and all sulfate reduction parameters were calibrated. Although some deviations were observed between model predictions and experimental values, it was shown that sulfates, total aqueous sulfide, free sulfides, methane, carbon dioxide and sulfide in the gas phase, gas flow, propionic and acetic acids, chemical oxygen demand (COD), and pH were accurately predicted during model validation. The model showed high (±10%) to medium (10%-30%) accuracy predictions with a mean absolute relative error ranging from 1% to 26%, and was able to predict failure of methanogenesis and sulfidogenesis when the sulfate loading rate increased. Therefore, the kinetic parameters and the model structure proposed in this work can be considered as valid for the sulfate reduction process in the anaerobic digestion of cane-molasses vinasse when sulfate and organic loading rates range from 0.36 to 1.57 kg [Formula: see text]  m(-3) d(-1) and from 7.66 to 12 kg COD m(-3) d(-1), respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Use of Acetate, Propionate, and Butyrate for Reduction of Nitrate and Sulfate and Methanogenesis in Microcosms and Bioreactors Simulating an Oil Reservoir.

PubMed

Chen, Chuan; Shen, Yin; An, Dongshan; Voordouw, Gerrit

2017-04-01

Acetate, propionate, and butyrate (volatile fatty acids [VFA]) occur in oil field waters and are frequently used for microbial growth of oil field consortia. We determined the kinetics of use of these VFA components (3 mM each) by an anaerobic oil field consortium in microcosms containing 2 mM sulfate and 0, 4, 6, 8, or 13 mM nitrate. Nitrate was reduced first, with a preference for acetate and propionate. Sulfate reduction then proceeded with propionate (but not butyrate) as the electron donor, whereas the fermentation of butyrate (but not propionate) was associated with methanogenesis. Microbial community analyses indicated that Paracoccus and Thauera ( Paracoccus - Thauera ), Desulfobulbus , and Syntrophomonas - Methanobacterium were the dominant taxa whose members catalyzed these three processes. Most-probable-number assays showed the presence of up to 10 7 /ml of propionate-oxidizing sulfate-reducing bacteria (SRB) in waters from the Medicine Hat Glauconitic C field. Bioreactors with the same concentrations of sulfate and VFA responded similarly to increasing concentrations of injected nitrate as observed in the microcosms: sulfide formation was prevented by adding approximately 80% of the nitrate dose needed to completely oxidize VFA to CO 2 in both. Thus, this work has demonstrated that simple time-dependent observations of the use of acetate, propionate, and butyrate for nitrate reduction, sulfate reduction, and methanogenesis in microcosms are a good proxy for these processes in bioreactors, monitoring of which is more complex. IMPORTANCE Oil field volatile fatty acids acetate, propionate, and butyrate were specifically used for nitrate reduction, sulfate reduction, and methanogenic fermentation. Time-dependent analyses of microcosms served as a good proxy for these processes in a bioreactor, mimicking a sulfide-producing (souring) oil reservoir: 80% of the nitrate dose required to oxidize volatile fatty acids to CO 2 was needed to prevent souring in both. Our data also suggest that propionate is a good substrate to enumerate oil field SRB. Copyright © 2017 American Society for Microbiology.

Sources and turnover of organic carbon and methane in fjord and shelf sediments off northern Norway

NASA Astrophysics Data System (ADS)

Sauer, Simone; Hong, Wei-Li; Knies, Jochen; Lepland, Aivo; Forwick, Matthias; Klug, Martin; Eichinger, Florian; Baranwal, Soma; Crémière, Antoine; Chand, Shyam; Schubert, Carsten J.

2016-10-01

To better understand the present and past carbon cycling and transformation processes in methane-influenced fjord and shelf areas of northern Norway, we compared two sediment cores from the Hola trough and from Ullsfjorden. We investigated (1) the organic matter composition and sedimentological characteristics to study the sources of organic carbon (Corg) and the factors influencing Corg burial, (2) pore water geochemistry to determine the contribution of organoclastic sulfate reduction and methanogenesis to total organic carbon turnover, and (3) the carbon isotopic signature of hydrocarbons to identify the carbon transformation processes and gas sources. High sedimentation and Corg accumulation rates in Ullsfjorden support the notion that fjords are important Corg sinks. The depth of the sulfate-methane-transition (SMT) in the fjord is controlled by the supply of predominantly marine organic matter to the sediment. Organoclastic sulfate reduction accounts for 60% of the total depth-integrated sulfate reduction in the fjord. In spite of the presence of ethane, propane, and butane, we suggest a purely microbial origin of light hydrocarbons in the sediments based on their low δ13C values. In the Hola trough, sedimentation and Corg accumulation rates changed during the deglacial-to-post-glacial transition from approximately 80 cm ka-1 to erosion at present. Thus, Corg burial in this part of the shelf is presently absent. Low organic matter content in the sediment and low rates of organoclastic sulfate reduction (only 3% of total depth-integrated sulfate reduction) entail that the shallow depth of the SMT is controlled mostly by ascending thermogenic methane from deeper sources.

Aerosol pH buffering in the southeastern US: Fine particles remain highly acidic despite large reductions in sulfate

NASA Astrophysics Data System (ADS)

Weber, R. J.; Guo, H.; Russell, A. G.; Nenes, A.

2015-12-01

pH is a critical aerosol property that impacts many atmospheric processes, including biogenic secondary organic aerosol formation, gas-particle phase partitioning, and mineral dust or redox metal mobilization. Particle pH has also been linked to adverse health effects. Using a comprehensive data set from the Southern Oxidant and Aerosol Study (SOAS) as the basis for thermodynamic modeling, we have shown that particles are currently highly acidic in the southeastern US, with pH between 0 and 2. Sulfate and ammonium are the main acid-base components that determine particle pH in this region, however they have different sources and their concentrations are changing. Over 15 years of network data show that sulfur dioxide emission reductions have resulted in a roughly 70 percent decrease in sulfate, whereas ammonia emissions, mainly link to agricultural activities, have been largely steady, as have gas phase ammonia concentrations. This has led to the view that particles are becoming more neutralized. However, sensitivity analysis, based on thermodynamic modeling, to changing sulfate concentrations indicates that particles have remained highly acidic over the past decade, despite the large reductions in sulfate. Furthermore, anticipated continued reductions of sulfate and relatively constant ammonia emissions into the future will not significantly change particle pH until sulfate drops to clean continental background levels. The result reshapes our expectation of future particle pH and implies that atmospheric processes and adverse health effects linked to particle acidity will remain unchanged for some time into the future.

Bioturbation and the role of microniches for sulfate reduction in coastal marine sediments.

PubMed

Bertics, Victoria J; Ziebis, Wiebke

2010-11-01

The effects of bioturbation in marine sediments are mainly associated with an increase in oxic and oxidized zones through an influx of oxygen-rich water deeper into the sediment and the rapid transport of particles between oxic and anoxic conditions. However, macrofaunal activity also can increase the occurrence of reduced microniches and anaerobic processes, such as sulfate reduction. Our goal was to determine the two-dimensional distribution of microniches associated with burrows of a ghost shrimp (Neotrypaea californiensis) and to determine microbial activities. In laboratory experiments, detailed measurements of sulfate reduction rates (SRR) were measured by injecting, in a 1 cm grid, radiolabelled sulfate directly into a narrow aquarium (40 cm × 30 cm × 3 cm) containing the complex burrow of an actively burrowing shrimp. Light-coloured oxidized burrow walls, along with black reduced microniches, were clearly visible through the aquarium walls. Direct injection of radiotracers allowed for whole-aquarium incubation to obtain two-dimensional documentation of sulfate reduction. Results indicated SRR were up to three orders of magnitude higher (140-790 nmol SO(4) (2-) cm(-3) day(-1) ) in reduced microniches associated with burrows when compared with the surrounding sediment. Additionally, some of the subsurface sulfate-reducing microniches associated with the burrow system appeared to be zones of dinitrogen fixation. Bioturbation may also lead to decreased sulfate reduction in other microniches and the sum of the activity in all microniches might not result in a total increase of sulfate reduction compared with non-bioturbated control sediments. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

Methanogenic and Sulfate-Reducing Activities in a Hypersaline Microbial Mat and Associated Microbial Diversity.

PubMed

Cadena, Santiago; García-Maldonado, José Q; López-Lozano, Nguyen E; Cervantes, Francisco J

2018-05-01

Methanogenesis and sulfate reduction are important microbial processes in hypersaline environments. However, key aspects determining substrate competition between these microbial processes have not been well documented. We evaluated competitive and non-competitive substrates for stimulation of both processes through microcosm experiments of hypersaline microbial mat samples from Guerrero Negro, Baja California Sur, Mexico, and we assessed the effect of these substrates on the microbial community composition. Methylotrophic methanogenesis evidenced by sequences belonging to methanogens of the family Methanosarcinaceae was found as the dominant methanogenic pathway in the studied hypersaline microbial mat. Nevertheless, our results showed that incubations supplemented with acetate and lactate, performed in absence of sulfate, also produced methane after 40 days of incubation, apparently driven by hydrogenotrophic methanogens affiliated to the family Methanomicrobiaceae. Sulfate reduction was mainly stimulated by addition of acetate and lactate; however, after 40 days of incubation, an increase of the H 2 S concentrations in microcosms amended with trimethylamine and methanol was also observed, suggesting that these substrates are putatively used for sulfate reduction. Moreover, 16S rRNA gene sequencing analysis showed remarkable differences in the microbial community composition among experimental treatments. In the analyzed sample amended with acetate, sulfate-reducing bacteria (SRB) belonging to the family Desulfobacteraceae were dominant, while members of Desulfohalobiaceae, Desulfomicrobiaceae, and Desulfovibrionaceae were found in the incubation with lactate. Additionally, we detected an unexpected high abundance of unclassified Hydrogenedentes (near 25%) in almost all the experimental treatments. This study contributes to better understand methanogenic and sulfate-reducing activities, which play an important role in the functioning of hypersaline environments.

Sulfide and methane production in sewer sediments: Field survey and model evaluation.

PubMed

Liu, Yiwen; Tugtas, A Evren; Sharma, Keshab R; Ni, Bing-Jie; Yuan, Zhiguo

2016-02-01

Sewer sediment processes have been reported to significantly contribute to overall sulfide and methane production in sewers, at a scale comparable to that of sewer biofilms. The physiochemical and biological characteristics of sewer sediments are heterogeneous; however, the variability of in-sediments sulfide and methane production rates among sewers has not been assessed to date. In this study, five sewer sediment samples were collected from two cities in Australia with different climatic conditions. Batch assays were conducted to determine the rates of sulfate reduction and methane production under different flow velocity (shear stress) conditions as well as under completely mixed conditions. The tests showed substantial and variable sulfate reduction and methane production activities among different sediments. Sulfate reduction and methane production from sewer sediments were confirmed to be areal processes, and were dependent on flow velocity/shear stress. Despite of the varying characteristics and reactions kinetics, the sulfate reduction and methane production processes in all sediments could be well described by a one-dimensional sewer sediment model recently developed based on results obtained from a laboratory sewer sediment reactor. Model simulations indicated that the in-situ contribution of sewer sediment emissions could be estimated without the requirement of measuring the specific sediment characteristics or the sediment depths. Copyright © 2015 Elsevier Ltd. All rights reserved.

Deducing the distribution of terminal electron-accepting processes in hydrologically diverse groundwater systems

USGS Publications Warehouse

Chapelle, Francis H.; McMahon, Peter B.; Dubrovsky, Neil M.; Fujii, Roger F.; Oaksford, Edward T.; Vroblesky, Don A.

1995-01-01

The distribution of microbially mediated terminal electron-accepting processes (TEAPs( was investigated in four hydrologically diverse groundwater systems by considering patterns of electron acceptor (nitrate, sulfate) consumption, intermediate product (hydrogen (H2)) concentrations, and final product (ferrous iron, sulfide, and methane) production. In each hydrologic system a determination of predominant TEAPs could be arrived at, but the level of confidence appropriate for each determination differed. In a portion of the lacustrine aquifer of the San Joaquin Valley, for example, all three indicators (sulfate concentrations decreasing, H2concentrations in the 1–2 nmol range, and sulfide concentrations increasing along flow paths identified sulfate reduction as the predominant TEAP, leading to a high degree of confidence in the determination. In portions of the Floridan aquifer and a petroleum hydrocarbon-contaminated aquifer, sulfate reduction and methanogenesis are indicated by production of sulfide and methane, and hydrogen oncentrations in the 1–4 nmol and 5–14 nmol range, respectively. However, because electron acceptor consumption could not be documented in these systems, less confidence is warranted in the TEAP determination. In the Black Creek aquifer, no pattern of sulfate consumption and sulfide production were observed, but H2 concentrations indicated sulfate reduction as the predominant TEAP. In this case, where just a single line of evidence is available, the least confidence in the TEAP diagnosis is justified. Because this methodology is based on measurable water chemistry parameters and upon the physiology of microbial electron transfer processes, it provides a better description of predominant redox processes in groundwater systems than more traditional Eh-based methods.

Development of Sulfidogenic Sludge from Marine Sediments and Trichloroethylene Reduction in an Upflow Anaerobic Sludge Blanket Reactor

PubMed Central

Guerrero-Barajas, Claudia; Ordaz, Alberto; García-Solares, Selene Montserrat; Garibay-Orijel, Claudio; Bastida-González, Fernando; Zárate-Segura, Paola Berenice

2015-01-01

The importance of microbial sulfate reduction relies on the various applications that it offers in environmental biotechnology. Engineered sulfate reduction is used in industrial wastewater treatment to remove large concentrations of sulfate along with the chemical oxygen demand (COD) and heavy metals. The most common approach to the process is with anaerobic bioreactors in which sulfidogenic sludge is obtained through adaptation of predominantly methanogenic granular sludge to sulfidogenesis. This process may take a long time and does not always eliminate the competition for substrate due to the presence of methanogens in the sludge. In this work, we propose a novel approach to obtain sulfidogenic sludge in which hydrothermal vents sediments are the original source of microorganisms. The microbial community developed in the presence of sulfate and volatile fatty acids is wide enough to sustain sulfate reduction over a long period of time without exhibiting inhibition due to sulfide. This protocol describes the procedure to generate the sludge from the sediments in an upflow anaerobic sludge blanket (UASB) type of reactor. Furthermore, the protocol presents the procedure to demonstrate the capability of the sludge to remove by reductive dechlorination a model of a highly toxic organic pollutant such as trichloroethylene (TCE). The protocol is divided in three stages: (1) the formation of the sludge and the determination of its sulfate reducing activity in the UASB, (2) the experiment to remove the TCE by the sludge, and (3) the identification of microorganisms in the sludge after the TCE reduction. Although in this case the sediments were taken from a site located in Mexico, the generation of a sulfidogenic sludge by using this procedure may work if a different source of sediments is taken since marine sediments are a natural pool of microorganisms that may be enriched in sulfate reducing bacteria. PMID:26555802

Development of Sulfidogenic Sludge from Marine Sediments and Trichloroethylene Reduction in an Upflow Anaerobic Sludge Blanket Reactor.

PubMed

Guerrero-Barajas, Claudia; Ordaz, Alberto; García-Solares, Selene Montserrat; Garibay-Orijel, Claudio; Bastida-González, Fernando; Zárate-Segura, Paola Berenice

2015-10-15

The importance of microbial sulfate reduction relies on the various applications that it offers in environmental biotechnology. Engineered sulfate reduction is used in industrial wastewater treatment to remove large concentrations of sulfate along with the chemical oxygen demand (COD) and heavy metals. The most common approach to the process is with anaerobic bioreactors in which sulfidogenic sludge is obtained through adaptation of predominantly methanogenic granular sludge to sulfidogenesis. This process may take a long time and does not always eliminate the competition for substrate due to the presence of methanogens in the sludge. In this work, we propose a novel approach to obtain sulfidogenic sludge in which hydrothermal vents sediments are the original source of microorganisms. The microbial community developed in the presence of sulfate and volatile fatty acids is wide enough to sustain sulfate reduction over a long period of time without exhibiting inhibition due to sulfide. This protocol describes the procedure to generate the sludge from the sediments in an upflow anaerobic sludge blanket (UASB) type of reactor. Furthermore, the protocol presents the procedure to demonstrate the capability of the sludge to remove by reductive dechlorination a model of a highly toxic organic pollutant such as trichloroethylene (TCE). The protocol is divided in three stages: (1) the formation of the sludge and the determination of its sulfate reducing activity in the UASB, (2) the experiment to remove the TCE by the sludge, and (3) the identification of microorganisms in the sludge after the TCE reduction. Although in this case the sediments were taken from a site located in Mexico, the generation of a sulfidogenic sludge by using this procedure may work if a different source of sediments is taken since marine sediments are a natural pool of microorganisms that may be enriched in sulfate reducing bacteria.

System evaluation and microbial analysis of a sulfur cycle-based wastewater treatment process for Co-treatment of simple wet flue gas desulfurization wastes with freshwater sewage.

PubMed

Qian, Jin; Liu, Rulong; Wei, Li; Lu, Hui; Chen, Guang-Hao

2015-09-01

A sulfur cycle-based wastewater treatment process, namely the Sulfate reduction, Autotrophic denitrification and Nitrification Integrated process (SANI(®) process) has been recently developed for organics and nitrogen removal with 90% sludge minimization and 35% energy reduction in the biological treatment of saline sewage from seawater toilet flushing practice in Hong Kong. In this study, sulfate- and sulfite-rich wastes from simple wet flue gas desulfurization (WFGD) were considered as a potential low-cost sulfur source to achieve beneficial co-treatment with non-saline (freshwater) sewage in continental areas, through a Mixed Denitrification (MD)-SANI process trialed with synthetic mixture of simple WFGD wastes and freshwater sewage. The system showed 80% COD removal efficiency (specific COD removal rate of 0.26 kg COD/kg VSS/d) at an optimal pH of 7.5 and complete denitrification through MD (specific nitrogen removal rate of 0.33 kg N/kg VSS/d). Among the electron donors in MD, organics and thiosulfate could induce a much higher denitrifying activity than sulfide in terms of both NO3(-) reduction and NO2(-) reduction, suggesting a much higher nitrogen removal rate in organics-, thiosulfate- and sulfide-based MD in MD-SANI compared to sulfide alone-based autotrophic denitrification in conventional SANI(®). Diverse sulfate/sulfite-reducing bacteria (SRB) genera dominated in the bacterial community of sulfate/sulfite-reducing up-flow sludge bed (SRUSB) sludge without methane producing bacteria detected. Desulfomicrobium-like species possibly for sulfite reduction and Desulfobulbus-like species possibly for sulfate reduction are the two dominant groups with respective abundance of 24.03 and 14.91% in the SRB genera. Diverse denitrifying genera were identified in the bacterial community of anoxic up-flow sludge bed (AnUSB) sludge and the Thauera- and Thiobacillus-like species were the major taxa. These results well explained the successful operation of the lab-scale MD-SANI process. Copyright © 2015 Elsevier Ltd. All rights reserved.

Modeling sulfate reduction in methane hydrate-bearing continental margin sediments: Does a sulfate-methane transition require anaerobic oxidation of methane?

USGS Publications Warehouse

Malinverno, A.; Pohlman, J.W.

2011-01-01

The sulfate-methane transition (SMT), a biogeochemical zone where sulfate and methane are metabolized, is commonly observed at shallow depths (1-30 mbsf) in methane-bearing marine sediments. Two processes consume sulfate at and above the SMT, anaerobic oxidation of methane (AOM) and organoclastic sulfate reduction (OSR). Differentiating the relative contribution of each process is critical to estimate methane flux into the SMT, which, in turn, is necessary to predict deeper occurrences of gas hydrates in continental margin sediments. To evaluate the relative importance of these two sulfate reduction pathways, we developed a diagenetic model to compute the pore water concentrations of sulfate, methane, and dissolved inorganic carbon (DIC). By separately tracking DIC containing 12C and 13C, the model also computes ??13C-DIC values. The model reproduces common observations from methane-rich sediments: a well-defined SMT with no methane above and no sulfate below and a ??13C-DIC minimum at the SMT. The model also highlights the role of upward diffusing 13C-enriched DIC in contributing to the carbon isotope mass balance of DIC. A combination of OSR and AOM, each consuming similar amounts of sulfate, matches observations from Site U1325 (Integrated Ocean Drilling Program Expedition 311, northern Cascadia margin). Without AOM, methane diffuses above the SMT, which contradicts existing field data. The modeling results are generalized with a dimensional analysis to the range of SMT depths and sedimentation rates typical of continental margins. The modeling shows that AOM must be active to establish an SMT wherein methane is quantitatively consumed and the ??13C-DIC minimum occurs. The presence of an SMT generally requires active AOM. Copyright 2011 by the American Geophysical Union.

Characterization of Two Subsurface H2-Utilizing Bacteria, Desulfomicrobium hypogeium sp. nov. and Acetobacterium psammolithicum sp. nov., and Their Ecological Roles

PubMed Central

Krumholz, Lee R.; Harris, Steve H.; Tay, Stephen T.; Suflita, Joseph M.

1999-01-01

We examined the relative roles of acetogenic and sulfate-reducing bacteria in H2 consumption in a previously characterized subsurface sandstone ecosystem. Enrichment cultures originally inoculated with ground sandstone material obtained from a Cretaceous formation in central New Mexico were grown with hydrogen in a mineral medium supplemented with 0.02% yeast extract. Sulfate reduction and acetogenesis occurred in these cultures, and the two most abundant organisms carrying out the reactions were isolated. Based on 16S rRNA analysis data and on substrate utilization patterns, these organisms were named Desulfomicrobium hypogeium sp. nov. and Acetobacterium psammolithicum sp. nov. The steady-state H2 concentrations measured in sandstone-sediment slurries (threshold concentration, 5 nM), in pure cultures of sulfate reducers (threshold concentration, 2 nM), and in pure cultures of acetogens (threshold concentrations 195 to 414 nM) suggest that sulfate reduction is the dominant terminal electron-accepting process in the ecosystem examined. In an experiment in which direct competition for H2 between D. hypogeium and A. psammolithicum was examined, sulfate reduction was the dominant process. PMID:10347005

Inhibitory Effects of Sulfate and Nitrate Reduction on Reductive Dechlorination of PCP in a Flooded Paddy Soil

PubMed Central

Xu, Yan; Xue, Lili; Ye, Qi; Franks, Ashley E.; Zhu, Min; Feng, Xi; Xu, Jianming; He, Yan

2018-01-01

Pentachlorophenol (PCP) is highly toxic and persistent in soils. Bioreduction of PCP often co-occurs with varying concentrations of sulfate and nitrate in flooded paddy soils where each can act as an electron acceptor. Anaerobic soil microcosms were constructed to evaluate the influence of sulfate and nitrate amendments and their redox processes. Microcosms with varying sulfate and nitrate concentrations demonstrated an inhibitory effect on reductive dechlorination of PCP compared to an untreated control. Compared to nitrate, sulfate exhibited a more significant impact on PCP dechlorination, as evidenced by a lower maximum reaction rate and a longer time to reach the maximum reaction rate. Dechlorination of PCP was initiated at the ortho-position, and then at the para- and meta-positions to form 3-CP as the final product in all microcosms. Deep sequencing of microbial communities in the microcosms revealed a strong variation in bacterial taxon among treatments. Specialized microbial groups, such as the genus of Desulfovibrio responding to the addition of sulfate, had a potential to mediate the competitive microbial dechlorination of PCP. Our results provide an insight into the competitive microbial-mediated reductive dechlorination of PCP in natural flooded soil or sediment environments. PMID:29643842

Biogeochemical controls on interactions of microbial iron and sulfate reduction

NASA Astrophysics Data System (ADS)

Kirk, M. F.; Paper, J. M.; Haller, B. R.; Shodunke, G. O.; Marquart, K. A.; Jin, Q.

2016-12-01

Although iron and sulfate reduction are two of the most common microbial electron accepting processes in anoxic settings, the relative influences of environmental factors that guide interactions between each are poorly known. Identifying these factors is a key to predicting how those interactions will respond to future environmental changes. In this study, we used semi-continuous bioreactors to examine the influence of pH, electron donor flux, and sulfate availability. The reactors contained 100 mL of aqueous media and 1 g of marsh sediment amended with goethite (1 mmol). One set of reactors received acidic media (pH 6) while the other set received alkaline media (pH 7.5). Media for both sets of reactors included acetate (0.25 and 1 mM), which served as an electron donor, and sulfate (2.5 mM). We also included sets of sulfate-deficient and acetate-deficient control reactors. We maintained a fluid residence time of 35 days in the reactors by sampling and feeding them every seven days during the 91-day incubation. Our results show that, under the conditions tested, pH had a larger influence on the balance between each reaction than acetate concentration. In acidic reactors, the molar amount of iron reduced exceeded the amount of sulfate reduced by a factor of 3 in reactors receiving media with 0 and 0.25 mM acetate and a factor of 2 in reactors receiving 1 mM acetate. Under alkaline conditions, iron and sulfate were reduced in nearly equal proportions, regardless of influent acetate concentration. Results from sulfate-deficient control reactors show that the presence of sulfate reduction increased the extent of iron reduction in all reactors, but particularly those with alkaline pH. Under acidic conditions, the amount of iron reduced was greater by a factor of 1.2 if sulfate reduction occurred simultaneously than if it did not. Under alkaline conditions, that factor increased to 8.2. Hence, pH influenced the extent to which sulfate reduction promoted iron reduction.

The carbon isotope biogeochemistry of (epsilon)CO2 production in a methanogenic marine sediment

NASA Technical Reports Server (NTRS)

Boehme, Susan E.

1993-01-01

To investigate the relationship between sigma(CO2) delta(C-13) values and rates of the dominant remineralization processes at the organic-rich field site of Cape Lookout Bight, NC, the isotopic composition of porewater sigma(CO2) was measured on a seasonal basis. The sigma(CO2) delta(C-13) values varies seasonally in response to changes in rates of sulfate reduction and methanogenesis, the dominant remineralization processes at this site. A tube incubation experiment was also performed to determine the isotopic signature of the sigma(CO2) produced by sulfate reduction and methanogenesis. The delta(C-13) of the sigma(CO2) produced in the sulfate reduction zone determined from the tube incubation was -14.3 plus or minus 1.9, a value enriched in C-13 relative to the labile organic fraction. The C-13-enrichment may be caused by low rates of methanogenesis occurring in the sulfate reduction zone. The delta(C-13) of the sigma(CO2) produced in the methanogenic zone was estimated to be +44 per mil, whereas the co-produced methane was -65 per mil. The fractionation factor for CO2 reduction was calculated to be 1.055, a value in agreement with previous estimates at this site. The measured concentration and delta(C-13) of the sigma(CO2) at Cape Lookout was closely reproduced by a diagenetic model using the measured rates of sulfate reduction and sigma(CO2) production, and the isotopic signature of the sigma(CO2) production in the two biogeochemical zones.

A cryptic sulfur cycle driven by iron in the methane zone of marine sediment (Aarhus Bay, Denmark)

NASA Astrophysics Data System (ADS)

Holmkvist, Lars; Ferdelman, Timothy G.; Jørgensen, Bo Barker

2011-06-01

Sulfate reduction and sulfur-iron geochemistry were studied in 5-6 m deep gravity cores of Holocene mud from Aarhus Bay (Denmark). A goal was to understand whether sulfate is generated by re-oxidation of sulfide throughout the sulfate and methane zones, which might explain the abundance of active sulfate reducers deep below the main sulfate zone. Sulfate penetrated down to 130 cm where methane started to build up and where the concentration of free sulfide peaked at 5.5 mM. Below this sulfate-methane transition, sulfide diffused downwards to a sulfidization front at 520 cm depth, below which dissolved iron, Fe 2+, accumulated in the pore water. Sulfate reduction rates measured by 35S-tracer incubations in the sulfate zone were high due to high concentrations of reactive organic matter. Within the sulfate-methane transition, sulfate reduction was distinctly stimulated by the anaerobic oxidation of methane. In the methane zone below, sulfate remained at positive "background" concentrations of <0.5 mM down to the sulfidization front. Sulfate reduction decreased steeply to rates which at 300-500 cm depth were 0.2-1 pmol SO 42- cm -3 d -1, i.e., 4-5 orders of magnitude lower than rates measured near the sediment surface. The turn-over time of sulfate increased from 3 years at 12 cm depth to 100-1000 years down in the methane zone. Sulfate reduction in the methane zone accounted for only 0.1% of sulfate reduction in the entire sediment column and was apparently limited by the low pore water concentration of sulfate and the low availability of organic substrates. Amendment of the sediment with both sulfate and organic substrates immediately caused a 10- to 40-fold higher, "potential sulfate reduction" which showed that a physiologically intact community of sulfate reducing bacteria was present. The "background" sulfate concentration appears to be generated from the reaction of downwards diffusing sulfide with deeply buried Fe(III) species, such as poorly-reactive iron oxides or iron bound in reactive silicates. The oxidation of sulfide to sulfate in the sulfidic sediment may involve the formation of elemental sulfur and thiosulfate and their further disproportionation to sulfide and sulfate. The net reaction of sulfide and Fe(III) to form pyrite requires an additional oxidant, irrespective of the formation of sulfate. This could be CO 2 which is reduced with H 2 to methane. The methane subsequently diffuses upwards to become re-oxidized at the sulfate-methane transition and thereby removes excess reducing power and enables the formation of excess sulfate. We show here how the combination of these well-established sulfur-iron-carbon reactions may lead to the deep formation of sulfate and drive a cryptic sulfur cycle. The iron-rich post-glacial sediments underlying Holocene marine mud stimulate the strong sub-surface sulfide reoxidation observed in Aarhus Bay and are a result of the glacial to interglacial history of the Baltic Sea area. Yet, processes similar to the ones described here probably occur widespread in marine sediments, in particular along the ocean margins.

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

USGS Publications Warehouse

Meshoulam, Alexander; Ellis, Geoffrey S.; Ahmad, Ward Said; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

2016-01-01

Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and provide important mechanistic details about the overall TSR process.

Techniques for the conversion to carbon dioxide of oxygen from dissolved sulfate in thermal waters

USGS Publications Warehouse

Nehring, N.L.; Bowen, P.A.; Truesdell, A.H.

1977-01-01

The fractionation of oxygen isotopes between dissolved sulfate ions and water provides a useful geothermometer for geothermal waters. The oxygen isotope composition of dissolved sulfate may also be used to indicate the source of the sulfate and processes of formation. The methods described here for separation, purification and reduction of sulfate to prepare carbon dioxide for mass spectrometric analysis are modifications of methods by Rafter (1967), Mizutani (1971), Sakai and Krouse (1971), and Mizutani and Rafter (1969). ?? 1976.

Removal of antimony (Sb(V)) from Sb mine drainage: biological sulfate reduction and sulfide oxidation-precipitation.

PubMed

Wang, Huawei; Chen, Fulong; Mu, Shuyong; Zhang, Daoyong; Pan, Xiangliang; Lee, Duu-Jong; Chang, Jo-Shu

2013-10-01

Antimony (Sb(V)) in Sb mine drainage has adverse effects on the receiving water environments. This study for the first time demonstrated the feasibility of using sulfate-reducing bacteria (SRB) to convert sulfate ions in SMD into sulfides that reduce Sb(V) to Sb(III) and to form complex with Sb(III) as precipitate. The principal compound in the precipitate was stibnite (Sb2S3) at pH 7 and pH 9. The Sb(V) removal mechanism is sulfate-reduction and sulfide oxidization-precipitation, different from the conventional SRB-precipitation processes for heavy metals. The Sb(V)/sulfate ratio is noted an essential parameter affecting the Sb removal efficiency from SMD. Copyright © 2013 Elsevier Ltd. All rights reserved.

COMPARISON OF HYDROGEN CONCENTRATIONS IN PCE-DEHALOGENATING AND SULFATE-REDUCING ESTUARINE SEDIMENTS

EPA Science Inventory

The primary transformation pathway for PCE in anoxic environments is through sequential reductive dehalogenation, and information concerning dehalogenation processes that occur in environments containing alternative electron acceptors (sulfate) is limited. Hydrogen is postulated ...

Salinity Responses of Benthic Microbial Communities in a Solar Saltern (Eilat, Israel)

PubMed Central

Sørensen, Ketil Bernt; Canfield, Donald E.; Oren, Aharon

2004-01-01

The salinity responses of cyanobacteria, anoxygenic phototrophs, sulfate reducers, and methanogens from the laminated endoevaporitic community in the solar salterns of Eilat, Israel, were studied in situ with oxygen microelectrodes and in the laboratory in slurries. The optimum salinity for the sulfate reduction rate in sediment slurries was between 100 and 120‰, and sulfate reduction was strongly inhibited at an in situ salinity of 215‰. Nevertheless, sulfate reduction was an important respiratory process in the crust, and reoxidation of formed sulfide accounted for a major part of the oxygen budget. Methanogens were well adapted to the in situ salinity but contributed little to the anaerobic mineralization in the crust. In slurries with a salinity of 180‰ or less, methanogens were inhibited by increased activity of sulfate-reducing bacteria. Unicellular and filamentous cyanobacteria metabolized at near-optimum rates at the in situ salinity, whereas the optimum salinity for anoxygenic phototrophs was between 100 and 120‰. PMID:15006785

Active Microbial Sulfate Reduction in Serpentinization Fluids of the Semail Ophiolite in Oman

NASA Astrophysics Data System (ADS)

Glombitza, C.; Rempfert, K. R.; Templeton, A. S.; Hoehler, T. M.

2017-12-01

Dissimilatory sulfate reduction (SR) is among the oldest known microbial processes on Earth. It is the predominant anaerobic microbial process in sulfur-rich marine sediments but it also occurs in subsurface lithoautotrophic ecosystems, where it is driven by radiolytically produced H2 and sulfate [1]. Serpentinization is a process by which H2 is generated in a reaction of water with peridotite rock. This abiotic generation of H2 suggests its potential to power life in rocks as a stand-alone process, independent of the photosynthetic biosphere, because the generated H2 is a key energy source for microbial metabolism. This is of particular interest in understanding the role of water-rock reactions in generating habitable conditions on and beyond Earth. Sulfate is plausibly available in several of the water-bearing environments now known beyond Earth, making SR a potentially important metabolism in those systems. Sulfate minerals are abundant on the surface of Mars [2], suggesting that Martian groundwaters may be sulfate-rich. Sulfate is also postulated to be a component of the oceans of Europa and Enceladus [3, 4]. The inferred presence of both sulfate and peridotite rocks in these environments points toward a potential niche for sulfate reducers and highlights the need to understand how and where SR occurs in serpentinizing systems on Earth. We incubated formation fluids sampled from in the Semail Ophiolite in Oman with a 35-S labelled sulfate tracer and determined the rates of in-situ microbial sulfate reduction. The selected fluids represent different environmental conditions, in particular varying substrate concentrations (sulfate, H2 and CH4) and pH (pH 8.4 to pH 11.2). We found active microbial SR at very low rates in almost all fluids, ranging from 2 fmol mL-1 d-1 to 2 pmol mL-1 d-2. Lowest rates were associated with the hyperalkaline fluids (pH > 10), that had also the lowest sulfate concentration (50-90 µmol L-1). In line with previously determined species richness in the well fluids [5], this suggests that pH is an important parameter for habitability in this environment. References:[1] Lin et al., 2006. Science 314, 479. [2] Gendrin et al., 2005. Science 307, 1587. [3] Brown and Hand, 2013. The Astronomical Journal 145, 110. [4] McKay et al., 2008. Astrobiology 8, 909 [5] Rempfert et al. 2017. Front. Microbiol. 8, 56.

Method of removing sulfur emissions from a fluidized-bed combustion process

DOEpatents

Vogel, Gerhard John; Jonke, Albert A.; Snyder, Robert B.

1978-01-01

Alkali metal or alkaline earth metal oxides are impregnated within refractory support material such as alumina and introduced into a fluidized-bed process for the combustion of coal. Sulfur dioxide produced during combustion reacts with the metal oxide to form metal sulfates within the porous support material. The support material is removed from the process and the metal sulfate regenerated to metal oxide by chemical reduction. Suitable pore sizes are originally developed within the support material by heat-treating to accommodate both the sulfation and regeneration while still maintaining good particle strength.

Reactive Transport Modeling Investigation of High Dissolved Sulfide Concentrations in Sedimentary Basin Rocks

NASA Astrophysics Data System (ADS)

Xie, M.; Mayer, U. K.; MacQuarrie, K. T. B.

2017-12-01

Water with total dissolved sulfide in excess of 1 mmol L-1is widely found in groundwater at intermediate depths in sedimentary basins, including regions of the Michigan basin in southeastern Ontario, Canada. Conversely, at deeper and shallower depths, relatively low total dissolved sulfide concentrations have been reported. The mechanisms responsible for the occurrence of these brackish sulfide-containing waters are not fully understood. Anaerobic microbial sulfate reduction is a common process resulting in the formation of high sulfide concentrations. Sulfate reduction rates depend on many factors including the concentration of sulfate, the abundance of organic substances, redox conditions, temperature, salinity and the species of sulfate reducing bacteria (SRB). A sedimentary basin-specific conceptual model considering the effect of salinity on the rate of sulfate reduction was developed and implemented in the reactive transport model MIN3P-THCm. Generic 2D basin-scale simulations were undertaken to provide a potential explanation for the dissolved sulfide distribution observed in the Michigan basin. The model is 440 km in the horizontal dimension and 4 km in depth, and contains fourteen sedimentary rock units including shales, sandstones, limestones, dolostone and evaporites. The main processes considered are non-isothermal density dependent flow, kinetically-controlled mineral dissolution/precipitation and its feedback on hydraulic properties, cation exchange, redox reactions, biogenic sulfate reduction, and hydromechanical coupling due to glaciation-deglaciation events. Two scenarios were investigated focusing on conditions during an interglacial period and the transient evolution during a glaciation-deglaciation cycle. Inter-glaciation simulations illustrate that the presence of high salinity brines strongly suppress biogenic sulfate reduction. The transient simulations show that glaciation-deglaciation cycles can have an impact on the maximum depth of elevated sulfide concentrations due to freshwater ingress and enhanced mixing. In all simulations the highest concentrations of total sulfide occur at depths of approximately 150 m, while concentrations at depths greater than 300 m typically remain below 0.03 mmol L-1, comparing well with observational data.

The nitrogen cycle in anaerobic methanotrophic mats of the Black Sea is linked to sulfate reduction and biomass decomposition.

PubMed

Siegert, Michael; Taubert, Martin; Seifert, Jana; von Bergen-Tomm, Martin; Basen, Mirko; Bastida, Felipe; Gehre, Matthias; Richnow, Hans-Hermann; Krüger, Martin

2013-11-01

Anaerobic methanotrophic (ANME) mats host methane-oxidizing archaea and sulfate-reducing prokaryotes. Little is known about the nitrogen cycle in these communities. Here, we link the anaerobic oxidation of methane (AOM) to the nitrogen cycle in microbial mats of the Black Sea by using stable isotope probing. We used four different (15)N-labeled sources of nitrogen: dinitrogen, nitrate, nitrite and ammonium. We estimated the nitrogen incorporation rates into the total biomass and the methyl coenzyme M reductase (MCR). Dinitrogen played an insignificant role as nitrogen source. Assimilatory and dissimilatory nitrate reduction occurred. High rates of nitrate reduction to dinitrogen were stimulated by methane and sulfate, suggesting that oxidation of reduced sulfur compounds such as sulfides was necessary for AOM with nitrate as electron acceptor. Nitrate reduction to dinitrogen occurred also in the absence of methane as electron donor but at six times slower rates. Dissimilatory nitrate reduction to ammonium was independent of AOM. Ammonium was used for biomass synthesis under all conditions. The pivotal enzyme in AOM coupled to sulfate reduction, MCR, was synthesized from nitrate and ammonium. Results show that AOM coupled to sulfate reduction along with biomass decomposition drive the nitrogen cycle in the ANME mats of the Black Sea and that MCR enzymes are involved in this process. © 2013 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

KEY CONCEPTS IN BIODEGRADATION

EPA Science Inventory

This one hour segment of the course identifies the biological processes that degrade petroleum hydrocarbons and MTBE. It reviews the stoichiometry of hydrocarbon degradation by aerobic respiration, nitrate reduction, sulfate reduction, iron (III) reduction, and methanogenesis. ...

Evidence for iron-sulfate coupling in salt marsh sediments

NASA Astrophysics Data System (ADS)

Mills, Jennifer; Antler, Gilad; Turchyn, Alexandra

2014-05-01

Organic carbon burial in shallow marine sediments represents an important net sink in the global carbon cycle. Microbially mediated oxidation of organic matter in oxic, suboxic, and anoxic sediments however, prevents the ultimate burial of organic carbon and its removal from the surface of the planet. Although the subsurface transformations of organic carbon have been studied extensively, an enigmatic question remains: when organic matter is deposited, what determines whether it will be buried, reoxidized, or undergo methanogenesis? One hypothesis is that the sulfur cycle, due to the abundance of sulfate in many surface environments, dominates the subsurface oxidation or other fate of organic carbon. However, it has also been suggested that iron may in turn play a key role in determining the behavior of the sulfur cycle. To better understand the controls on these processes, we are using stable isotope and geochemical techniques to explore the microbially mediated oxidation of organic carbon in salt marsh sediments in North Norfolk, UK. In these sediments there is a high supply of organic carbon, iron, and sulfate (from diurnal tidal cycles). Thus these environments may provide insight into the nature of interactions between the carbon, iron, and sulfur cycles. A series of sampling missions was undertaken in the autumn and winter of 2013-2014. In subsurface fluid samples we observe very high ferrous iron concentrations (>1mM), indicative of extended regions of iron reduction (to over 30cm depth). Within these zones of iron reduction we would predict no sulfate reduction, and as expected δ34Ssulfate remains unchanged with depth. However, δ18Osulfate exhibits significant enrichments of up to 5 permil. This decoupling in the sulfur and oxygen isotopes of sulfate is suggestive of a sulfate recycling process in which sulfate is reduced to an intermediate sulfur species and subsequently reoxidized to sulfate. Taken together, these data suggest that microbial assemblages in these salt marsh sediments facilitate a cryptic cycling of sulfur, potentially mediated by iron species in the zone of iron reduction.

Bioassessment of heavy metal toxicity and enhancement of heavy metal removal by sulfate-reducing bacteria in the presence of zero valent iron.

PubMed

Guo, Jing; Kang, Yong; Feng, Ying

2017-12-01

A simple and valid toxicity evaluation of Zn 2+ , Mn 2+ and Cr 6+ on sulfate-reducing bacteria (SRB) and heavy metal removal were investigated using the SRB system and SRB+Fe 0 system. The heavy metal toxicity coefficient (β) and the heavy metal concentration resulting in 50% inhibition of sulfate reduction (I) from a modeling process were proposed to evaluate the heavy metal toxicity and nonlinear regression was applied to search for evaluation indices β and I. The heavy metal toxicity order was Cr 6+  > Mn 2+  > Zn 2+ . Compared with the SRB system, the SRB+Fe 0 system exhibited a better capability for sulfate reduction and heavy metal removal. The heavy metal removal was above 99% in the SRB+Fe 0 system, except for Mn 2+ . The energy-dispersive spectroscopy (EDS) analysis showed that the precipitates were removed primarily as sulfide for Zn 2+ and hydroxide for Mn 2+ and Cr 6+ .The method of evaluating the heavy metal toxicity on SRB was of great significance to understand the fundamentals of the heavy metal toxicity and inhibition effects on the microorganism and regulate the process of microbial sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of common groundwater ions on chromate removal by magnetite: Importance of chromate adsorption

DOE PAGES

Meena, Amanda H.; Arai, Yuji

2016-04-29

Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (< a few hr) reduction of soluble Cr(VI) to insoluble Cr(III) species by Fe(II) in magnetite has been the primary focus of the Cr(VI) removal process in the past. However, the contribution of simultaneous Cr(VI) adsorption processes in aged magnetite has been largely ignored, leaving uncertainties in evaluating the application of in situ Cr remediation technologies for aqueous systems. In this study, effects of common groundwater ions (i.e., nitrate and sulfate) on Cr(VI) sorption to magnetite were investigated using batchmore » geochemical experiments in conjunction with X-ray absorption spectroscopy. As a result, in both nitrate and sulfate electrolytes, batch sorption experiments showed that Cr(VI) sorption decreases with increasing pH from 4 to 8. In this pH range, Cr(VI) sorption decreased with increasing ionic strength of sulfate from 0.01 to 0.1 M whereas nitrate concentrations did not alter the Cr(VI) sorption behavior. This indicates the background electrolyte specific Cr(VI) sorption process in magnetite. Under the same ionic strength, Cr(VI) removal in sulfate containing solutions was greater than that in nitrate solutions. This is because the oxidation of Fe(II) by nitrate is more thermodynamically favorable than by sulfate, leaving less reduction capacity of magnetite to reduce Cr(VI) in the nitrate media. X-ray absorption spectroscopy analysis supports the macroscopic evidence that more than 75 % of total Cr on the magnetite surfaces was adsorbed Cr(VI) species after 48 h. In conclusion, this experimental geochemical study showed that the adsorption process of Cr(VI) anions was as important as the reductive precipitation of Cr(III) in describing the removal of Cr(VI) by magnetite, and these interfacial adsorption processes could be impacted by common groundwater ions like sulfate and nitrate. The results of this study highlight new information about the large quantity of adsorbed Cr(VI) surface complexes at the magnetite-water interface. It has implications for predicting the long-term stability of Cr at the magnetite-water interface.« less

Anaerobic oxidation of methane coupled to thiosulfate reduction in a biotrickling filter.

PubMed

Cassarini, Chiara; Rene, Eldon R; Bhattarai, Susma; Esposito, Giovanni; Lens, Piet N L

2017-09-01

Microorganisms from an anaerobic methane oxidizing sediment were enriched with methane gas as the substrate in a biotrickling filter (BTF) using thiosulfate as electron acceptor for 213days. Thiosulfate disproportionation to sulfate and sulfide were the dominating sulfur conversion process in the BTF and the sulfide production rate was 0.5mmoll -1 day -1 . A specific group of sulfate reducing bacteria (SRB), belonging to the Desulforsarcina/Desulfococcus group, was enriched in the BTF. The BTF biomass showed maximum sulfate reduction rate (0.38mmoll -1 day -1 ) with methane as sole electron donor, measured in the absence of thiosulfate in the BTF. Therefore, a BTF fed with thiosulfate as electron acceptor can be used to enrich SRB of the DSS group and activate the inoculum for anaerobic oxidation of methane coupled to sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of common groundwater ions on chromate removal by magnetite: importance of chromate adsorption.

PubMed

Meena, Amanda H; Arai, Yuji

2016-01-01

Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (

Regeneration of sulfated metal oxides and carbonates

DOEpatents

Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

1978-03-28

Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

Laboratory Investigations of Enhanced Sulfate Reduction as a Groundwater Arsenic Remediation Strategy

PubMed Central

KEIMOWITZ, A. R.; MAILLOUX, B. J.; COLE, P.; STUTE, M.; SIMPSON, H. J.; CHILLRUD, S. N.

2011-01-01

Landfills have the potential to mobilize arsenic via induction of reducing conditions in groundwater and subsequent desorption from or dissolution of arsenic-bearing iron phases. Laboratory incubation experiments were conducted with materials from a landfill where such processes are occurring. These experiments explored the potential for induced sulfate reduction to immobilize dissolved arsenic in situ. The native microbial community at this site reduced sulfate in the presence of added acetate. Acetate respiration and sulfate reduction were observed concurrent with dissolved iron concentrations initially increasing from 0.6 μM (0.03 mg L−1) to a maximum of 111 μM (6.1 mg L−1) and subsequently decreasing to 0.74 μM (0.04 mg L−1). Dissolved arsenic concentrations initially covaried with iron but subsequently increased again as sulfide accumulated, consistent with the formation of soluble thioarsenite complexes. Dissolved arsenic concentrations subsequently decreased again from a maximum of 2 μM (148 μg L−1) to 0.3 μM (22 μg L−1), consistent with formation of sulfide mineral phases or increased arsenic sorption at higher pH values. Disequilibrium processes may also explain this second arsenic peak. The maximum iron and arsenic concentrations observed in the lab represent conditions most equivalent to the in situ conditions. These findings indicate that enhanced sulfate reduction merits further study as a potential in situ groundwater arsenic remediation strategy at landfills and other sites with elevated arsenic in reducing groundwater. PMID:17969686

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: interaction of seawater with fayalite and magnetite at 200–350°C

USGS Publications Warehouse

Shanks, Wayne C.; Bischoff, James L.; Rosenbauer, Robert J.

1981-01-01

Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H2S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.

Sulfur and oxygen isotope fractionation during benzene, toluene, ethyl benzene, and xylene degradation by sulfate-reducing bacteria.

PubMed

Knöller, Kay; Vogt, Carsten; Richnow, Hans-Herrmann; Weise, Stephan M

2006-06-15

We examined the oxygen and sulfur isotope fractionation of sulfate during anaerobic degradation of toluene by sulfate-reducing bacteria in culture experiments with Desulfobacula toluolica as a type strain and with an enrichment culture Zz5-7 obtained from a benzene, toluene, ethylbenzene, and xylene (BTEX)-contaminated aquifer. Sulfur isotope fractionation can show considerable variation upon sulfate reduction and may react extremely sensitively to changes in environmental conditions. In contrast, oxygen isotope fractionation seems to be less sensitive to environmental changes. Our results clearly indicate that oxygen isotope fractionation is dominated by isotope exchange with ambient water. To verify our experimental results and to test the applicability of oxygen and sulfur isotope investigations under realistic field conditions, we evaluated isotope data from two BTEX-contaminated aquifers presented in the recent literature. On a field scale, bacterial sulfate reduction may be superimposed by processes such as dispersion, adsorption, reoxidation, or mixing. The dual isotope approach enables the identification of such sulfur transformation processes. This identification is vital for a general qualitative evaluation of the natural attenuation potential of the contaminated aquifer.

New insights into the transport processes controlling the sulfate-methane-transition-zone near methane vents.

PubMed

Sultan, Nabil; Garziglia, Sébastien; Ruffine, Livio

2016-05-27

Over the past years, several studies have raised concerns about the possible interactions between methane hydrate decomposition and external change. To carry out such an investigation, it is essential to characterize the baseline dynamics of gas hydrate systems related to natural geological and sedimentary processes. This is usually treated through the analysis of sulfate-reduction coupled to anaerobic oxidation of methane (AOM). Here, we model sulfate reduction coupled with AOM as a two-dimensional (2D) problem including, advective and diffusive transport. This is applied to a case study from a deep-water site off Nigeria's coast where lateral methane advection through turbidite layers was suspected. We show by analyzing the acquired data in combination with computational modeling that a two-dimensional approach is able to accurately describe the recent past dynamics of such a complex natural system. Our results show that the sulfate-methane-transition-zone (SMTZ) is not a vertical barrier for dissolved sulfate and methane. We also show that such a modeling is able to assess short timescale variations in the order of decades to centuries.

Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

USGS Publications Warehouse

Tuttle, Michele L.W.; Breit, George N.; Cozzarelli, Isabelle M.

2009-01-01

The δ34S and δ18O values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the δ34SSO4 and δ18OSO4 values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO4 concentrations) and isotopic composition (δ2HH2Oand δ18OH2O) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The δ34SSO4 and δ18OSO4 values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (δ34SSO4 = 8–12‰ and δ18OSO4 = 10‰), iron sulfides oxidized by molecular oxygen during low water-table levels (δ34SSO4 = − 16‰ and δ18OSO4 = 10‰), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (δ34SSO4 = 8‰ and δ18OSO4 = 6‰). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing δ34SSO4 and δ18OSO4 values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by εH2S–SO4 = − 23‰) results in the steady increase of δ34SSO4values to greater than 70‰. Equilibrium isotope fractionation during exchange of sulfate oxygen and water oxygen, a process not commonly observed in field-based studies, is documented in δ18OSO4 values asymptotically approaching 21‰, the value predicted for conditions at the study site (εSO4–H2O = 27‰). These results show that recognition of all potential sulfate sources is a critical first step to resolving complexities in δ34SSO4 and δ18OSO4 data. The approach taken in this study can be used in other aquifer systems where the identification of multiple sulfate sources and sulfur redox cycling is important to understanding natural processes and anthropogenic influences.

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 1. Sulfate from confining beds as an oxidant in microbial CO2 production

USGS Publications Warehouse

Chapelle, F.H.; McMahon, P.B.

1991-01-01

A primary source of dissolved inorganic carbon (DIC) in the Black Creek aquifer of South Carolina is carbon dioxide produced by microbially mediated oxidation of sedimentary organic matter. Groundwater chemistry data indicate, however, that the available mass of inorganic electron acceptors (oxygen, Fe(III), and sulfate) and observed methane production is inadequate to account for observed CO2 production. Although sulfate concentrations are low (approximately 0.05-0.10 mM) in aquifer water throughout the flow system, sulfate concentrations are greater in confining-bed pore water (0.4-20 mM). The distribution of culturable sulfate-reducing bacteria in these sediments suggests that this concentration gradient is maintained by greater sulfate-reducing activity in sands than in clays. Calculations based on Fick's Law indicate that possible rates of sulfate diffusion to aquifer sediments are sufficient to explain observed rates of CO2 production (about 10-5 mmoll-1 year-1), thus eliminating the apparent electron-acceptor deficit. Furthermore, concentrations of dissolved hydrogen in aquifer water are in the range characteristic of sulfate reduction (2-6 nM), which provides independent evidence that sulfate reduction is the predominant terminal electron-accepting process in this system. The observed accumulation of pyrite- and calcite-cemented sandstones at sand-clay interfaces is direct physical evidence that these processes have been continuing over the history of these sediments. ?? 1991.

ASSESSMENT OF SULFATE REDUCTION RATES IN LABORATORY EXPERIMENTS

EPA Science Inventory

Two successful field demonstrations of sulfate reducing bacteria (SRB) bioreactors showed needs for research: 1) improve the understanding of the processes in the bioreactor and its longetivity and 2) improve and quantify the design of the bioreactors. An important component of t...

Inhibitory Effects of Silver Nanoparticles on Removal of Organic Pollutants and Sulfate in an Anaerobic Biological Wastewater Treatment Process.

PubMed

Rasool, Kashif; Lee, Dae Sung

2016-05-01

The increasing use of silver nanoparticles (AgNPs) in commercial products and industrial processes raises issues regarding the toxicity of sludge biomass in biological wastewater treatment plants, due to potential antimicrobial properties. This study investigated the effects of AgNPs on removal of organic pollutants and sulfate in an anaerobic biological sulfate reduction process. At AgNPs concentrations of up to 10 mg/L, no significant inhibition of sulfate and COD removal was observed. However, at higher concentrations (50-200 mg/L) sulfate and COD removal efficiencies were significantly decreased to 51.8% and 33.6%, respectively. Sulfate and COD reduction followed first-order kinetics at AgNPs concentrations of up to 10 mg/L and second-order kinetics at AgNPs concentrations of 50-200 mg/L. Lactate dehydrogenase release profiles showed increases in cytotoxicity at AgNPs concentrations greater than 50 mg/L suggesting cell membrane disruption. Analysis of extracellular polymeric substances (EPS) from sulfidogenic sludge biomass and of Fourier transform infrared (FT-IR) spectra showed a decrease in concentrations of carbohydrates, proteins, humic substances, and lipids in the presence of AgNPs. Moreover, the interaction of AgNPs with sludge biomass and the damage caused to cell walls were confirmed through scanning electron microscopy with energy dispersive X-ray spectroscopy.

Mechanisms of sulfate removal from subsurface calcium chloride brines: Heletz-Kokhav oilfields, Israel

NASA Astrophysics Data System (ADS)

Gavrieli, Ittai; Starinsky, Avraham; Spiro, Baruch; Aizenshtat, Zeev; Nielsen, Heimo

1995-09-01

The evolution of the Ca-chloride brines in the Heletz Formation, Lower Cretaceous, in the southern coastal plain of Israel was reconstructed through the study of its sulfate concentration and isotopic composition. Particular emphasis was given to the brine-oil interaction in the oilfields and to the sulfate depletion and lower SO 4/Cl ratio in brines in contact with hydrocarbons (oil brines) relative to "oil-free" from dry wells in the same oilfields. A method is presented for a calculation of the amount of sulfate removed from the original seawater in the various stages of its evolution to Ca-chloride brine. These stages include evaporation, dolomitization, and sulfate reduction in different stages of its evolution, from early diagenetic processes to the contact with crude oil. In the present study, based on the δ34S SO 4 and SO 4/Cl ratio, it was found that in the Heletz brines most of the sulfate (80-94%) was removed from the original seawater prior to their interaction with the hydrocarbons and only a negligible fraction of few percent of the sulfate was removed during the crude oil-water contact. The Ca-chloride brines evolved from Messinian (Upper Miocene) seawater that underwent evaporation during the desiccation of the Mediterranean. Sulfate was removed from Messinian lagoon (s) during gypsum precipitation due to evaporation and dolomitization. Bacterial sulfate reduction further depleted the brine in sulfate and changed its isotopic composition, from its original Miocene seawater composition of δ34S SO 4 ˜ 20%o, 26%o. Overall, some 50% of the original sulfate, as normalized to chloride, was removed from the original lagoon through the above processes, mostly by gypsum precipitation. Eastward migration of the Messinian Ca-Chloride brine into the Heletz Formation was accompanied by dolomitization of the country rock. Final depletion of sulfate from the brines took place, and possibly still occurs, in the presence of crude oil in the oilfields. The two oil-producing fields, Heletz and Kokhav, occupy different areas on a Rayleigh distillation diagram. Sulfate depletion in both fields is accompanied by an increase in δ34S SO 4, which reaches a maximum value of 59%o. The above correlation is explained by bacterial sulfate reduction facilitated by the contact with the crude. Samples collected from the same boreholes at time intervals of several months show two opposing trends: sulfate concentration decrease accompanied by increase in δ34S SO 4, and vice versa. While the first can be explained as in situ bacterial sulfate reduction, the latter attest to subsurface brine migration, as would be expected in oil-producing fields.

Consortia of low-abundance bacteria drive sulfate reduction-dependent degradation of fermentation products in peat soil microcosms

DOE PAGES

Hausmann, Bela; Knorr, Klaus-Holger; Schreck, Katharina; ...

2016-03-25

A cryptic sulfur cycle and effectively competes with methanogenic degradation pathways sustains dissimilatory sulfate reduction in peatlands. In a series of peat soil microcosms incubated over 50 days, we identified bacterial consortia that responded to small, periodic additions of individual fermentation products (formate, acetate, propionate, lactate or butyrate) in the presence or absence of sulfate. Under sulfate supplementation, net sulfate turnover (ST) steadily increased to 16–174 nmol cm –3 per day and almost completely blocked methanogenesis. 16S rRNA gene and cDNA amplicon sequencing identified microorganisms whose increases in ribosome numbers strongly correlated to ST. Natively abundant (greater than or equalmore » to0.1% estimated genome abundance) species-level operational taxonomic units (OTUs) showed no significant response to sulfate. In contrast, low-abundance OTUs responded significantly to sulfate in incubations with propionate, lactate and butyrate. These OTUs included members of recognized sulfate-reducing taxa (Desulfosporosinus, Desulfopila, Desulfomonile, Desulfovibrio) and also members of taxa that are either yet unknown sulfate reducers or metabolic interaction partners thereof. The most responsive OTUs markedly increased their ribosome content but only weakly increased in abundance. Responsive Desulfosporosinus OTUs even maintained a constantly low population size throughout 50 days, which suggests a novel strategy of rare biosphere members to display activity. Interestingly, two OTUs of the non-sulfate-reducing genus Telmatospirillum (Alphaproteobacteria) showed strongly contrasting preferences towards sulfate in butyrate-amended microcosms, corroborating that closely related microorganisms are not necessarily ecologically coherent. We show that diverse consortia of low-abundance microorganisms can perform peat soil sulfate reduction, a process that exerts control on methane production in these climate-relevant ecosystems.« less

MICROBIAL DEGRADATION OF TOLUENE UNDER SULFATE- REDUCING CONDITIONS AND THE INFLUENCE OF IRON ON THE PROCESS

EPA Science Inventory

Toluene degradation occurred concomitantly with sulfate reduction in anaerobic microcosms inoculated with contaminated subsurface soil from an aviation fuel storage facility near the Patuxent River (Md.). Similar results were obtained for enrichment cultures in which toluene was ...

Reduction of orthophosphates loss in agricultural soil by nano calcium sulfate.

PubMed

Chen, Dong; Szostak, Paul; Wei, Zongsu; Xiao, Ruiyang

2016-01-01

Nutrient loss from soil, especially phosphorous (P) from farmlands to natural water bodies via surface runoff or infiltration, have caused significant eutrophication problems. This is because dissolved orthophosphates are usually the limiting nutrient for algal blooms. Currently, available techniques to control eutrophication are surprisingly scarce. Calcium sulfate or gypsum is a common soil amendment and has a strong complexation to orthophosphates. The results showed that calcium sulfate reduced the amount of water extractable P (WEP) through soil incubation tests, suggesting less P loss from farmlands. A greater decrease in WEP occurred with a greater dosage of calcium sulfate. Compared to conventional coarse calcium sulfate, nano calcium sulfate further reduced WEP by providing a much greater specific surface area, higher solubility, better contact with the fertilizer and the soil particles, and superior dispersibility. The enhancement of the nano calcium sulfate for WEP reduction is more apparent for a pellet- than a powdered- fertilizer. At the dosage of Ca/P weight ratio of 2.8, the WEP decreased by 31±5% with the nano calcium sulfate compared to 20±5% decrease with the coarse calcium sulfate when the pellet fertilizer was used. Computation of the chemical equilibrium speciation shows that calcium hydroxyapatite has the lowest solubility. However, other mineral phases such as hydroxydicalcium phosphate, dicalcium phosphate dihydrate, octacalcium phosphate, and tricalcium phosphate might form preceding to calcium hydroxyapatite. Since calcium sulfate is the major product of the flue gas desulfurization (FGD) process, this study demonstrates a potential beneficial reuse and reduction of the solid FGD waste. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of NO2(-) on stable isotope fractionation during bacterial sulfate reduction.

PubMed

Einsiedl, Florian

2009-01-01

The effects of low NO2(-) concentrations on stable isotope fractionation during dissimilatory sulfate reduction by strain Desulfovibrio desulfuricans were investigated. Nitrite, formed as an intermediate during nitrification and denitrification processes in marine and freshwater habitats, inhibits the reduction of the sulfuroxy intermediate SO3(2-) to H2S even at low concentrations. To gain an understanding of the inhibition effect of the reduction of the sulfuroxy intermediate on stable isotope fractionation in sulfur and oxygen during bacterial sulfate reduction, nitrite was added in the form of short pulses. In the batch experiments that contained 0.02, 0.05, and 0.1 mM nitrite, sulfur enrichment factors epsilon of -12 +/- 1.6, -15 +/- 1.1, and -26 +/- 1.3 per thousand, respectively were observed. In the control experiment (no addition of nitrite) a sulfur enrichment factor epsilon of around -11 per thousand was calculated. In the experiments that contained no 18O enriched water (delta18O: -10 per thousand) and nitrite concentrations of 0.02, 0.05, and 0.1 mM, delta18O values in the remaining sulfate were fairly constant during the experiments (delta18O sulfate: approximately equal to 10 per thousand) and were similar to those obtained from the control experiment (no nitrite and no enriched water). However, in the batch experiments that contained 18O enriched water (+700 per thousand) and nitrite concentrations of 0.05 and 0.1 mM increasing delta18O values in the remaining sulfate from around 15 per thousand to approximately 65 and 85 per thousand, respectively, were found. Our experiments that contained isotopic enriched water and nitrite show clear evidence that the ratio of forward and backward fluxes regulated by adenosine-5'-phosphosulfate reductase (APSR) controls the extent of sulfur isotope fractionation during bacterial sulfate reduction in strain Desulfovibrio desulfuricans. Since the metabolic sulfuroxy intermediate SO3(2-) exchanges with water, evidence of 18O enriched water in the remaining sulfate in the experiments that contained nitrite also demonstrates that SO3(2-) recycling to sulfate affects sulfur and oxygen isotope fractionation during bacterial sulfate reduction to some extent. Even though reduction of adenosine-5'-phosphosulfate (APS) to sulfite of -25 per thousand was not fully expressed, SO3(2-) was recycled to SO4(2-). On the basis of the results of this study a sulfur isotope fractionation for APSR of upto approximately -30 per thousand can be assumed. However, reported NO2(-) concentrations of up to 20 microM in freshwater and marine habitats may not significantly impact the ability to use stable isotope analysis in assessing bacterial sulfate reduction.

Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps

DOE PAGES

Sivan, Orit; Antler, Gilad; Turchyn, Alexandra V.; ...

2014-09-22

Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sediments incubated with 13C-labeled methane showed co-occurring sulfate reduction, AOM, and methanogenesis. The isotope fractionation factors for sulfur and oxygen isotopes in sulfate were about 40‰ and 22‰, respectively, reinforcing the difference between microbial sulfate reduction in methane seeps versus other sedimentary environments (for example, sulfur isotope fractionation above 60‰ in sulfate reduction coupled to organicmore » carbon oxidation or in diffusive sedimentary sulfate–methane transition zone). The addition of hematite to these microcosm experiments resulted in significant microbial iron reduction as well as enhancing sulfate-driven AOM. The magnitude of the isotope fractionation of sulfur and oxygen isotopes in sulfate from these incubations was lowered by about 50%, indicating the involvement of iron oxides during sulfate reduction in methane seeps. The similar relative change between the oxygen versus sulfur isotopes of sulfate in all experiments (with and without hematite addition) suggests that oxidized forms of iron, naturally present in the sediment incubations, were involved in sulfate reduction, with hematite addition increasing the sulfate recycling or the activity of sulfur-cycling microorganisms by about 40%. Furthermore, these results highlight a role for natural iron oxides during bacterial sulfate reduction in methane seeps not only as nutrient but also as stimulator of sulfur recycling.« less

Processes controlling the seasonal and spatial variations in sulfate profiles in the pore water of the sediments surrounding Qi'ao Island, Pearl River Estuary, Southern China

NASA Astrophysics Data System (ADS)

Wu, Zijun; Zhou, Huaiyang; Ren, Dezhang; Gao, Hang; Li, Jiangtao

2015-04-01

Marine sediments are the main sink for seawater sulfate and bacterial sulfate reduction is a major component of the global sulfur cycle. Nevertheless, the factors controlling sulfate reduction in the coastal estuary sediments that undergo spatial and temporal variations are still not fully understood. In this study, we measured the concentrations of SO42-, Cl-, CH4, and DIC, and the δ13C of DIC in the pore water of five sampling stations surrounding the Qi'ao Island, Pearl River Estuary, Southern China during the dry season in November 2011 and during the wet season in May 2012. The results showed that the dilution-mixing of the Pearl River with low-concentration sulfate significantly affects the downcore profiles of the sulfate concentrations in the pore water of these estuary sediments. During the wet season, the dilution-mixing of the layers from the top of the sediments to a depth of 14-18 cm occurred at the different sampling stations. In this layer, the sulfate reduction is not appreciable based on the plot of the pore water Cl- and SO42-. Below the dilution-mixing layers, however, sulfate reduction that is driven by the anaerobic oxidation of methane (AOM) occurs. In our comparison, it appeared that the AOM played more important role in the consumption of the pore water sulfate in May 2012 than in November 2011. Meanwhile, we observed a relatively good correlation (r2=0.64) between the depth of the sulfate-methane interface (SMI) and the sulfate concentration in the pore water of the top sediments in dry season, indicating that the pore water sulfate concentration appears to be a primary controlling factor for the depth of the SMI in this estuary. These results highlight the need for an integrated analysis of the hydrologically driven the variations in the sulfate profiles to improve our understanding of the biogeochemical cycling of C, Fe and S and their budgets in estuarine environments.

Energy for biologic sulfate reduction in a hydrothermally formed ocean on Europa

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Y.; Shock, Everett L.

2003-04-01

Formation of a sulfate-bearing ocean on Jupiter's satellite Europa by quenched hydrothermal fluids provides a source of metabolic energy for low-temperature sulfate-reducing organisms that use dissolved H2 as an electron donor. Inhibition of thermodynamically favorable sulfate reduction in cooled hydrothermal fluids creates the potential for biologic reduction. Both high temperature and reduced conditions of ocean-forming hydrothermal solutions favor sulfate reduction in quenched fluids. The maximum amount of energy available to support autotrophic sulfate reduction is on the order of a few kilojoules per kilogram of water and is limited by the low abundances of either H2 or sulfate in ocean-forming fluids. Although this irreplaceable energy source might have supported early life on Europa, maintenance of biologic sulfate reduction throughout the ocean's history would require a supply of organic compounds from endogenic sources or from the satellite's surface.

Quantification and isotopic analysis of intracellular sulfur metabolites in the dissimilatory sulfate reduction pathway

NASA Astrophysics Data System (ADS)

Sim, Min Sub; Paris, Guillaume; Adkins, Jess F.; Orphan, Victoria J.; Sessions, Alex L.

2017-06-01

Microbial sulfate reduction exhibits a normal isotope effect, leaving unreacted sulfate enriched in 34S and producing sulfide that is depleted in 34S. However, the magnitude of sulfur isotope fractionation is quite variable. The resulting changes in sulfur isotope abundance have been used to trace microbial sulfate reduction in modern and ancient ecosystems, but the intracellular mechanism(s) underlying the wide range of fractionations remains unclear. Here we report the concentrations and isotopic ratios of sulfur metabolites in the dissimilatory sulfate reduction pathway of Desulfovibrio alaskensis. Intracellular sulfate and APS levels change depending on the growth phase, peaking at the end of exponential phase, while sulfite accumulates in the cell during stationary phase. During exponential growth, intracellular sulfate and APS are strongly enriched in 34S. The fractionation between internal and external sulfate is up to 49‰, while at the same time that between external sulfate and sulfide is just a few permil. We interpret this pattern to indicate that enzymatic fractionations remain large but the net fractionation between sulfate and sulfide is muted by the closed-system limitation of intracellular sulfate. This 'reservoir effect' diminishes upon cessation of exponential phase growth, allowing the expression of larger net sulfur isotope fractionations. Thus, the relative rates of sulfate exchange across the membrane versus intracellular sulfate reduction should govern the overall (net) fractionation that is expressed. A strong reservoir effect due to vigorous sulfate reduction might be responsible for the well-established inverse correlation between sulfur isotope fractionation and the cell-specific rate of sulfate reduction, while at the same time intraspecies differences in sulfate uptake and/or exchange rates could account for the significant scatter in this relationship. Our approach, together with ongoing investigations of the kinetic isotope fractionation by key enzymes in the sulfate reduction pathway, should provide an empirical basis for a quantitative model relating the magnitude of microbial isotope fractionation to their environmental and physiological controls.

Activity and phylogenetic diversity of sulfate-reducing microorganisms in low-temperature subsurface fluids within the upper oceanic crust

PubMed Central

Robador, Alberto; Jungbluth, Sean P.; LaRowe, Douglas E.; Bowers, Robert M.; Rappé, Michael S.; Amend, Jan P.; Cowen, James P.

2015-01-01

The basaltic ocean crust is the largest aquifer system on Earth, yet the rates of biological activity in this environment are unknown. Low-temperature (<100°C) fluid samples were investigated from two borehole observatories in the Juan de Fuca Ridge (JFR) flank, representing a range of upper oceanic basement thermal and geochemical properties. Microbial sulfate reduction rates (SRR) were measured in laboratory incubations with 35S-sulfate over a range of temperatures and the identity of the corresponding sulfate-reducing microorganisms (SRM) was studied by analyzing the sequence diversity of the functional marker dissimilatory (bi)sulfite reductase (dsrAB) gene. We found that microbial sulfate reduction was limited by the decreasing availability of organic electron donors in higher temperature, more altered fluids. Thermodynamic calculations indicate energetic constraints for metabolism, which together with relatively higher cell-specific SRR reveal increased maintenance requirements, consistent with novel species-level dsrAB phylotypes of thermophilic SRM. Our estimates suggest that microbially-mediated sulfate reduction may account for the removal of organic matter in fluids within the upper oceanic crust and underscore the potential quantitative impact of microbial processes in deep subsurface marine crustal fluids on marine and global biogeochemical carbon cycling. PMID:25642212

Microbial sulfate reduction rates and sulfur and oxygen isotope fractionations at oil and gas seeps in deepwater Gulf of Mexico

NASA Astrophysics Data System (ADS)

Aharon, Paul; Fu, Baoshun

2000-01-01

Sulfate reduction and anaerobic methane oxidation are the dominant microbial processes occurring in hydrate-bearing sediments at bathyal depths in the Gulf of Mexico where crude oil and methane are advecting through fault conduits to the seafloor. The oil and gas seeps are typically overlain by chemosynthetic communities consisting of thiotrophic bacterial mats (Beggiatoa spp.) and methanotrophic mussels (Bathymodiolus spp.), respectively. Cores were recovered with a manned submersible from fine-grained sediments containing dispersed gas hydrates at the threshold of stability. Estimated sulfate reduction rates are variable but generally are substantially higher in crude oil seeps (up to 50 times) and methane seeps (up to 600 times) relative to a non-seep reference sediment (0.0043 μmol SO 42- cm -3 day -1). Sulfur and oxygen isotope fractionation factors are highest in the reference sediment (α S = 1.027; α O = 1.015) but substantially lower in the seep sediments (α S = 1.018 to 1.009; α O = 1.006 to 1.002) and are controlled primarily by kinetic factors related to sulfate reduction rates. Kinetic effects also control the δ 34S/δ 18O ratios such that slow microbial rates yield low ratios whereas faster rates yield progressively higher ratios. The seep data contradict previous claims that δ 34S/δ 18O ratios are diagnostic of either microbial sulfate reduction at a fixed δ 34S/δ 18O ratio of 4/1 or lower ratios caused by SO 4-H 2O equilibration at ambient temperatures. The new results offer a better understanding of methane removal via anaerobic oxidation in the sulfate reduction zone of hydrate-bearing sediments and have significant implications regarding the origin and geochemical history of sedimentary sulfate reconstructed on the basis of δ 34S and δ 18O compositions.

In Situ Rates of Sulfate Reduction in Response to Geochemical Perturbations

USGS Publications Warehouse

Kneeshaw, T.A.; McGuire, J.T.; Cozzarelli, I.M.; Smith, E.W.

2011-01-01

Rates of in situ microbial sulfate reduction in response to geochemical perturbations were determined using Native Organism Geochemical Experimentation Enclosures (NOGEEs), a new in situ technique developed to facilitate evaluation of controls on microbial reaction rates. NOGEEs function by first trapping a native microbial community in situ and then subjecting it to geochemical perturbations through the introduction of various test solutions. On three occasions, NOGEEs were used at the Norman Landfill research site in Norman, Oklahoma, to evaluate sulfate-reduction rates in wetland sediments impacted by landfill leachate. The initial experiment, in May 2007, consisted of five introductions of a sulfate test solution over 11 d. Each test stimulated sulfate reduction with rates increasing until an apparent maximum was achieved. Two subsequent experiments, conducted in October 2007 and February 2008, evaluated the effects of concentration on sulfate-reduction rates. Results from these experiments showed that faster sulfate-reduction rates were associated with increased sulfate concentrations. Understanding variability in sulfate-reduction rates in response to perturbations may be an important factor in predicting rates of natural attenuation and bioremediation of contaminants in systems not at biogeochemical equilibrium. Copyright ?? 2011 The Author(s). Journal compilation ?? 2011 National Ground Water Association.

[Acclimatization and characteristics of microbial community in sulphate-dependent anaerobic methane oxidation].

PubMed

Xi, Jing-Ru; Liu, Su-Qin; Li, Lin; Liu, Jun-Xin

2014-12-01

The greenhouse effect of methane is 26 times worse than that of carbon dioxide, and wastewater containing high concentrations of sulfate is harmful to water, soil and plants. Therefore, anaerobic oxidation of methane driven by sulfate is one of the effective ways for methane reduction. In this paper, with sulfate as the electron accepter, a microbial consortium capable of oxidating methane under anaerobic condition was cultured. The diversity and characteristics of bacterial and archaeal community were investigated by PCR-DGGE, and phylogenetic analysis of the dominant microorganisms was also carried out. The DGGE fingerprints showed that microbial community structure changed distinctly, and the abundance of methane-oxidizing archea and sulfate-reducing bacteria increased in the acclimatization system added sulfate. After acclimatization, the bacterial diversity increased, while archaea diversity decreased slightly. The representative bands in the DGGE profiles were excised and sequenced. Results indicated that the dominant species in the acclimatization system were Spirochaetes, Desulfuromonadales, Methanosarcinales, Methanosaeta. Methane converted into carbon dioxide while sulfate transformed into hydrogen sulfide and sulfur in the process of anaerobic methane oxidation accompanied by sulphate reduction.

Simultaneous heterotrophic and sulfur-oxidizing autotrophic denitrification process for drinking water treatment: control of sulfate production.

PubMed

Sahinkaya, Erkan; Dursun, Nesrin; Kilic, Adem; Demirel, Sevgi; Uyanik, Sinan; Cinar, Ozer

2011-12-15

A long-term performance of a packed-bed bioreactor containing sulfur and limestone was evaluated for the denitrification of drinking water. Autotrophic denitrification rate was limited by the slow dissolution rate of sulfur and limestone. Dissolution of limestone for alkalinity supplementation increased hardness due to release of Ca(2+). Sulfate production is the main disadvantage of the sulfur autotrophic denitrification process. The effluent sulfate concentration was reduced to values below drinking water guidelines by stimulating the simultaneous heterotrophic and autotrophic denitrification with methanol supplementation. Complete removal of 75 mg/L NO(3)-N with effluent sulfate concentration of around 225 mg/L was achieved when methanol was supplemented at methanol/NO(3)-N ratio of 1.67 (mg/mg), which was much lower than the theoretical value of 2.47 for heterotrophic denitrification. Batch studies showed that sulfur-based autotrophic NO(2)-N reduction rate was around three times lower than the reduction rate of NO(3)-N, which led to NO(2)-N accumulation at high loadings. Copyright © 2011 Elsevier Ltd. All rights reserved.

Life cycle energy and greenhouse gas profile of a process for the production of ammonium sulfate from nitrogen-fixing photosynthetic cyanobacteria.

PubMed

Razon, Luis F

2012-03-01

In this paper, an alternative means for nitrogen fixation that may consume less energy and release less greenhouse gases than the Haber-Bosch process is explored. A life-cycle assessment was conducted on a process to: culture the cyanobacterium, Anabaena sp. ATCC 33047, in open ponds; harvest the biomass and exopolysaccharides and convert these to biogas; strip and convert the ammonia from the biogas residue to ammonium sulfate; dry the ammonium sulfate solution to ammonium sulfate crystals and transport the finished product. The results suggest that substantial reductions in non-renewable energy use and greenhouse gas emissions may be realized. The study opens the possibility that Haber-Bosch ammonia may be replaced with ammonia from a biomass process which simultaneously generates renewable energy. The process is intrinsically safer than the Haber-Bosch process. However, there are trade-offs in terms of land use and possibly, water. Copyright © 2011 Elsevier Ltd. All rights reserved.

Anaerobic Transformation of Chlorinated Aliphatic Hydrocarbons in a Sand Aquifer Based on Spatial Chemical Distributions

NASA Astrophysics Data System (ADS)

Semprini, Lewis; Kitanidis, Peter K.; Kampbell, Don H.; Wilson, John T.

1995-04-01

We estimated the distribution of chlorinated aliphatic hydrocarbons (CAHs) from groundwater samples collected along three transects in a sand aquifer. Trichloroethylene (TCE) leaked and contaminated the aquifer probably more than a decade before we collected the measurements. The data show significant concentrations of TCE, cis-l,2-dichloroethylene (c-DCE), vinyl chloride (VC), and ethene. We attributed DCE, VC, and ethene to the reductive dehalogenation of TCE. The CAH concentrations varied significantly with depth and correlate with sulfate and methane concentrations. Anoxic aquifer conditions exist with methane present at relatively high concentrations at depth. High concentrations of TCE correspond with the absence of methane or low methane concentrations, whereas products of TCE dehalogenation are associated with higher methane concentrations and low sulfate concentrations. Indications are that the dechlorination of TCE and DCE to VC and ethene is associated with sulfate reduction and active methanogenesis. TCE dechlorination to DCE is likely occurring under the less reducing conditions of sulfate reduction, with further reductions to VC and ethene occurring under methanogenic conditions. We estimated that about 20% of TCE has dechlorinated to ethene. The analysis of the data enhanced our knowledge of natural in situ transformation and transport processes of CAHs.

A Critical Look at the Combined Use of Sulfur and Oxygen Isotopes to Study Microbial Metabolisms in Methane-Rich Environments

PubMed Central

Antler, Gilad; Pellerin, André

2018-01-01

Separating the contributions of anaerobic oxidation of methane and organoclastic sulfate reduction in the overall sedimentary sulfur cycle of marine sediments has benefited from advances in isotope biogeochemistry. Particularly, the coupling of sulfur and oxygen isotopes measured in the residual sulfate pool (δ18OSO4 vs. δ34SSO4). Yet, some important questions remain. Recent works have observed patterns that are inconsistent with previous interpretations. We differentiate the contributions of oxygen and sulfur isotopes to separating the anaerobic oxidation of methane and organoclastic sulfate reduction into three phases; first evidence from conventional high methane vs. low methane sites suggests a clear relationship between oxygen and sulfur isotopes in porewater and the metabolic process taking place. Second, evidence from pure cultures and organic matter rich sites with low levels of methane suggest the signatures of both processes overlap and cannot be differentiated. Third, we take a critical look at the use of oxygen and sulfur isotopes to differentiate metabolic processes (anaerobic oxidation of methane vs. organoclastic sulfate reduction). We identify that it is essential to develop a better understanding of the oxygen kinetic isotope effect, the degree of isotope exchange with sulfur intermediates as well as establishing their relationships with the cell-specific metabolic rates if we are to develop this proxy into a reliable tool to study the sulfur cycle in marine sediments and the geological record. PMID:29681890

Kinetics of sulfate and hydrogen uptake by the thermophilic sulfate-reducing bacteria Thermodesulfobacterium sp. strain JSP and Thermodesulfovibrio sp. strain R1Ha3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sonne-Hansen, J.; Ahring, B.K.; Westermann, P.

1999-03-01

Dissimilatory sulfate reduction and methanogenesis are the main terminal processes in the anaerobic food chain. Both the sulfate-reducing bacteria (SRB) and the methane-producing archaea (MPA) use acetate and hydrogen as substrates and, therefore, compete for common electron donors in sulfate-containing natural environments. Due to a higher affinity for the electron donors acetate and hydrogen, SRB outcompete MPA for these compounds whenever sulfate is present in sufficient concentrations. Half-saturation constants (K{sub m}), maximum uptake rates (V{sub max}), and threshold concentrations for sulfate and hydrogen were determined for two thermophilic sulfate-reducing bacteria (SRB) in an incubation system without headspace. K{sub m} valuesmore » determined for the thermophilic SRB were similar to the constants described for mesophilic SRB isolated from environments with low sulfate concentrations.« less

Modeling Reduction of Uranium U(VI) under Variable Sulfate Concentrations by Sulfate-Reducing Bacteria

PubMed Central

Spear, John R.; Figueroa, Linda A.; Honeyman, Bruce D.

2000-01-01

The kinetics for the reduction of sulfate alone and for concurrent uranium [U(VI)] and sulfate reduction, by mixed and pure cultures of sulfate-reducing bacteria (SRB) at 21 ± 3°C were studied. The mixed culture contained the SRB Desulfovibrio vulgaris along with a Clostridium sp. determined via 16S ribosomal DNA analysis. The pure culture was Desulfovibrio desulfuricans (ATCC 7757). A zero-order model best fit the data for the reduction of sulfate from 0.1 to 10 mM. A lag time occurred below cell concentrations of 0.1 mg (dry weight) of cells/ml. For the mixed culture, average values for the maximum specific reaction rate, Vmax, ranged from 2.4 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1) at 0.25 mM sulfate to 5.0 ± 1.1 μmol of sulfate/mg (dry weight) of SRB · h−1 at 10 mM sulfate (average cell concentration, 0.52 mg [dry weight]/ml). For the pure culture, Vmax was 1.6 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1 at 1 mM sulfate (0.29 mg [dry weight] of cells/ml). When both electron acceptors were present, sulfate reduction remained zero order for both cultures, while uranium reduction was first order, with rate constants of 0.071 ± 0.003 mg (dry weight) of cells/ml · min−1 for the mixed culture and 0.137 ± 0.016 mg (dry weight) of cells/ml · min−1 (U0 = 1 mM) for the D. desulfuricans culture. Both cultures exhibited a faster rate of uranium reduction in the presence of sulfate and no lag time until the onset of U reduction in contrast to U alone. This kinetics information can be used to design an SRB-dominated biotreatment scheme for the removal of U(VI) from an aqueous source. PMID:10966381

[Achievement of Sulfate-Reducing Anaerobic Ammonium Oxidation Reactor Started with Nitrate-Reducting Anaerobic Ammonium Oxidation].

PubMed

Liu, Zheng-chuan; Yuan, Lin-jiang; Zhou, Guo-biao; Li, Jing

2015-09-01

The transformation of nitrite-reducing anaerobic ammonium oxidation to sulfate-reducing anaerobic ammonium oxidation in an UASB was performed and the changes in microbial community were studied. The result showed that the sulfate reducing anaerobic ammonium oxidation process was successfully accomplished after 177 days' operation. The removal rate of ammonium nitrogen and sulfate were up to 58. 9% and 15. 7%, the removing load of ammonium nitrogen and sulfate were 74. 3 mg.(L.d)-1 and 77. 5 mg.(L.d)-1 while concentration of ammonium nitrogen and sulfate of influent were 130 mg.(L.d)-1 and 500 mg.(L.d)-1, respectively. The lost nitrogen and sulphur was around 2 in molar ratio. The pH value of the effluent was lower than that of the influent. Instead of Candidatus brocadia in nitrite reducing anaerobic ammonium oxidation granular sludge, Bacillus benzoevorans became the dominant species in sulfate reducing anaerobic ammonium oxidation sludge. The dominant bacterium in the two kinds of anaerobic ammonium oxidation process is different. Our results imply that the two anaerobic ammonium oxidation processes are carried out by different kind of bacterium.

Uranium Sequestration During Biostimulated Reduction and In Response to the Return of Oxic Conditions In Shallow Aquifers

USGS Publications Warehouse

Fuller, Christopher C.; Johnson, Kelly J.; Akstin, Katherine; Singer, David M.; Yabusaki, Steven B.; Fang, Yilin; Fuhrmann, M.

2015-01-01

A proposed approach for groundwater remediation of uranium contamination is to generate reducing conditions by stimulating the growth of microbial populations through injection of electron donor compounds into the subsurface. Sufficiently reducing conditions will result in reduction of soluble hexavalent uranium, U(VI), and precipitation of the less soluble +4 oxidation state uranium, U(IV). This process is termed biostimulated reduction. A key issue in the remediation of uranium (U) contamination in aquifers by biostimulated reduction is the long term stability of the sequestered uranium. Three flow-through column experiments using aquifer sediment were used to evaluate the remobilization of bioreduced U sequestered under conditions in which biostimulation extended well into sulfate reduction to enhance precipitation of reduced sulfur phases such as iron sulfides. One column received added ferrous iron, Fe(II), increasing production of iron sulfides, to test their effect on remobilization of the sequestered uranium, either by serving as a redox buffer by competing for dissolved oxygen, or by armoring the reduced uranium. During biostimulation of the ambient microbial population with acetate, dissolved uranium was lowered by a factor of 2.5 or more with continued removal for over 110 days of biostimulation, well after the onset of sulfate reduction at ~30 days. Sequestered uranium was essentially all U(IV) resulting from the formation of nano-particulate uraninite that coated sediment grains to a thickness of a few 10’s of microns, sometimes in association with S and Fe. A multicomponent biogeochemical reactive transport model simulation of column effluents during biostimulation was generally able to describe the acetate oxidation, iron, sulfate, and uranium reduction for all three columns using parameters derived from simulations of field scale biostimulation experiments. Columns were eluted with artificial groundwater at equilibrium with atmospheric oxygen to simulate the upper limit of dissolved oxygen in recharge water. Overall about 9% of total uranium removed from solution during biostimulation was remobilized. Release of U during oxic elution was a continuous process over 140 days with dissolved uranium concentrations about 0.2 and 0.8 aM for columns with and without ferrous iron addition, respectively. Uranium remaining on the sediment was in the reduced form. The prolonged period of biostimulation and concomitant sulfate reduction appears to limit the rate of U(IV) oxidative remobilization in contrast to a large release observed for columns in previous studies that did not undergo sulfate reduction. Although continued sulfate reduction may cause decreased permeability from precipitation of iron sulfide, the greater apparent stability of the sequestered U(IV) provided by the sustained biostimulation should be considered in design of field scale remediation efforts. Remobilization of uranium following biostimulated reduction should be tested further at the field scale.

Kinetics of nitrate and sulfate removal using a mixed microbial culture with or without limited-oxygen fed.

PubMed

Xu, Xi-Jun; Chen, Chuan; Wang, Ai-Jie; Guo, Hong-Liang; Yuan, Ye; Lee, Duu-Jong; Ren, Nan-Qi

2014-07-01

The biological degradation of nitrate and sulfate was investigated using a mixed microbial culture and lactate as the carbon source, with or without limited-oxygen fed. It was found that sulfate reduction was slightly inhibited by nitrate, since after nitrate depletion the sulfate reduction rate increased from 0.37 mg SO4 (2-)/mg VSS d to 0.71 mg SO4 (2-)/mg VSS d, and the maximum rate of sulfate reduction in the presence of nitrate corresponded to 56 % of the non-inhibited sulfate reduction rate determined after nitrate depleted. However, simultaneous but not sequential reduction of both oxy-anions was observed in this study, unlike some literature reports in which sulfate reduction starts only after depletion of nitrate, and this case might be due to the fact that lactate was always kept above the limiting conditions. At limited oxygen, the inhibited effect on sulfate reduction by nitrate was relieved, and the sulfate reduction rate seemed relatively higher than that obtained without limited-oxygen fed, whereas kept almost constant (0.86-0.89 mg SO4 (2-)/mg VSS d) cross the six ROS states. In contrast, nitrate reduction rates decreased substantially with the increase in the initial limited-oxygen fed, showing an inhibited effect on nitrate reduction by oxygen. Kinetic parameters determined for the mixed microbial culture showed that the maximum specific sulfate utilization rate obtained (0.098 ± 0.022 mg SO4 (2-)/(mg VSS h)) was similar to the reported typical value (0.1 mg SO4 (2-)/(mg VSS h)), also indicating a moderate inhibited effect by nitrate.

A simple and reliable method reducing sulfate to sulfide for multiple sulfur isotope analysis.

PubMed

Geng, Lei; Savarino, Joel; Savarino, Clara A; Caillon, Nicolas; Cartigny, Pierre; Hattori, Shohei; Ishino, Sakiko; Yoshida, Naohiro

2018-02-28

Precise analysis of four sulfur isotopes of sulfate in geological and environmental samples provides the means to extract unique information in wide geological contexts. Reduction of sulfate to sulfide is the first step to access such information. The conventional reduction method suffers from a cumbersome distillation system, long reaction time and large volume of the reducing solution. We present a new and simple method enabling the process of multiple samples at one time with a much reduced volume of reducing solution. One mL of reducing solution made of HI and NaH 2 PO 2 was added to a septum glass tube with dry sulfate. The tube was heated at 124°C and the produced H 2 S was purged with inert gas (He or N 2 ) through gas-washing tubes and then collected by NaOH solution. The collected H 2 S was converted into Ag 2 S by adding AgNO 3 solution and the co-precipitated Ag 2 O was removed by adding a few drops of concentrated HNO 3 . Within 2-3 h, a 100% yield was observed for samples with 0.2-2.5 μmol Na 2 SO 4 . The reduction rate was much slower for BaSO 4 and a complete reduction was not observed. International sulfur reference materials, NBS-127, SO-5 and SO-6, were processed with this method, and the measured against accepted δ 34 S values yielded a linear regression line which had a slope of 0.99 ± 0.01 and a R 2 value of 0.998. The new methodology is easy to handle and allows us to process multiple samples at a time. It has also demonstrated good reproducibility in terms of H 2 S yield and for further isotope analysis. It is thus a good alternative to the conventional manual method, especially when processing samples with limited amount of sulfate available. © 2017 The Authors. Rapid Communications in Mass Spectrometry Pubished by John Wiley & Sons Ltd.

Methane and sulfate dynamics in sediments from mangrove-dominated tropical coastal lagoons, Yucatan, Mexico

USGS Publications Warehouse

Chuang, P. C.; Young, Megan B.; Dale, Andrew W.; Miller, Laurence G.; Herrera-Silveira, Jorge A.; Paytan, Adina

2016-01-01

Porewater profiles in sediment cores from mangrove-dominated coastal lagoons (Celestún and Chelem) on the Yucatán Peninsula, Mexico, reveal the widespread coexistence of dissolved methane and sulfate. This observation is interesting since dissolved methane in porewaters is typically oxidized anaerobically by sulfate. To explain the observations we used a numerical transport-reaction model that was constrained by the field observations. The model suggests that methane in the upper sediments is produced in the sulfate reduction zone at rates ranging between 0.012 and 31 mmol m−2 d−1, concurrent with sulfate reduction rates between 1.1 and 24 mmol SO42− m−2 d−1. These processes are supported by high organic matter content in the sediment and the use of non-competitive substrates by methanogenic microorganisms. Indeed sediment slurry incubation experiments show that non-competitive substrates such as trimethylamine (TMA) and methanol can be utilized for microbial methanogenesis at the study sites. The model also indicates that a significant fraction of methane is transported to the sulfate reduction zone from deeper zones within the sedimentary column by rising bubbles and gas dissolution. The shallow depths of methane production and the fast rising methane gas bubbles reduce the likelihood for oxidation, thereby allowing a large fraction of the methane formed in the sediments to escape to the overlying water column.

Distribution of microbial methanogenesis, methane oxidation, and sulfate reduction in a high-temperature subduction system of the Nankai Trough off Cape Muroto (IODP Expedition 370 T-Limit, Site C0023)

NASA Astrophysics Data System (ADS)

Treude, T.; Kallmeyer, J.; Beulig, F.; Glombitza, C.; Schubert, F.; Krause, S.; Heuer, V.; Inagaki, F.; Morono, Y.

2017-12-01

The aim of the IODP Expedition 370 is to explore the temperature limit of the deep biosphere in a sub-seafloor environment located in the Nankai Trough, where in-situ sediment temperature increases from 2°C at the seafloor to about 120°C at the 1.2 km deep sediment/basement interface. Our study focuses on the exploration of potential microbial methanogenesis, anaerobic oxidation of methane (AOM), and sulfate reduction in sediments from different depths (from ca. 200 to 1170 mbsf) exposed to several temperature settings in the laboratory (40, 60, 75/80 and 95°C). The drill site, which features a décollement between ca. 758-796 mbsf, includes a sulfate-poor methanogenic zone from approx. 400 to 600 mbsf, followed by a deep methane-sulfate transition zone between approx. 600 to 800 m, which transitions into a deep sulfate-rich zone. Potential microbial activity of hydrogenotrophic methanogenesis, AOM, and sulfate reduction was determined in incubations of sediment slurries produced from whole-round cores with H2-added artificial seawater medium using radioisotope techniques (14C-bicarbonate, 14C-methane, and 35S-sulfate, respectively). Preliminary results revealed two peaks of methanogenesis activity with rates in the order of 0.2 to 0.5 pmol g-1dw d-1. One peak was located within the methane-rich zone passing into the methane-sulfate transition zone (60 to 80°C incubations), while the second peak occurred close to the basement (below 1000 mbsf, 95°C incubation). Sulfate reduction activity was generally highest above 400 mbsf ( 1000 pmol cm-3 d-1, 40°C incubation). Below 400 mbsf, rates declined to levels between 0.1 and 10 pmol cm-3 d-1 (60-95 °C incubations) without a clear trend and continued until close to the bottom of the core. The results point to potentially thermophilic and hypothermophilic microorganisms that exist under very low energy conditions. Samples from AOM incubations are currently being processed and preliminary results will be presented at the meeting as well as the results for sulfate reduction incubations with methane and acetate amendments.

Removing organic matter from sulfate-rich wastewater via sulfidogenic and methanogenic pathways.

PubMed

Vilela, Rogerio Silveira; Damianovic, Márcia Helena Rissato Zamariolli; Foresti, Eugenio

2014-01-01

The simultaneous organic matter removal and sulfate reduction in synthetic sulfate-rich wastewater was evaluated for various chemical oxygen demand (COD)/sulfate ratios applied in a horizontal-flow anaerobic immobilized sludge (HAIS) reactor. At higher COD/sulfate ratios (12.5 and 7.5), the removal of organic matter was stable, likely due to methanogenesis. A combination of sulfate reduction and methanogenesis was clearly established at COD/sulfate ratios of 3.0 and 1.9. At a COD/sulfate ratio of 1.0, the organic matter removal was likely influenced by methanogenesis inhibition. The quantity of sulfate removed at a COD/sulfate ratio of 1.0 was identical to that obtained at a ratio of 1.9, indicating a lack of available electron donors for sulfidogenesis. The sulfate reduction and organic matter removal were not maximized at the same COD/sulfate ratio; therefore, competitive inhibition must be the predominant mechanism in establishing an electron flow.

Sulfur cycling in plays an important role in the development of Ocean Anoxic Events

NASA Astrophysics Data System (ADS)

Gomes, M. L.; Raven, M. R.; Fike, D. A.; Gill, B. C.; Johnston, D. T.

2017-12-01

Ocean Anoxic Events (OAEs) are major carbon cycle perturbations marked by enhanced organic carbon deposition in the marine realm and carbon isotope excursions in organic and inorganic carbon. Although not as severe as the "big five" mass extinctions, OAEs had dire consequences for marine ecosystems and thus influenced Mesozoic evolutionary patterns. Sulfur cycle reconstructions provide insight into the biogeochemical processes that played a role in the development of OAEs because the sulfur cycle is linked with the carbon and oxygen cycles. We present sulfur and oxygen isotope records from carbonate-associated sulfate from the Toarcian OAE that documents a positive sulfate-oxygen isotope excursion of +6‰, which is similar to the magnitude of the positive sulfur isotope excursion documented at the same site and other globally distributed sites. This high-resolution record allows us to explore temporal variability in the onset of the isotopic excursions: the onset of the positive sulfate-oxygen isotope excursion occurs at the same stratigraphic interval as the onset of the positive carbon isotope excursion and both precede the onset of the positive sulfate-sulfur isotope excursion. Because oxygen is rapidly recycled during oxidative sulfur cycling, changes in oxidative sulfur cycling affect oxygen isotope values of sulfate without impacting sulfur isotope values. Thus, the early onset of the sulfate-oxygen isotope excursion implies a change in oxidative sulfur cycling, which is likely due to a shoaling of the zone of sulfate reduction. We explore the consequences of sulfate reduction zone shoaling for organic carbon preservation. Specifically, the sulfurization of organic matter, which makes organic matter less susceptible to degradation, occurs more rapidly when the top of the zone of sulfate reduction is near or above the sediment water interface. Therefore, we suggest that the shoaling of the sulfate reduction zone locally changed pathways of oxidative sulfur cycling and enhanced organic carbon preservation. Given synchronous changes in similar, globally-distributed depositional environments, this impacted the global biogeochemical cycles of oxygen, carbon, and nutrients in ways that sustained decreased oxygen availability and influenced extinction patterns of marine organisms.

Isotope effects associated with the anaerobic oxidation of sulfite and thiosulfate by the photosynthetic bacterium, Chromatium vinosum

NASA Technical Reports Server (NTRS)

Fry, B.; Gest, H.; Hayes, J. M.

1985-01-01

The purple photosynthetic bacterium Chromatium vinosum, strain D, catalyzes several oxidations of reduced sulfur compounds under anaerobic conditions in the light: e.g., sulfide --> sulfur --> sulfate, sulfite --> sulfate, and thiosulfate --> sulfur + sulfate. Here it is shown that no sulfur isotope effect is associated with the last of these processes; isotopic compositions of the sulfur and sulfate produced can differ, however, if the sulfane and sulfonate positions within the thiosulfate have different isotopic compositions. In the second process, an observed change from an inverse to a normal isotope effect during oxidation of sulfite may indicate the operation of 2 enzymatic pathways. In contrast to heterotrophic anaerobic reduction of oxidized sulfur compounds, anaerobic oxidations of inorganic sulfur compounds by photosynthetic bacteria are characterized by relatively small isotope effects.

Early diagenesis in the sediments of the Congo deep-sea fan dominated by massive terrigenous deposits: Part II - Iron-sulfur coupling

NASA Astrophysics Data System (ADS)

Taillefert, Martial; Beckler, Jordon S.; Cathalot, Cécile; Michalopoulos, Panagiotis; Corvaisier, Rudolph; Kiriazis, Nicole; Caprais, Jean-Claude; Pastor, Lucie; Rabouille, Christophe

2017-08-01

Deep-sea fans are well known depot centers for organic carbon that should promote sulfate reduction. At the same time, the high rates of deposition of unconsolidated metal oxides from terrigenous origin may also promote metal-reducing microbial activity. To investigate the eventual coupling between the iron and sulfur cycles in these environments, shallow sediment cores (< 50 cm) across various channels and levees in the Congo River deep-sea fan ( 5000 m) were profiled using a combination of geochemical methods. Interestingly, metal reduction dominated suboxic carbon remineralization processes in most of these sediments, while dissolved sulfide was absent. In some 'hotspot' patches, however, sulfate reduction produced large sulfide concentrations which supported chemosynthetic-based benthic megafauna. These environments were characterized by sharp geochemical boundaries compared to the iron-rich background environment, suggesting that FeS precipitation efficiently titrated iron and sulfide from the pore waters. A companion study demonstrated that methanogenesis was active in the deep sediment layers of these patchy ecosystems, suggesting that sulfate reduction was promoted by alternative anaerobic processes. These highly reduced habitats could be fueled by discrete, excess inputs of highly labile natural organic matter from Congo River turbidites or by exhumation of buried sulfide during channel flank erosion and slumping. Sulfidic conditions may be maintained by the mineralization of decomposition products from local benthic macrofauna or bacterial symbionts or by the production of more crystalline Fe(III) oxide phases that are less thermodynamically favorable than sulfate reduction in these bioturbated sediments. Overall, the iron and sulfur biogeochemical cycling in this environment is unique and much more similar to a coastal ecosystem than a deep-sea environment.

The effects of acid deposition on sulfate reduction and methane production in peatlands

NASA Technical Reports Server (NTRS)

Murray, Georgia L.; Hines, Mark E.; Bayley, Suzanne E.

1992-01-01

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

On the Occurrence of Anoxic Microniches, Denitrification, and Sulfate Reduction in Aerated Activated Sludge

PubMed Central

Schramm, Andreas; Santegoeds, Cecilia M.; Nielsen, Helle K.; Ploug, Helle; Wagner, Michael; Pribyl, Milan; Wanner, Jiri; Amann, Rudolf; de Beer, Dirk

1999-01-01

A combination of different methods was applied to investigate the occurrence of anaerobic processes in aerated activated sludge. Microsensor measurements (O2, NO2−, NO3−, and H2S) were performed on single sludge flocs to detect anoxic niches, nitrate reduction, or sulfate reduction on a microscale. Incubations of activated sludge with 15NO3− and 35SO42− were used to determine denitrification and sulfate reduction rates on a batch scale. In four of six investigated sludges, no anoxic zones developed during aeration, and consequently denitrification rates were very low. However, in two sludges anoxia in flocs coincided with significant denitrification rates. Sulfate reduction could not be detected in any sludge in either the microsensor or the batch investigation, not even under short-term anoxic conditions. In contrast, the presence of sulfate-reducing bacteria was shown by fluorescence in situ hybridization with 16S rRNA-targeted oligonucleotide probes and by PCR-based detection of genes coding for the dissimilatory sulfite reductase. A possible explanation for the absence of anoxia even in most of the larger flocs might be that oxygen transport is not only diffusional but enhanced by advection, i.e., facilitated by flow through pores and channels. This possibility is suggested by the irregularity of some oxygen profiles and by confocal laser scanning microscopy of the three-dimensional floc structures, which showed that flocs from the two sludges in which anoxic zones were found were apparently denser than flocs from the other sludges. PMID:10473433

Selective catalytic reduction system and process for treating NOx emissions using a zinc or titanium promoted palladium-zirconium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-08-02

A process and system (18) for reducing NO.sub.x in a gas using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream (29) with a catalyst system (38) comprising sulfated zirconia washcoat particles (41), palladium, a pre-sulfated zirconia binder (44), and a promoter (45) comprising at least one of titanium, zinc, or a mixture thereof. The presence of zinc or titanium increases the resistance of the catalyst system to a sulfur and water-containing gas stream.

Increase in Nutrients, Mercury, and Methylmercury as a Consequence of Elevated Sulfate Reduction to Sulfide in Experimental Wetland Mesocosms

NASA Astrophysics Data System (ADS)

Myrbo, A.; Swain, E. B.; Johnson, N. W.; Engstrom, D. R.; Pastor, J.; Dewey, B.; Monson, P.; Brenner, J.; Dykhuizen Shore, M.; Peters, E. B.

2017-11-01

Microbial sulfate reduction (MSR) in both freshwater and marine ecosystems is a pathway for the decomposition of sedimentary organic matter (OM) after oxygen has been consumed. In experimental freshwater wetland mesocosms, sulfate additions allowed MSR to mineralize OM that would not otherwise have been decomposed. The mineralization of OM by MSR increased surface water concentrations of ecologically important constituents of OM: dissolved inorganic carbon, dissolved organic carbon, phosphorus, nitrogen, total mercury, and methylmercury. Increases in surface water concentrations, except for methylmercury, were in proportion to cumulative sulfate reduction, which was estimated by sulfate loss from the surface water into the sediments. Stoichiometric analysis shows that the increases were less than would be predicted from ratios with carbon in sediment, indicating that there are processes that limit P, N, and Hg mobilization to, or retention in, surface water. The highest sulfate treatment produced high levels of sulfide that retarded the methylation of mercury but simultaneously mobilized sedimentary inorganic mercury into surface water. As a result, the proportion of mercury in the surface water as methylmercury peaked at intermediate pore water sulfide concentrations. The mesocosms have a relatively high ratio of wall and sediment surfaces to the volume of overlying water, perhaps enhancing the removal of nutrients and mercury to periphyton. The presence of wild rice decreased sediment sulfide concentrations by 30%, which was most likely a result of oxygen release from the wild rice roots. An additional consequence of the enhanced MSR was that sulfate additions produced phytotoxic levels of sulfide in sediment pore water.

Influence of sulfur oxyanions on reductive dehalogenation activities in Desulfomonile tiedjei.

PubMed Central

Townsend, G T; Suflita, J M

1997-01-01

The inhibition of aryl reductive dehalogenation reactions by sulfur oxyanions has been demonstrated in environmental samples, dehalogenating enrichments, and the sulfate-reducing bacterium Desulfomonile tiedjei; however, this phenomenon is not well understood. We examined the effects of sulfate, sulfite, and thiosulfate on reductive dehalogenation in the model microorganism D. tiedjei and found separate mechanisms of inhibition due to these oxyanions under growth versus nongrowth conditions. Dehalogenation activity was greatly reduced in extracts of cells grown in the presence of both 3-chlorobenzoate, the substrate or inducer for the aryl dehalogenation activity, and either sulfate, sulfite, or thiosulfate, indicating that sulfur oxyanions repress the requisite enzymes. In extracts of fully induced cells, thiosulfate and sulfite, but not sulfate, were potent inhibitors of aryl dehalogenation activity even in membrane fractions lacking the cytoplasmically located sulfur oxyanion reductase. These results suggest that under growth conditions, sulfur oxyanions serve as preferred electron acceptors and negatively influence dehalogenation activity in D. tiedjei by regulating the amount of active aryl dehalogenase in cells. Additionally, in vitro inhibition by sulfur oxyanions is due to the interaction of the reactive species with enzymes involved in dehalogenation and need not involve competition between two respiratory processes for reducing equivalents. Sulfur oxyanions also inhibited tetrachloroethylene dehalogenation by the same mechanisms, further indicating that chloroethylenes are fortuitously dehalogenated by the aryl dehalogenase. The commonly observed inhibition of reductive dehalogenation reactions under sulfate-reducing conditions may be due to similar regulation mechanisms in other dehalogenating microorganisms that contain multiple respiratory activities. PMID:9293011

Genome Sequence of the Moderately Acidophilic Sulfate-Reducing Firmicute Desulfosporosinus acididurans (Strain M1T)

PubMed Central

Petzsch, Patrick; Poehlein, Anja; Johnson, D. Barrie; Daniel, Rolf; Schlömann, Michael

2015-01-01

Microbial dissimilatory sulfate reduction is commonplace in many anaerobic environments, though few acidophilic bacteria are known to mediate this process. We report the 4.64-Mb draft genome of the type strain of the moderate acidophile Desulfosporosinus acididurans, which was isolated from acidic sediment in a river draining the Soufrière volcano, Montserrat. PMID:26251501

Sulfur Isotope Fractionation in Marine Pore waters from the Offshore Southwestern Taiwan

NASA Astrophysics Data System (ADS)

Yu, T. L.; Chen, N. C.; Wang, B. S.; Lin, L. H.; Yang, T. F.; Chen, Y. G.; Shen, C. C.

2017-12-01

In this study, we selected two marine sediment cores, 474cm C11 and 252cm EN1, with different sulfate reduction rate due to anaerobic oxidation of methane (AOM) in offshore southwestern Taiwan, to clarify the regional sulfur biogeochemical process. Sulfur isotopic composition in pore waters was determined on a multi-collector inductively coupled mass spectrometer, Thermo NEPTUNE, with 2-sigma reproducibility of ±0.18‰. Our results show that correlation between δ34S values of 21.7-40.6‰ and 21.5-54.3‰, and sulfate contents of 7.1-26.6 and 1.2-27.6mM follows a closed system Rayleigh fractionation model above the sulfate-methane transition zone (SMTZ) at depths of 172.5 cm for core C11 and 212.5 cm for core EN1 below sea floor. At the SMTZ, δ34S reaches the summit of 40.6 ‰, followed by a decreasing trend to 16-20‰ at depth of 172.5-470.0 cm for core C11. Our results suggest that sulfur in pore fluids offshore southwestern Taiwan is controlled by multiple processes including microbial sulfate reduction, barite dissolution and clay dehydration.

Kinetic comparison of microbial assemblages for the anaerobic treatment of wastewater with high sulfate and heavy metal contents.

PubMed

Sinbuathong, Nusara; Sirirote, Pramote; Liengcharernsit, Winai; Khaodhiar, Sutha; Watts, Daniel J

2009-01-01

Mixed-microbial assemblages enriched from a septic tank, coastal sediment samples, the digester sludge of a brewery wastewater treatment plant and acidic sulfate soil samples were compared on the basis of growth rate, waste and sulfate reduction rate under sulfate reducing conditions at 30 degrees C. The specific growth rate of various cultures was in the range 0.0013-0.0022 hr(-1). Estimates of waste and sulfate reduction rate were obtained by fitting substrate depletion and sulfate reduction data with the Michaelis-Menten equation. The waste reduction rates were in the range 4x10(-8)-1x10(-7) I mg(-1) hr(-1) and generally increased in the presence of copper, likely by copper sulfide precipitation that reduced sulfide and copper toxicity and thus protected the anaerobic microbes. Anaerobic microorganisms from a brewery digester sludge were found to be the most appropriate culture for the treatment of wastewater with high sulfate and heavy metal content due to their growth rate, and waste and sulfate reduction rate.

Fractionation of Sulfur Isotopes by Desulfovibrio vulgaris Mutants Lacking Periplasmic Hydrogenases or the Type I Tetraheme Cytochrome c3

NASA Astrophysics Data System (ADS)

Sim, M.; Ono, S.; Bosak, T.

2012-12-01

A large fraction of anaerobic mineralization of organic compounds relies on microbial sulfate reduction. Sulfur isotope fractionation by these microbes has been widely used to trace the biogeochemical cycling of sulfur and carbon, but intracellular mechanisms behind the wide range of fractionations observed in nature and cultures are not fully understood. In this study, we investigated the influence of electron transport chain components on the fractionation of sulfur isotopes by culturing Desulfovibrio vulgaris Hildenborough mutants lacking hydrogenases or type I tetraheme cytochrome c3 (Tp1-c3). The mutants were grown both in batch and continuous cultures. All tested mutants grew on lactate or pyruvate as the sole carbon and energy sources, generating sulfide. Mutants lacking cytoplasmic and periplasmic hydrogenases exhibited similar growth physiologies and sulfur isotope fractionations to their parent strains. On the other hand, a mutant lacking Tp1-c3 (ΔcycA) fractionated the 34S/32S ratio more than the wild type, evolving H2 in the headspace and exhibiting a lower specific respiration rate. In the presence of high concentrations of pyruvate, the growth of ΔcycA relied largely on fermentation rather than sulfate reduction, even when sulfate was abundant, producing the largest sulfur isotope effect observed in this study. Differences between sulfur isotope fractionation by ΔcycA and the wild type highlight the effect of electron transfer chains on the magnitude of sulfur isotope fractionation. Because Tp1-c3 is known to exclusively shuttle electrons from periplasmic hydrogenases to transmembrane complexes, electron transfers in the absence of Tp1-c3 should bypass the periplasmic hydrogen cycling, and the loss of reducing equivalents in the form of H2 can impair the flow of electrons from organic acids to sulfur, increasing isotope fractionation. Larger fractionation by ΔcycA can inform interpretations of sulfur isotope data at an environmental scale as well, because intracellular concentrations of electron transport components can be altered by environmental factors such as iron availability. Simultaneous sulfate reduction and fermentation, and their corresponding sulfur isotope effects, also generate a hypothesis that links sulfur isotope fractionation to the cellular energy budget. Theoretically, the largest fractionation during microbial sulfate reduction occurs when the backward fluxes equal the forward fluxes in sulfate reduction pathway. However, when the generation of ATP depends exclusively on sulfate respiration, a minimum respiration rate is required to fulfill the maintenance energy requirement. In contrast, when sulfate reduction occurs simultaneously with fermentation, the latter process may contribute toward maintenance energy, enabling slower and more reversible sulfate reduction, and leading to larger fractionation. Given that many sulfate-reducing microbes are also facultative fermenters, fermentation by sulfate reducing microbes in natural habitats and sulfur isotope signatures produced by such communities deserve further exploration.

An integrated bioremediation process for petroleum hydrocarbons removal and odor mitigation from contaminated marine sediment.

PubMed

Zhang, Zhen; Lo, Irene M C; Yan, Dickson Y S

2015-10-15

This study developed a novel integrated bioremediation process for the removal of petroleum hydrocarbons and the mitigation of odor induced by reduced sulfur from contaminated marine sediment. The bioremediation process consisted of two phases. In Phase I, acetate was dosed into the sediment as co-substrate to facilitate the sulfate reduction process. Meanwhile, akaganeite (β-FeOOH) was dosed in the surface layer of the sediment to prevent S(2-) release into the overlying seawater. In Phase II, NO3(-) was injected into the sediment as an electron acceptor to facilitate the denitrification process. After 20 weeks of treatment, the sequential integration of the sulfate reduction and denitrification processes led to effective biodegradation of total petroleum hydrocarbons (TPH), in which about 72% of TPH was removed. In Phase I, the release of S(2-) was effectively controlled by the addition of akaganeite. The oxidation of S(2-) by Fe(3+) and the precipitation of S(2-) by Fe(2+) were the main mechanisms for S(2-) removal. In Phase II, the injection of NO3(-) completely inhibited the sulfate reduction process. Most of residual AVS and S(0) were removed within 4 weeks after NO3(-) injection. The 16S rRNA clone library-based analysis revealed a distinct shift of bacterial community structure in the sediment over different treatment phases. The clones affiliated with Desulfobacterales and Desulfuromonadales were the most abundant in Phase I, while the clones related to Thioalkalivibrio sulfidophilus, Thiohalomonas nitratireducens and Sulfurimonas denitrificans predominated in Phase II. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biological Sulfate Reduction Rates in Hydrothermal Recharge Zones

NASA Astrophysics Data System (ADS)

Crowell, B.; Lowell, R. P.

2007-12-01

We develop a model to determine the rate of removal of seawater sulfate in the recharge regions of deep-sea hydrothermal systems as a result of biogenic sulfate reduction. The rate of sulfate reduction as a function of temperature derived from laboratory measurements on cores from the Guaymas Basin in Mexico [Jorgensen et al., 1992] is incorporated into a steady state 1-D advection-diffusion temperature equation, and a 1-D, steady- state, advection dominated conservation of solute equation. The diffusivity of sulfate in seawater is on the order of ~ 10-10 m2/s, and unless the flow speeds are < 10-12 m/s, the effects of diffusion are negligible, except within thin diffusive boundary layers. This model is then compared with a model that utilizes Gibbs free energy to quantify biogenic sulfate reduction [Bach and Edwards, 2003] in the upper oceanic crust of aging lithosphere. Using the high rates determined by Jorgensen et al. [1992], our model indicates that biological activity would reduce all seawater sulfate transported into the system within the upper 10 meters or less of the crust, which is inconsistent with the estimates of Bach and Edwards [2003]. Sulfate concentrations from ODP borehole Legs 64 and 168, at the sedimented Guaymas Basin and Juan de Fuca Ridge, respectively, show that most of the seawater sulfate is removed in the upper 100 meters. If the sulfate is assumed to all be reduced biogenically, the sulfate reduction rates at the ODP sites are at least 2 orders of magnitude less than the laboratory estimates of Jorgenson et al. [1992]. Finally, we compare the rate of seawater sulfate removal as a result of the precipitation of anhydrite, with the rate of biogenic sulfate reduction. We find that if hydrothermal recharge occurs rapidly through highly permeable faults, that biogenic sulfate reduction is negligible and that anhydrite precipitation would rapidly clog the recharge zone [Lowell and Yao, 2002]. If recharge occurs through broad zones of slow downwelling (u

Flow-through Column Experiments and Modeling of Microbially Mediated Cr(VI) Reduction at Hanford 100H

NASA Astrophysics Data System (ADS)

Yang, L.; Molins, S.; Beller, H. R.; Brodie, E. L.; Steefel, C.; Nico, P. S.; Han, R.

2010-12-01

Microbially mediated Cr(VI) reduction at the Hanford 100H area was investigated by flow-through column experiments. Three separate experiments were conducted to promote microbial activities associated with denitrification, iron and sulfate reduction, respectively. Replicate columns packed with natural sediments from the site under anaerobic environment were injected with 5mM Lactate as the electron donor and 5 μM Cr(VI) in all experiments. Sulfate and nitrate solutions were added to act as the main electron acceptors in the respective experiments, while iron columns relied on the indigenous sediment iron (and manganese) oxides as electron acceptors. Column effluent solutions were analyzed by IC and ICP-MS to monitor the microbial consumption/conversion of lactate and the associated Cr(VI) reduction. Biogeochemical reactive transport modeling was performed to gain further insights into the reaction mechanisms and Cr(VI) bioreduction rates. All experimental columns showed a reduction of the injected Cr(VI). Columns under denitrifying conditions showed the least Cr(VI) reduction at early stages (<60 days) compared to columns run under other experimental conditions, but became more active over time, and ultimately showed the most consistent Cr(VI) reduction. A strong correlation between denitrification and Cr(VI) reduction processes was observed and was in agreement with the results obtained in batch experiments with a denitrifying bacterium isolated from the Hanford site. The accumulation of nitrite does not appear to have an adverse effect on Cr(VI) reduction rates. Reactive transport simulations indicated that biomass growth completely depleted influent ammonium, and called for an additional source of N to account for the measured reduction rates. Iron columns were the least active with undetectable consumption of the injected lactate, slowest cell growth, and the smallest change in Cr(VI) concentrations during the course of the experiment. In contrast, columns under sulfate-reducing/fermentative conditions exhibited the greatest Cr(VI) reduction capacity. Two sulfate columns evolved to complete lactate fermentation with acetate and propionate produced in the column effluent after 40 days of experiments. These fermenting columns showed a complete removal of injected Cr(VI), visible precipitation of sulfide minerals, and a significant increase in effluent Fe and Mn concentrations. Reactive transport simulations suggested that direct reduction of Cr(VI) by Fe(II) and Mn(II) released from the sediment could account for the observed Cr(VI) removal. The biogeochemical modeling was employed to test two hypotheses that could explain the release of Fe(II) and Mn(II) from the column sediments: 1) acetate produced by lactate fermentation provided the substrate for the growth of iron(III) and manganese(IV) oxide reducers, and 2) direct reduction of iron(III) and manganese(IV) oxides by hydrogen sulfide generated during sulfate reduction. Overall, experimental and modeling results suggested that Cr(VI) reduction in the sulfate-reducing columns occurred through a complex network of microbial reactions that included fermentation, sulfate reduction, and possibly the stimulated iron-reducing communities.

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands.

PubMed

Dalcin Martins, Paula; Hoyt, David W; Bansal, Sheel; Mills, Christopher T; Tfaily, Malak; Tangen, Brian A; Finocchiaro, Raymond G; Johnston, Michael D; McAdams, Brandon C; Solensky, Matthew J; Smith, Garrett J; Chin, Yu-Ping; Wilkins, Michael J

2017-08-01

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions. © 2017 John Wiley & Sons Ltd.

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dalcin Martins, Paula; Hoyt, David W.; Bansal, Sheel

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxesmore » to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR, and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations, or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield non-competitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.« less

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

USGS Publications Warehouse

Martins, Paula; Hoyt, David W.; Bansal, Sheel; Mills, Christopher T.; Tfaily, Malak; Tangen, Brian; Finocchiaro, Raymond; Johnston, Michael D.; McAdams, Brandon C.; Solensky, Matthew J.; Smith, Garrett J.; Chin, Yu-Ping; Wilkins, Michael J.

2017-01-01

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.

Relationship between microbial sulfate reduction rates and sulfur isotopic fractionation

NASA Astrophysics Data System (ADS)

Matsu'Ura, F.

2009-12-01

Sulfate reduction is one of the common processes to obtain energy for certain types of microorganisms.They use hydrogen gas or organic substrates as electron donor and sulfates as electron acceptor, and reduce sulfates to sulfides. Sulfate reducing microbes extend across domains Archea and Bacteria, and are believed to be one of the earliest forms of terrestrial life (Shen 2004). The origin of 34S-depleted (light) sulfide sulfur, especially δ34S < -30 ‰, around hydrothermal vents or beneath the sea-floor is speculated to be the products of sulfate reducers. But laboratory experiments using sulfate reducers fail to produce such light sulfur, and many models were proposed to explain the discrepancy. Canfield et al. (2006) proposed so-called "standard model" based on previous studies. The standard model explained the reason for the large fractionation by temperature dependence of sulfur isotopic fractionation factor and rate of sulfate reduction, which indicated the growth conditions of microbes. However, they failed to prove their model by their other experiments (Canfield et al., 2006). In this study, I performed laboratory culture experiment of sulfate reducing bacteria (SRB) to explain the 34S-depleted sulfide sulfur. [Experiments] To compare the result with Canfield et al. (2006), I used Desulfovibrio desulfuricans for my laboratory culture experiment. D. desulfuricans was inoculated into glass vials, which contain 40ml of liquid culture media slightly modified from DSMZ #63 medium.Excess amount of Fe (II) is added to the DSMZ#63 medium to precipitate sulfide as iron sulfide. The vials were incubated at 25°C, 30°C, and 37°C, respectively. 21 vials were used for one temperature and sulfide and sulfate was collected from each three glass vials at every 12 hours from 72 hours to 144 hours after start of incubation. The sulfide was precipitated as iron sulfide and the sulfate was precipitated as barite. Sulfur isotope compositions of sulfate and sulfide were measured by standard method using Delta Plus mass-spectrometer. [Results and Discussion] The fractionation between sulfide and sulfate ranged from 2.7 to 11.0. The fractionation values varied among the different incubation temperature and growth phase of D. desulfuricans. The maximum fractionation values of three incubation temperatures were 9.9, 11.0, and 9.7, for 25 °C, 30°C, and 37°C, respectively. These results were different from standard model and Canfield et al. (2006). I could not find the clear correlation between ∂34S values and incubation temperatures in this experiment. The measured fractionation values during the incubation varied with incubation stage. The fractionation values clearly increased with incubation time at every temperature, and at 25°C ∂34S value was 3.6 at the 72h and it increased to 7.9 at 144 hours. This indicated the difference of sulfate reduction rate due to the growth phase of SRB. In the early logarithmic growth phase, metabolic activity of SRB is high and sulfate reduction rate is fast. In contrast at the stationary phase, SRB stop growing and sulfate reduction rate get slower. My result suggested that the sulfur isotopic fractionation is controlled by growth phase of SRB and lighter sulfide would be produced by the stationary phase or half-dormant SRB in natural environment.

Electrodeposition of CuZn Alloys from the Non-Cyanide Alkaline Baths

NASA Astrophysics Data System (ADS)

Li, Minggang; Wei, Guoying; Hu, Shuangshuang; Xu, Shuhan; Yang, Yejiong; Miao, Qinfang

2015-10-01

Effect of copper sulfate on CuZn alloys electroplating from non-cyanide baths are investigated by different electrochemical methods. Cyclic voltammetry and current transient measurements are used to characterize the CuZn alloys electroplating system in order to analyze the nucleation and growth mechanism. The reduction of Cu and CuZn alloy on sheet iron substrates shows an instantaneous nucleation process. However, the reduction of Zn on sheet iron substrates shows a progressive nucleation process. The structure and surface morphology of CuZn alloys are analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The morphology of CuZn alloys obtained with 50 g L-1 copper sulfate presents a smooth and compact deposit and the size of crystal particle is uniform.

Sulfate-reducing anaerobic ammonium oxidation as a potential treatment method for high nitrogen-content wastewater.

PubMed

Rikmann, Ergo; Zekker, Ivar; Tomingas, Martin; Tenno, Taavo; Menert, Anne; Loorits, Liis; Tenno, Toomas

2012-07-01

After sulfate-reducing ammonium oxidation (SRAO) was first assumed in 2001, several works have been published describing this process in laboratory-scale bioreactors or occurring in the nature. In this paper, the SRAO process was performed using reject water as a substrate for microorganisms and a source of NH(4) (+), with SO(4) (2-) being added as an electron acceptor. At a moderate temperature of 20°C in a moving bed biofilm reactor (MBBR) sulfate reduction along with ammonium oxidation were established. In an upflow anaerobic sludge blanket reactor (UASBR) the SRAO process took place at 36°C. Average volumetric TN removal rates of 0.03 kg-N/m³/day in the MBBR and 0.04 kg-N/m³/day in the UASBR were achieved, with long-term moderate average removal efficiencies, respectively. Uncultured bacteria clone P4 and uncultured planctomycete clone Amx-PAn30 were detected from the biofilm of the MBBR, from sludge of the UASBR uncultured Verrucomicrobiales bacterium clone De2102 and Uncultured bacterium clone ATB-KS-1929 were found also. The stoichiometrical ratio of NH(4) (+) removal was significantly higher than could be expected from the extent of SO(4) (2-) reduction. This phenomenon can primarily be attributed to complex interactions between nitrogen and sulfur compounds and organic matter present in the wastewater. The high NH(4) (+) removal ratio can be attributed to sulfur-utilizing denitrification/denitritation providing the evidence that SRAO is occurring independently and is not a result of sulfate reduction and anammox. HCO(3) (-) concentrations exceeding 1,000 mg/l were found to have an inhibiting effect on the SRAO process. Small amounts of hydrazine were naturally present in the reaction medium, indicating occurrence of the anammox process. Injections of anammox intermediates, hydrazine and hydroxylamine, had a positive effect on SRAO process performance, particularly in the case of the UASBR.

Anaerobic hydrocarbon degradation in petroleum-contaminated harbor sediments under sulfate-reducing and artificially imposed iron-reducing conditions

USGS Publications Warehouse

Coates, J.D.; Anderson, R.T.; Woodward, J.C.; Phillips, E.J.P.; Lovley, D.R.

1996-01-01

The potential use of iron(III) oxide to stimulate in-situ hydrocarbon degradation in anaerobic petroleum-contaminated harbor sediments was investigated. Previous studies have indicated that Fe(III)-reducing bacteria (FeRB) can oxidize some electron donors more effectively than sulfate- reducing bacteria (SRB). In contrast to previous results in freshwater sediments, the addition of Fe(III) to marine sediments from San Diego Bay, CA did not switch the terminal electron-accepting process (TEAP) from sulfate reduction to Fe-(III) reduction. Addition of Fe(III) also did not stimulate anaerobic hydrocarbon oxidation. Exposure of the sediment to air [to reoxidize Fe(II) to Fe(III)] followed by anaerobic incubation of the sediments, resulted in Fe-(III) reduction as the TEAP, but contaminant degradation was not stimulated and in some instances was inhibited. The difference in the ability of FeRB to compete with the SRB in the different sediment treatments was related to relative population sizes. Although the addition of Fe(III) did not stimulate hydrocarbon degradation, the results presented here as well as other recent studies demonstrate that there may be significant anaerobic hydrocarbon degradation under sulfate-reducing conditions in harbor sediments.

A novel approach to realize SANI process in freshwater sewage treatment--Use of wet flue gas desulfurization waste streams as sulfur source.

PubMed

Jiang, Feng; Zhang, Liang; Peng, Guo-Liang; Liang, Si-Yun; Qian, Jin; Wei, Li; Chen, Guang-Hao

2013-10-01

SANI (Sulfate reduction, Autotrophic denitrification and Nitrification Integrated) process has been approved to be a sludge-minimized sewage treatment process in warm and coastal cities with seawater supply. In order to apply this sulfur-based process in inland cold areas, wet flue gas desulfurization (FGD) can be simplified and integrated with SANI process, to provide sulfite as electron carrier for sulfur cycle in sewage treatment. In this study, a lab-scale system of the proposed novel process was developed and run for over 200 days while temperature varied between 30 and 5 °C, fed with synthetic FGD wastewaters and sewage. The sulfite-reducing upflow anaerobic sludge bed (SrUASB) reactor, as the major bioreactor of the system, removed 86.9% of organics while the whole system removed 94% of organics even when water temperature decreased to around 10 °C. The bactericidal effect of sulfite was not observed in the SrUASB reactor, while thiosulfate was found accumulated under psychrophilic conditions. The sludge yield of the SrUASB reactor was determined to be 0.095 kg VSS/kg COD, higher than of sulfate reduction process but still much lower than of conventional activated sludge processes. The dominant microbes in the SrUASB reactor were determined as Lactococcus spp. rather than sulfate-reducing bacteria, but sulfite reduction still contributed 85.5% to the organic carbon mineralization in this reactor. Ammonia and nitrate were effectively removed in the aerobic and anoxic filters, respectively. This study confirms the proposed process was promising to achieve sludge-minimized sewage treatment integrating with flue gas desulfurization in inland and cold areas. Copyright © 2013 Elsevier Ltd. All rights reserved.

Significant role of organic sulfur in supporting sedimentary sulfate reduction in low-sulfate environments

NASA Astrophysics Data System (ADS)

Fakhraee, Mojtaba; Li, Jiying; Katsev, Sergei

2017-09-01

Dissimilatory sulfate reduction (DSR) is a major carbon mineralization pathway in aquatic sediments, soils, and groundwater, which regulates the production of hydrogen sulfide and the mobilization rates of biologically important elements such as phosphorus and mercury. It has been widely assumed that water-column sulfate is the main sulfur source to fuel this reaction in sediments. While this assumption may be justified in high-sulfate environments such as modern seawater, we argue that in low-sulfate environments mineralization of organic sulfur compounds can be an important source of sulfate. Using a reaction-transport model, we investigate the production of sulfate from sulfur-containing organic matter for a range of environments. The results show that in low sulfate environments (<500 μM) the in-sediment production of sulfate can support a substantial portion (>50%) of sulfate reduction. In well-oxygenated systems, porewater sulfate profiles often exhibit sub-interface peaks so that sulfate fluxes are directed out of the sediment. Our measurements in Lake Superior, the world's largest lake, corroborate this conclusion: offshore sediments act as sources rather than sinks of sulfate for the water column, and sediment DSR is supported entirely by the in-sediment production of sulfate. Sulfate reduction rates are correlated to the depth of oxygen penetration and strongly regulated by the supply of reactive organic matter; rate co-regulation by sulfate availability becomes appreciable below 500 μM level. The results indicate the need to consider the mineralization of organic sulfur in the biogeochemical cycling in low-sulfate environments, including several of the world's largest freshwater bodies, deep subsurface, and possibly the sulfate-poor oceans of the Early Earth.

Sources of sulfate supporting anaerobic metabolism in a contaminated aquifer

USGS Publications Warehouse

Ulrich, G.A.; Breit, G.N.; Cozzarelli, I.M.; Suflita, J.M.

2003-01-01

Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis-Menten-like relationship with an apparent Km and Vmax of approximately 80 and 0.83 ??M SO4-2??day-1, respectively. The concentration of sulfate in the core of the leachate plume was well below 20 ??M and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (???100 ??M) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.

Geomicrobiological Features of Ferruginous Sediments from Lake Towuti, Indonesia

PubMed Central

Vuillemin, Aurèle; Friese, André; Alawi, Mashal; Henny, Cynthia; Nomosatryo, Sulung; Wagner, Dirk; Crowe, Sean A.; Kallmeyer, Jens

2016-01-01

Lake Towuti is a tectonic basin, surrounded by ultramafic rocks. Lateritic soils form through weathering and deliver abundant iron (oxy)hydroxides but very little sulfate to the lake and its sediment. To characterize the sediment biogeochemistry, we collected cores at three sites with increasing water depth and decreasing bottom water oxygen concentrations. Microbial cell densities were highest at the shallow site—a feature we attribute to the availability of labile organic matter (OM) and the higher abundance of electron acceptors due to oxic bottom water conditions. At the two other sites, OM degradation and reduction processes below the oxycline led to partial electron acceptor depletion. Genetic information preserved in the sediment as extracellular DNA (eDNA) provided information on aerobic and anaerobic heterotrophs related to Nitrospirae, Chloroflexi, and Thermoplasmatales. These taxa apparently played a significant role in the degradation of sinking OM. However, eDNA concentrations rapidly decreased with core depth. Despite very low sulfate concentrations, sulfate-reducing bacteria were present and viable in sediments at all three sites, as confirmed by measurement of potential sulfate reduction rates. Microbial community fingerprinting supported the presence of taxa related to Deltaproteobacteria and Firmicutes with demonstrated capacity for iron and sulfate reduction. Concomitantly, sequences of Ruminococcaceae, Clostridiales, and Methanomicrobiales indicated potential for fermentative hydrogen and methane production. Such first insights into ferruginous sediments showed that microbial populations perform successive metabolisms related to sulfur, iron, and methane. In theory, iron reduction could reoxidize reduced sulfur compounds and desorb OM from iron minerals to allow remineralization to methane. Overall, we found that biogeochemical processes in the sediments can be linked to redox differences in the bottom waters of the three sites, like oxidant concentrations and the supply of labile OM. At the scale of the lacustrine record, our geomicrobiological study should provide a means to link the extant subsurface biosphere to past environments. PMID:27446046

Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Farquhar, J.; Guo, W.

2015-12-01

Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate reduction models and other sulfur-redox processes in nature.

Formation of carbonate pipes in the northern Okinawa Trough linked to strong sulfate exhaustion and iron supply

NASA Astrophysics Data System (ADS)

Peng, Xiaotong; Guo, Zixiao; Chen, Shun; Sun, Zhilei; Xu, Hengchao; Ta, Kaiwen; Zhang, Jianchao; Zhang, Lijuan; Li, Jiwei; Du, Mengran

2017-05-01

The microbial anaerobic oxidation of methane (AOM), a key biogeochemical process that consumes substantial amounts of methane produced in seafloor sediments, can lead to the formation of carbonate deposits at or beneath the sea floor. Although Fe oxide-driven AOM has been identified in cold seep sediments, the exact mode by which it may influence the formation of carbonate deposits remains poorly understood. Here, we characterize the morphology, petrology and geochemistry of a methane-derived Fe-rich carbonate pipe in the northern Okinawa Trough (OT). We detect abundant authigenic pyrites, as well as widespread trace Fe, within microbial mat-like carbonate veins in the pipe. The in situ δ34S values of these pyrites range from -3.9 to 31.6‰ (VCDT), suggesting a strong consumption of seawater sulfate by sulfate-driven AOM at the bottom of sulfate reduction zone. The positive δ56Fe values of pyrite and notable enrichment of Fe in the OT pipe concurrently indicate that the pyrites are primarily derived from Fe oxides in deep sediments. We propose that the Fe-rich carbonate pipe formed at the bottom of sulfate reduction zone, below which Fe-driven AOM, rather than Fe-oxide reduction coupled to organic matter degradation, might be responsible for the abundantly available Fe2+ in the fluids from which pyrites precipitated. The Fe-rich carbonate pipe described in this study probably represents the first fossil example of carbonate deposits linked to Fe-driven AOM. Because Fe-rich carbonate deposits have also been found at other cold seeps worldwide, we infer that similar processes may play an essential role in biogeochemical cycling of sub-seafloor methane and Fe at continental margins.

Genome Sequence of the Moderately Acidophilic Sulfate-Reducing Firmicute Desulfosporosinus acididurans (Strain M1T).

PubMed

Petzsch, Patrick; Poehlein, Anja; Johnson, D Barrie; Daniel, Rolf; Schlömann, Michael; Mühling, Martin

2015-08-06

Microbial dissimilatory sulfate reduction is commonplace in many anaerobic environments, though few acidophilic bacteria are known to mediate this process. We report the 4.64-Mb draft genome of the type strain of the moderate acidophile Desulfosporosinus acididurans, which was isolated from acidic sediment in a river draining the Soufrière volcano, Montserrat. Copyright © 2015 Petzsch et al.

Recovery of lead from lead paste in spent lead acid battery by hydrometallurgical desulfurization and vacuum thermal reduction.

PubMed

Ma, Yunjian; Qiu, Keqiang

2015-06-01

Lead sulfate, lead oxides and lead metal are the main component of lead paste in spent lead acid battery. When lead sulfate was desulfurized and transformed into lead carbonate by sodium carbonate, lead metal and lead oxides remained unchanged. Lead carbonate is easily decomposed to lead oxide and carbon dioxide under high temperature. Namely, vacuum thermal process is the reduction reaction of lead oxides. A compatible environmental process consisted of hydrometallurgical desulfurization and vacuum thermal reduction to recycle lead was investigated in this research. Lead paste was firstly desulfurized with sodium carbonate, by which, the content of sulfur declined from 7.87% to 0.26%. Then, the desulfurized lead paste was reduced by charcoal under vacuum. Under the optimized reaction conditions, i.e., vacuum thermal reduction at temperature 850°C under 20 Pa for 45 min, a 22.11×10(-2) g cm(-2) min(-1) reduction rate, and a 98.13% direct recovery ratio of fine lead (99.77%) had been achieved, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fractionation of sulfur and oxygen isotopes in sulfate by soil sorption

NASA Astrophysics Data System (ADS)

Van Stempvoort, D. R.; Reardon, E. J.; Fritz, P.

1990-10-01

Both field and laboratory data indicate that there is no significant isotope fractionation of sulfate during sorption in upland forest Podzols. The dominant sulfate sorption process in these soils is adsorption onto mineral surfaces. In the Plastic Lake watershed, Dorset, Ontario, Canada, fractions of sulfate from Podzol B-horizons have the following mean isotope (%.) compositions: water soluble sulfate, δ34S = +6.4; δ18O = -5.3; bicarbonate-exchanged sulfate by two methods, δ34S = + 4.5 and + 3.4; δ18O =-6.2 and -5.6; dissolved sulfate in B-horizon soilwater seepage, δ34S = + 4.8; δ18O = -5.4. These data indicate that soil sorption enriches dissolved sulfate in 34S by approximately 1 ± 1%. and in 18O by 0 +- 1 %. relative to sorbed sulfate. Similar results were obtained by laboratory sorption of sulfate by prepared goethite, which is a mineral representative of soil sorption sites in acidic Podzols like the one at Plastic Lake. The mean fractionation between sorbed and dissolved sulfate was found to be - 0.3%. for 34S and 0.1 %. for 18O. Earlier literature has confused the term adsorption; in many cases the more general term sorption, or retention, should be used. Pronounced fractionation of S and O isotopes in sulfate by lake and ocean sediments has been attributed to "adsorption" or "retention" but is more likely the result of sulfate reduction. Apparently, at Earth-surface conditions the only substantial isotope shifts in sulfate occur during microbial processes.

Sulfate-dependent Anaerobic Oxidation of Methane as a Generation Mechanism for Calcite Cap Rock in Gulf Coast Salt Domes

NASA Astrophysics Data System (ADS)

Caesar, K. H.; Kyle, R.; Lyons, T. W.; Loyd, S. J.

2015-12-01

Gulf Coast salt domes, specifically their calcite cap rocks, have been widely recognized for their association with significant reserves of crude oil and natural gas. However, the specific microbial reactions that facilitate the precipitation of these cap rocks are still largely unknown. Insight into the mineralization mechanism(s) can be obtained from the specific geochemical signatures recorded in these structures. Gulf Coast cap rocks contain carbonate and sulfur minerals that exhibit variable carbon (d13C) and sulfur isotope (δ34S) signatures. Calcite d13C values are isotopically depleted and show a large range of values from -1 to -52‰, reflecting a mixture of various carbon sources including a substantial methane component. These depleted carbon isotope compositions combined with the presence of abundant sulfide minerals in cap rocks have led to interpretations that invoke microbial sulfate reduction as an important carbonate mineral-yielding process in salt dome environments. Sulfur isotope data from carbonate-associated sulfate (CAS: trace sulfate incorporated within the carbonate mineral crystal lattice) provide a more direct proxy for aqueous sulfate in salt dome systems and may provide a means to directly fingerprint ancient sulfate reduction. We find CAS sulfur isotope compositions (δ34SCAS) significantly greater than those of the precursor Jurassic sulfate-salt deposits (which exhibit δ34S values of ~ +15‰). This implies that cap rock carbonate generation occurred via microbial sulfate reduction under closed-system conditions. The co-occurrence of depleted carbonate d13C values (< ~30‰) and the enriched δ34SCAS values are evidence for sulfate-dependent anaerobic oxidation of methane (AOM). AOM, which has been shown to yield extensive seafloor carbonate authigenesis, is also potentially partly responsible for the carbonate minerals of the Gulf Coast calcite cap rocks through concomitant production of alkalinity. Collectively, these data shed new light on a potential hotspot of microbial activity in the deep biosphere.

A novel aerobic sulfate reduction process in landfill mineralized refuse.

PubMed

Liu, Weijia; Long, Yuyang; Fang, Yuan; Ying, Luyao; Shen, Dongsheng

2018-05-08

It is thought that mineralized refuse could be excavated from almost-full landfill sites to provide space for the increasing burden of municipal solid waste. When excavating, however, the H 2 S emissions from the mineralized waste need to be considered carefully. In an attempt to understand how H 2 S emissions might change during this excavation process, we carried out a series of tests, including exposing anaerobic mineralized refuse to oxygen, isolating and determining possible functional bacteria, and characterizing the electron donors and/or acceptors. The results showed that H 2 S would be released when landfill mineralized refuse was exposed to oxygen (O 2 ), and could reach concentrations of 6 mg m -3 , which was 3 times the concentrations of H 2 S released from anaerobic mineralized refuse. Sulfur-metabolized microorganisms accounted for only 0.5% of the microbial functional bacteria (MFB) derived from the mineralized refuse when exposed to O 2 for 60 days, and SRB were not present. The MFB maintained H 2 S production by aerobic sulfate reduction using SO 4 2- and S 2 O 3 2- as electron acceptors, and sulfate-reducing rates of 16% and 55%, respectively, were achieved. Lactate and S 2 O 3 2- were the preferred electron donor and acceptor, respectively. By enhancing the carbon source and electron transfer, MFB may undergo strong aerobic sulfate reduction even at low abundances of sulfur-metabolized microorganisms. Copyright © 2018 Elsevier B.V. All rights reserved.

An Exploratory Study on the Pathways of Cr (VI) Reduction in Sulfate-reducing Up-flow Anaerobic Sludge Bed (UASB) Reactor

PubMed Central

Qian, Jin; Wei, Li; Liu, Rulong; Jiang, Feng; Hao, Xiaodi; Chen, Guang-Hao

2016-01-01

Electroplating wastewater contains both Cr (VI) and sulfate. So Cr (VI) removal under sulfate-rich condition is quite complicated. This study mainly investigates the pathways for Cr (VI) removal under biological sulfate-reducing condition in the up-flow anaerobic sludge bed (UASB) reactor. Two potential pathways are found for the removal of Cr (VI). The first one is the sulfidogenesis-induced Cr (VI) reduction pathway (for 90% Cr (VI) removal), in which Cr (VI) is reduced by sulfide generated from biological reduction of sulfate. The second one leads to direct reduction of Cr (VI) which is utilized by bacteria as the electron acceptor (for 10% Cr (VI) removal). Batch test results confirmed that sulfide was oxidized to elemental sulfur instead of sulfate during Cr (VI) reduction. The produced extracellular polymeric substances (EPS) provided protection to the microbes, resulting in effective removal of Cr (VI). Sulfate-reducing bacteria (SRB) genera accounted for 11.1% of the total bacterial community; thus they could be the major organisms mediating the sulfidogenesis-induced reduction of Cr (VI). In addition, chromate-utilizing genera (e.g. Microbacterium) were also detected, which were possibly responsible for the direct reduction of Cr (VI) using organics as the electron donor and Cr (VI) as the electron acceptor. PMID:27021522

Bioreduction of para-chloronitrobenzene in a hydrogen-based hollow-fiber membrane biofilm reactor: effects of nitrate and sulfate.

PubMed

Li, Haixiang; Zhang, Zhiqiang; Xu, Xiaoyin; Liang, Jun; Xia, Siqing

2014-04-01

A continuous-stirred, hydrogen-based, hollow-fiber membrane biofilm reactor (HFMBfR) that was active in nitrate and sulfate reductions was shown to be effective for degradation or detoxification of para-chloronitrobenzene (p-CNB) in water by biotransforming it first to para-chloroaniline (nitro-reduction) and then to aniline (reductive dechlorination) with hydrogen (H2) as an electron donor. A series of short-term experiments examined the effects of nitrate and sulfate on p-CNB bioreduction. The results obtained showed both higher nitrate and sulfate concentration declined the p-CNB bioreduction in the biofilm, and this suggests the competition for H2 caused less H2 available for the p-CNB bioreduction when the H2 demand for the reductions was larger. Denitrification and sulfate reduction intermediates were thought to be potential factors inhibiting the p-CNB bioreduction. Analysis of electron-equivalent fluxes and reaction orders in the biofilm further demonstrated both denitrification and sulfate reduction competed more strongly for H2 availability than p-CNB bioreduction. These findings have significant implications for the HFMBfR used for degrading p-CNB under denitrifying and/or sulfate reducing conditions.

Field Investigation of Natural Attenuation of a Petroleum Hydrocarbon Contaminated Aquifer, Gyeonggi Province, Korea

NASA Astrophysics Data System (ADS)

Yang, J.; Lee, K.; Bae, G.

2004-12-01

In remediation of a petroleum hydrocarbon contaminated aquifer, natural attenuation may be significant as a remedial alternative. Therefore, natural attenuation should be investigated in the field in order to effectively design and evaluate the remediation strategy at the contaminated site. This study focused on evaluating the natural attenuation for benzene, toluene, ethylbenzene, and xylene (BTEX) at a contaminated site in South Korea. At the study site, the aquifer is composed of a high permeable gravel layer and relatively low permeable sandy-silt layers. Groundwater level vertically fluctuated between 1m and 2m throughout the year (April, 2003~June, 2004) and showed direct response to rainfall events. Chemical analyses of sampled groundwater were performed to investigate the concentrations of various chemical species which are associated with the natural attenuation processes. To evaluate the degree of the biodegradation, the expressed biodegradation capacity (EBC) analysis was done using aerobic respiration, nitrate reduction, manganese reduction, ferric iron reduction, and sulfate reduction as an indicator. High EBC value of sulfate indicate that anaerobic biodegradation by sulfate reduction was a dominant process of mineralization of BTEX at this site. The EBC values decrease sensitively when heavy rainfall occurs due to the dilution and inflow of electron acceptors through a gravel layer. The first-order biodegradation rates of BTEX were estimated by means of the Buscheck and Alcantar method (1995). Results show that the natural attenuation rate of benzene was the highest among the BTEX.

H2 enrichment from synthesis gas by Desulfotomaculum carboxydivorans for potential applications in synthesis gas purification and biodesulfurization.

PubMed

Sipma, Jan; Osuna, M Begoña; Parshina, Sofiya N; Lettinga, Gatze; Stams, Alfons J M; Lens, Piet N L

2007-08-01

Desulfotomaculum carboxydivorans, recently isolated from a full-scale anaerobic wastewater treatment facility, is a sulfate reducer capable of hydrogenogenic growth on carbon monoxide (CO). In the presence of sulfate, the hydrogen formed is used for sulfate reduction. The organism grows rapidly at 200 kPa CO, pH 7.0, and 55 degrees C, with a generation time of 100 min, producing nearly equimolar amounts of H(2) and CO(2) from CO and H(2)O. The high specific CO conversion rates, exceeding 0.8 mol CO (g protein)(-1) h(-1), makes this bacterium an interesting candidate for a biological alternative of the currently employed chemical catalytic water-gas shift reaction to purify synthesis gas (contains mainly H(2), CO, and CO(2)). Furthermore, as D. carboxydivorans is capable of hydrogenotrophic sulfate reduction at partial CO pressures exceeding 100 kPa, it is also a good candidate for biodesulfurization processes using synthesis gas as electron donor at elevated temperatures, e.g., in biological flue gas desulfurization. Although high maximal specific sulfate reduction rates (32 mmol (g protein)(-1) h(-1)) can be obtained, its sulfide tolerance is rather low and pH dependent, i.e., maximally 9 and 5 mM sulfide at pH 7.2 and pH 6.5, respectively.

Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer

PubMed Central

Avrahamov, N; Antler, G; Yechieli, Y; Gavrieli, I; Joye, S B; Saxton, M; Turchyn, A V; Sivan, O

2014-01-01

Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ13CDIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed (34ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate-driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment. PMID:25039851

Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer.

PubMed

Avrahamov, N; Antler, G; Yechieli, Y; Gavrieli, I; Joye, S B; Saxton, M; Turchyn, A V; Sivan, O

2014-11-01

Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ(13) CDIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed ((34) ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate-driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment. © 2014 The Authors. Geobiology Published by John Wiley & Sons Ltd.

Assessing sulfate reduction and methane cycling in a high salinity pore water system in the northern Gulf of Mexico

USGS Publications Warehouse

Pohlman, J.W.; Ruppel, C.; Hutchinson, D.R.; Downer, R.; Coffin, R.B.

2008-01-01

Pore waters extracted from 18 piston cores obtained on and near a salt-cored bathymetric high in Keathley Canyon lease block 151 in the northern Gulf of Mexico contain elevated concentrations of chloride (up to 838 mM) and have pore water chemical concentration profiles that exhibit extensive departures (concavity) from steady-state (linear) diffusive equilibrium with depth. Minimum ??13C dissolved inorganic carbon (DIC) values of -55.9??? to -64.8??? at the sulfate-methane transition (SMT) strongly suggest active anaerobic oxidation of methane (AOM) throughout the study region. However, the nonlinear pore water chemistry-depth profiles make it impossible to determine the vertical extent of active AOM or the potential role of alternate sulfate reduction pathways. Here we utilize the conservative (non-reactive) nature of dissolved chloride to differentiate the effects of biogeochemical activity (e.g., AOM and/or organoclastic sulfate reduction) relative to physical mixing in high salinity Keathley Canyon sediments. In most cases, the DIC and sulfate concentrations in pore waters are consistent with a conservative mixing model that uses chloride concentrations at the seafloor and the SMT as endmembers. Conservative mixing of pore water constituents implies that an undetermined physical process is primarily responsible for the nonlinearity of the pore water-depth profiles. In limited cases where the sulfate and DIC concentrations deviated from conservative mixing between the seafloor and SMT, the ??13C-DIC mixing diagrams suggest that the excess DIC is produced from a 13C-depleted source that could only be accounted for by microbial methane, the dominant form of methane identified during this study. We conclude that AOM is the most prevalent sink for sulfate and that it occurs primarily at the SMT at this Keathley Canyon site.

Sedimentary sulfides in dune sands of Spiekeroog Island, southern North Sea: A biogeochemical study of sulfur isotope partitioning

NASA Astrophysics Data System (ADS)

Seibert, Stephan; Schubert, Florian; Schmiedinger, Iris; Böttcher, Michael E.; Massmann, Gudrun

2017-04-01

The formation of iron sulfides in sandy sediments and the associated development of stable isotope signatures is still mechanistically not understood. In dune sands under impact of both fresh and saline water several physico-chemical gradients may develop leading to distinctly different biogeochemical zones. In the present study, a 10 m long core from a dune base at the North Eastern part of Spiekeroog Island, southern North Sea, was investigated for the elemental and stable isotope composition. The pyrite (TRIS) content was quantitatively extracted via an acidic Cr(II) distillation procedure and the stable sulfur isotope composition was determined by means of C-irmMS. The pore waters display a downcore increase in salt contents and a mixing between fresh and salt water. The accumulation of metabolites at depth indicate an increasing superimposition of mixing by microbial decomposition of dissolved organic matter with only limited net sulfate reduction. This indicates an essential open system with respect to dissolved sulfate. The sands were found to be very low in TOC, TIC, and TRIS and dominated by quartz minerals. Under the assumption that North Sea water sulfate was the only substantial sulfate source (d34S = + 21per mil), the sedimentary sulfides indicate an overall sulfur isotope discrimination upon microbial sulfate reduction between 39 and 52 per mil, which is within the range of results from other fully marine sands from the Spiekeroog area and laboratory studies with pure cultures of sulfate-reducing bacteria under low cellular sulfate reduction rates. Further investigations are on the way to understand the processes leading to the iron sulfide formation in these organic-poor substrates.

Impact of electron acceptor availability on the anaerobic oxidation of methane in coastal freshwater and brackish wetland sediments

NASA Astrophysics Data System (ADS)

Segarra, Katherine E. A.; Comerford, Christopher; Slaughter, Julia; Joye, Samantha B.

2013-08-01

Methane, a powerful greenhouse gas, is both produced and consumed in anoxic coastal sediments via microbial processes. Although the anaerobic oxidation of methane (AOM) is almost certainly an important process in coastal freshwater and salt marsh sediments, the factors that control the rates and pathways of AOM in these habitats are poorly understood. Here, we present the first direct measurements of AOM activity in freshwater (0 PSU) and brackish (25 PSU) wetland sediments. Despite disparate sulfate concentrations, both environments supported substantial rates of AOM. Higher sulfate reduction (SR) rates were measured in the freshwater site and SR at both sites was of sufficient magnitude to support the observed AOM activity. Laboratory incubations of freshwater and brackish tidal, wetland sediments amended with either nothing [control], sulfate, nitrate, manganese oxide (birnessite) or iron oxide (ferrihydrite) and supplied with a methane headspace were used to evaluate the impact(s) of electron acceptor availability on potential AOM rates. Maximum AOM rates in brackish slurries occurred in the sulfate amendments. In contrast, addition of sulfate and several possible electron acceptors to the freshwater slurries decreased AOM rates relative to the control. High ratios of AOM activity relative to SR activity in the nitrate, birnessite, and ferrihydrite treatments of both the brackish and freshwater slurries provided evidence of AOM decoupled from SR. This study demonstrates that both freshwater and brackish coastal wetland sediments support considerable rates of anaerobic methanotrophy and provides evidence for sulfate-independent AOM that may be coupled to nitrate, iron, or manganese reduction in both environments.

Anaerobic oxidation of ethene coupled to sulfate reduction in microcosms and enrichment cultures.

PubMed

Fullerton, Heather; Crawford, Michael; Bakenne, Ademola; Freedman, David L; Zinder, Stephen H

2013-01-01

Ethene is considered recalcitrant under anaerobic conditions, but biological reduction to ethane and oxidation to CO2 have been reported; however, little is known about these processes or the organisms carrying them out. In this report we describe sulfate dependent ethene consumption in microcosms prepared with sediments from a freshwater canal. A first dose of 0.6 mmol/L ethene was consumed within 77 days, and a second dose was largely consumed twelve days later. Material from this microcosm was transferred into growth medium with ethene as the only electron donor (except for trace amounts of vitamins) and sulfate as the electron acceptor. Four doses of ethene were consumed at increasing rates, and the cultures have been transferred at least eight times in this medium. Conversion of [(14)C]ethene primarily to (14)CO2 was demonstrated in fifth and sixth generation cultures, as well as production of sulfide in other cultures, confirming the ethene/sulfate couple. Ovoid cells 1-2 μm in diameter were found in cultures containing ethene and sulfate, and quantitative PCR showed large increases in bacterial 16S rRNA gene copy number. Over half of a 16S rRNA gene clone library from a sixth-generation culture was a phylotype with a sequence ca. 90% identical with a clade of Deltaproteobacteria that includes Desulfovirga adipica and several Syntrophobacter spp. These studies have solidified the concept that deficits in mass balances for chloroethene fate in sulfate reducing zones of contaminated groundwater sites may be due to ethene oxidation, and suggest a unique phylotype is involved in this process.

Effect of sulfate on anaerobic reduction of nitrobenzene with acetate or propionate as an electron donor.

PubMed

Huang, Jingang; Wen, Yue; Ding, Ning; Xu, Yue; Zhou, Qi

2012-09-15

Sulfate is frequently found in wastewaters that contain nitrobenzene. To reveal the effect of sulfate on the reductive transformation of nitrobenzene to aniline--with acetate or propionate as potential electron donors in anaerobic systems--an acetate series (R1-R5) and a propionate series (R6-R10) were set up. Each of these was comprised of five laboratory-scale sequence batch reactors. The two series were amended with the same amount of nitrobenzene and electron donor electron equivalents, whereas with increasing sulfate concentrations. Results indicated that the presence of sulfate could depress nitrobenzene reduction. Such depression is linked to the inhibition of nitroreductase activity and/or the shift of electron flow. In the acetate series, although sulfate did not strongly compete with nitrobenzene for electron donors, noncompetitive inhibition of specific nitrobenzene reduction rates by sulfate was observed, with an inhibition constant of 0.40 mM. Propionate, which can produce intermediate H₂ as preferred reducing equivalent, is a more effective primary electron donor for nitrobenzene reduction as compared to acetate. In the propionate series, sulfate was found to be a preferential electron acceptor as compared to nitrobenzene, resulting in a quick depletion of propionate and then a likely termination of H₂-releasing under higher sulfate concentrations (R9 and R10). In such a situation, nitrobenzene reduction slowed down, occurring two-stage zero-order kinetics. Copyright © 2012 Elsevier Ltd. All rights reserved.

Impact of clay minerals on sulfate-reducing activity in aquifers

USGS Publications Warehouse

Wong, D.; Suflita, J.M.; McKinley, J.P.; Krumholz, L.R.

2004-01-01

Previous studies have shown that sulfate-reduction activity occurs in a heterogeneous manner throughout the terrestrial subsurface. Low-activity regions are often observed in the presence of clay minerals. Here we report that clays inhibit sulfate reduction activity in sediments and in a pure culture of Desulfovibriovulgaris. Clay minerals including bentonite and kaolinite inhibited sulfate reduction by 70–90% in sediments. Intact clays and clay colloids or soluble components, capable of passing through a 0.2-µm filter, were also inhibitory to sulfate-reducing bacteria. Other adsorbent materials, including anion or cation exchangers and a zeolite, did not inhibit sulfate reduction in sediments, suggesting that the effect of clays was not due to their cation-exchange capacity. We observed a strong correlation between the Al2O3content of clays and their relative ability to inhibit sulfate reduction in sediments (r2 = 0.82). This suggested that inhibition might be a direct effect of Al3+ (aq) on the bacteria. We then tested pure aluminum oxide (Al2O3) and showed it to act in a similar manner to clay. As dissolved aluminum is known to be toxic to a variety of organisms at low concentrations, our results suggest that the effects of clay on sulfate-reducing bacteria may be directly due to aluminum. Thus, our experiments provide an explanation for the lack of sulfate-reduction activity in clay-rich regions and presents a mechanism for the effect.

Effect of hydrogen limitation and temperature on the fractionation of sulfur isotopes by a deep-sea hydrothermal vent sulfate-reducing bacterium

NASA Astrophysics Data System (ADS)

Hoek, Joost; Reysenbach, Anna-Louise; Habicht, Kirsten S.; Canfield, Donald E.

2006-12-01

The fractionation of sulfur isotopes by the thermophilic chemolithoautotrophic Thermodesulfatator indicus was explored during sulfate reduction under excess and reduced hydrogen supply, and the full temperature range of growth (40-80 °C). Fractionation of sulfur isotopes measured under reduced H 2 conditions in a fed-batch culture revealed high fractionations (24-37‰) compared to fractionations produced under excess H 2 supply (1-6‰). Higher fractionations correlated with lower sulfate reduction rates. Such high fractionations have never been reported for growth on H 2. For temperature-dependant fractionation experiments cell-specific rates of sulfate reduction increased with increasing temperatures to 70 °C after which sulfate-reduction rates rapidly decreased. Fractionations were relatively high at 40 °C and decreased with increasing temperature from 40-60 °C. Above 60 °C, fractionation trends switched and increased again with increasing temperatures. These temperature-dependant fractionation trends have not previously been reported for growth on H 2 and are not predicted by a generally accepted fractionation model for sulfate reduction, where fractionations are controlled as a function of temperature, by the balance of the exchange of sulfate across the cell membrane, and enzymatic reduction rates of sulfate. Our results are reproduced with a model where fractionation is controlled by differences in the temperature response of enzyme reaction rates and the exchange of sulfate in and out of the cell.

Evaluating the role of sulfur and hyporheic exchange in biogeochemical cycling in riparian wetlands

NASA Astrophysics Data System (ADS)

Ng, G. H. C.; O'Hara, P. A.; Santelli, C. M.; Rosenfeld, C.; Yourd, A.

2017-12-01

Although the mixing of surface water and groundwater is well-recognized to support hotspots of redox activities such as denitrification, few hyporheic zone studies have examined sulfur reactions. Because sulfate concentrations in wetlands, lake beds, and stream beds are low compared to in marine settings, the hierarchical redox tower dictates that sulfate reduction should play a substantially lesser role in biogeochemical cycling than nitrate or iron reduction when these sediments become anoxic. However, recent experiments challenge the classically held redox sequence by revealing "cryptic" sulfur cycling that can support unexpectedly high sulfate reduction rates and could be driving iron and carbon cycling through coupled reactions. Sulfur biogeochemical processes remain poorly understood in field settings, where little is known about the impact of hydrologic fluxes. Our study examines how hyporheic flux can "kick" forward cryptic sulfur cycling and related iron and carbon reactions by perturbing geochemical gradients to which microbial communities respond. We evaluate field-scale cycling of iron, sulfur, and carbon through a combination of hydrologic monitoring, microbial and geochemical analyses, and reactive-transport modeling at a riparian wetland site in northeastern Minnesota that is impacted by mining practices. In particular, we assess how varying fluxes between high sulfate concentration surface water and lower sulfate concentration groundwater over a season could be (1) facilitating intensified sulfur cycling coupled to abiotic iron reduction and (2) altering methane release possibly through anaerobic methane oxidation. Our findings can help clarify the importance of sulfur in non-marine biogeochemical cycling and provide better understanding of how anthropogenic activities can impact critical freshwater systems.

Recalibrating the concentration of Precambrian seawater sulfate

NASA Astrophysics Data System (ADS)

Johnston, D. T.; Bradley, A. S.; Hoarfrost, A.; Girguis, P. R.

2010-12-01

The isotopic offset between sulfate sulfur and sulfide sulfur (δ34Ssulfate-sulfide) is widely used in the Precambrian as a paleo-indicator of seawater sulfate concentrations. Popularized by experimental work proposing an increase in seawater sulfate at the Archean - Proterozoic boundary, the concept of using a calibrated physiological process (dissimilatory sulfate reduction) to extract environmental information holds the potential to unlock numerous geological questions. To that end, the interpretability of sulfur isotope records relies on the degree to which strict quantitative constraints have been placed on the relationship between sulfate concentrations and sulfate reducing bacteria. Our work serves to extend those constraints. Here we present data from a series of replicate quasi-chemostat microbial reactors, inoculated with marine sediment from Monterey Bay and incubated with artificial seawater ([SO42-]< 5 mM). Our experimental design continuously removes sulfide and allows for systematic tracking of the dependence of δ34Ssulfate-sulfide on seawater sulfate concentration. In addition to expanding the existing δ34S context, we target high-precision multiple sulfur isotope data, which allows for a greater interpretability of both the overall result and its mapping onto environmental records. Further, we use natural abundance and δ18O spiked water within our experiments to assay rates of cellular re-oxidation (within the sulfate reduction pathway) and to constrain natural δ18O effects within these systems. Finally, we use modern molecular biological techniques to track community structure as a function of time and environmental conditions. Together, these data provide an integrated metric with which to interpret complex natural sulfur isotope records.

Sulfate reduction and oxic respiration in marine sediments: implications for organic carbon preservation in euxinic environments

NASA Technical Reports Server (NTRS)

Canfield, D. E.; DeVincenzi, D. L. (Principal Investigator)

1989-01-01

Compilations have been made of sulfate reduction rates and oxic respiration rates over the entire range of marine sedimentation rates, and sedimentary environments, including several euxinic sites. These data show, consistent with the findings of Jorgensen (1982, Nature, 296, 643-645), that sulfate reduction and oxic respiration oxidize equal amounts of organic carbon in nearshore sediments. As sedimentation rates decrease, oxic respiration, becomes progressively more important, and in deep-sea sediments 100-1000 times more organic carbon is oxidized by oxic respiration than by sulfate reduction. By contrast, nearly as much organic carbon is oxidized by sulfate reduction in euxinic sediments as is oxidized by the sum of sulfate reduction and oxic respiration in normal marine sediments of similar deposition rate. This observation appears at odds with the enhanced preservation of organic carbon observed in euxinic sediments. However, only small reductions in (depth-integrated) organic carbon decomposition rates (compared to normal marine) are required to give both high organic carbon concentrations and enhanced carbon preservation in euxinic sediments. Lower rates of organic carbon decomposition (if only by subtle amounts) are explained by the diminished ability of anaerobic bacteria to oxidize the full suite of sedimentary organic compounds.

Acetate Production from Oil under Sulfate-Reducing Conditions in Bioreactors Injected with Sulfate and Nitrate

PubMed Central

Callbeck, Cameron M.; Agrawal, Akhil

2013-01-01

Oil production by water injection can cause souring in which sulfate in the injection water is reduced to sulfide by resident sulfate-reducing bacteria (SRB). Sulfate (2 mM) in medium injected at a rate of 1 pore volume per day into upflow bioreactors containing residual heavy oil from the Medicine Hat Glauconitic C field was nearly completely reduced to sulfide, and this was associated with the generation of 3 to 4 mM acetate. Inclusion of 4 mM nitrate inhibited souring for 60 days, after which complete sulfate reduction and associated acetate production were once again observed. Sulfate reduction was permanently inhibited when 100 mM nitrate was injected by the nitrite formed under these conditions. Pulsed injection of 4 or 100 mM nitrate inhibited sulfate reduction temporarily. Sulfate reduction resumed once nitrate injection was stopped and was associated with the production of acetate in all cases. The stoichiometry of acetate formation (3 to 4 mM formed per 2 mM sulfate reduced) is consistent with a mechanism in which oil alkanes and water are metabolized to acetate and hydrogen by fermentative and syntrophic bacteria (K. Zengler et al., Nature 401:266–269, 1999), with the hydrogen being used by SRB to reduce sulfate to sulfide. In support of this model, microbial community analyses by pyrosequencing indicated SRB of the genus Desulfovibrio, which use hydrogen but not acetate as an electron donor for sulfate reduction, to be a major community component. The model explains the high concentrations of acetate that are sometimes found in waters produced from water-injected oil fields. PMID:23770914

Acetate production from oil under sulfate-reducing conditions in bioreactors injected with sulfate and nitrate.

PubMed

Callbeck, Cameron M; Agrawal, Akhil; Voordouw, Gerrit

2013-08-01

Oil production by water injection can cause souring in which sulfate in the injection water is reduced to sulfide by resident sulfate-reducing bacteria (SRB). Sulfate (2 mM) in medium injected at a rate of 1 pore volume per day into upflow bioreactors containing residual heavy oil from the Medicine Hat Glauconitic C field was nearly completely reduced to sulfide, and this was associated with the generation of 3 to 4 mM acetate. Inclusion of 4 mM nitrate inhibited souring for 60 days, after which complete sulfate reduction and associated acetate production were once again observed. Sulfate reduction was permanently inhibited when 100 mM nitrate was injected by the nitrite formed under these conditions. Pulsed injection of 4 or 100 mM nitrate inhibited sulfate reduction temporarily. Sulfate reduction resumed once nitrate injection was stopped and was associated with the production of acetate in all cases. The stoichiometry of acetate formation (3 to 4 mM formed per 2 mM sulfate reduced) is consistent with a mechanism in which oil alkanes and water are metabolized to acetate and hydrogen by fermentative and syntrophic bacteria (K. Zengler et al., Nature 401:266-269, 1999), with the hydrogen being used by SRB to reduce sulfate to sulfide. In support of this model, microbial community analyses by pyrosequencing indicated SRB of the genus Desulfovibrio, which use hydrogen but not acetate as an electron donor for sulfate reduction, to be a major community component. The model explains the high concentrations of acetate that are sometimes found in waters produced from water-injected oil fields.

Localized sulfate-reducing zones in a coastal plain aquifer

USGS Publications Warehouse

Brown, C.J.; Coates, J.D.; Schoonen, M.A.A.

1999-01-01

High concentrations of dissolved iron in ground water of coastal plain or alluvial aquifers contribute to the biofouling of public supply wells for which treatment and remediation is costly. Many of these aquifers, however, contain zones in which microbial sulfate reduction and the associated precipitation of iron-sulfide minerals decreases iron mobility. The principal water-bearing aquifer (Magothy Aquifer of Cretaceous age) in Suffolk County, New York, contains localized sulfate-reducing zones in and near lignite deposits, which generally are associated with clay lenses. Microbial analyses of core samples amended with [14C]-acetate indicate that microbial sulfate reduction is the predominant terminal-electron-accepting process (TEAP) in poorly permeable, lignite-rich sediments at shallow depths and near the ground water divide. The sulfate-reducing zones are characterized by abundant lignite and iron-sulfide minerals, low concentrations of Fe(III) oxyhydroxides, and by proximity to clay lenses that contain pore water with relatively high concentrations of sulfate and dissolved organic carbon. The low permeability of these zones and, hence, the long residence time of ground water within them, permit the preservation and (or) allow the formation of iron-sulfide minerals, including pyrite and marcasite. Both sulfate-reducing bacteria (SRB) and iron-reducing bacteria (IRB) are present beneath and beyond the shallow sulfate-reducing zones. A unique Fe(III)-reducing organism, MD-612, was found in core sediments from a depth of 187 m near the southern shore of Long Island. The distribution of poorly permeable, lignite-rich, sulfate-reducing zones with decreased iron concentration is varied within the principal aquifer and accounts for the observed distribution of dissolved sulfate, iron, and iron sulfides in the aquifer. Locating such zones for the placement of production wells would be difficult, however, because these zones are of limited aerial extent.

The Effect of Temperature and Hydrogen Limited Growth on the Fractionation of Sulfur Isotopes by Thermodesulfatator indicus, a Deep-sea Hydrothermal Vent Sulfate-Reducing Bacterium

NASA Astrophysics Data System (ADS)

Hoek, J.; Reysenbach, A.; Habicht, K.; Canfield, D. E.

2004-12-01

Sulfate-reducing bacteria fractionate sulfur isotopes during dissimilatory sulfate reduction, producing sulfide depleted in 34S. Although isotope fractionation during sulfate reduction of pure cultures has been extensively studied, most of the research to date has focused on mesophilic sulfate reducers, particularly for the species Desulfovibrio desulfuricans. Results from these studies show that: 1) fractionations range from 3-46‰ with an average around 18‰ , 2) when organic electron donors are utilized, the extent of fractionation is dependent on the rate of sulfate reduction, with decreasing fractionations observed with higher specific rates, 3) fractionations are suppressed with low sulfate concentrations, and when hydrogen is used as the electron donor. High specific sulfate-reduction rates are encountered when sulfate-reducing bacteria metabolize at their optimal temperature and under non-limiting substrate conditions. Changes in both temperature and substrate availability could shift fractionations from those expressed under optimal growth conditions. Sulfate reducers may frequently experience substrate limitation and sub-optimal growth temperatures in the environment. Therefore it is important to understand how sulfate-reducing bacteria fractionate sulfur isotopes under conditions that more closely resemble the restrictions imposed by the environment. In this study the fractionation of sulfur isotopes by Thermodesulfatator indicus was explored during sulfate reduction under a wide range of temperatures and with both hydrogen-saturating and hydrogen-limited conditions. T. indicus is a thermophilic (temperature optimum = 70° C) chemolithotrophic sulfate-reducing bacterium, which was recently isolated from a deep-sea hydrothermal vent on the Central Indian Ridge. This bacterium represents the type species of a new genus and to date is the most deeply branching sulfate-reducing bacterium known. T. indicus was grown in carbonate-buffered salt-water medium with H2 as the sole electron donor, and CO2 as primary carbon source. The fractionation of sulfur isotopes was measured in batch cultures and in a thermal gradient block over the full temperature range of growth (40-80° C). For experiments in the gradient block, cell-specific rates of sulfate reduction increased with increasing temperatures to 70° C after which sulfate-reduction rates rapidly decreased. The range of fractionations (1.5-10‰ ) was typical for growth with hydrogen as the electron donor. Fractionations decreased with increasing temperature from 40--60° C, and increased with increasing temperatures from 60-80° C. Growth under H2-limited conditions in a fed-batch culture revealed high fractionations of 24-37‰ . This is the first report of sulfur isotope fractionation under H2 limited growth and indicates that large fractionations are produced when H2 is supplied as a limiting substrate. Our results suggest that fractionation is controlled by the competition of forward and reverse enzymatic reaction rates during sulfate reduction and by sulfate transport into the cell.

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate

PubMed Central

Thorup, Casper; Schramm, Andreas

2017-01-01

ABSTRACT This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus. Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. PMID:28720728

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

METHANOGENESIS AND SULFATE REDUCTION IN CHEMOSTATS: I. KINETIC STUDIES AND EXPERIMENTS

EPA Science Inventory

Six anaerobic chemostats containing mixed microbial cultures were used to investigate the interactions between sulfate reduction and methanogenesis for three substrates: acetic acid, methanol and formic acid. Sulfate reducers outcompeted methanogens in acetate-fed chemostats whil...

Evaluation of in situ layers for treatment of acid mine drainage: a field comparison.

PubMed

Hulshof, Andrea H M; Blowes, David W; Gould, W Douglas

2006-05-01

Reactive treatment layers, containing labile organic carbon, were evaluated to determine their ability to promote sulfate reduction and metal sulfide precipitation within a tailings impoundment, thereby treating tailings effluent prior to discharge. Organic carbon materials, including woodchips and pulp waste, were mixed with the upper meter of tailings in two separate test cells, a third control cell contained only tailings. In the woodchip cell sulfate reduction rates were 500 mg L-1a-1, (5.2 mmol L-1a-1) this was coupled with the gradual removal of 350 mg L-1 Zn (5.4 mmol L-1). Decreased delta13CDIC values from -3 per thousand to as low as -12 per thousand indicated that sulfate reduction was coupled with organic carbon oxidation. In the pulp waste cell the most dramatic change was observed near the interface between the pulp waste amended tailings and the underlying undisturbed tailings. Sulfate reduction rates were 5000 mg L-1a-1 (52 mmol L-1a-1), Fe concentrations decreased by 80-99.5% (148 mmol L-1) and Zn was consistently <5 mg L-1. Rates of sulfate reduction and metal removal decreased as the pore water migrated upward into the shallower tailings. Increased rates of sulfate reduction in the pulp waste cell were consistent with decreased delta13CDIC values, to as low as -22 per thousand, and increased populations of sulfate reducing bacteria. Lower concentrations of the nutrients, phosphorus, organic carbon and nitrogen in the woodchip material contribute to the lower sulfate reduction rates observed in the woodchip cell.

INHIBITION OF REDUCTIVE DECHLORINATION BY SULFATE REDUCTION IN MICROCOSMS (ABSTRACT ONLY)

EPA Science Inventory

High sulfate (>1,000 mg/L) concentrations are potentially problematic for field implementation of in situ bioremediation of chlorinated ethenes because its reduction competes for electron donor with reductive dechlorination. As a result of this competition, reductive dechl...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Surdam, R.C.; MacGowan, D.B.

At temperatures less than 80/degree/C, the diagenetic reactions producing carbonate cements in sandstones can be explained nicely by the model proposed in 1986 by C.D. Curtis and M.L. Coleman. Briefly, the distribution of early carbonate cements is controlled by dissolved sulfate concentration and is a function of the processes which affect sulfate concentration (i.e., depositional water composition, microbial sulfate reduction, and water mixing). In order to use this model in a predictive sense, a knowledge of the original depositional environment's hydrology and hydrochemistry is necessary. Predictive models for sandstone diagenesis in the 80/degree/ to 130/degree/C thermal interval can be developedmore » based on carboxylic acid/CO/sub 2/ distributions and ratios. The model assumes that over this thermal interval the alkalinity in the reservoir facies is dominated by carboxylic acids and that a significant portion of CO/sub 2/ present is the product of decarboxylation of the acids (assuming there has been no significant mixing of water bodies). Furthermore, it is assumed that the stability of carbonates is a function of the carboxylic acid/CO/sub 2/ ratio, and the stability of framework grains is a function of the distribution and concentration of carboxylic acids. At temperatures greater than 130/degree/C, diagenetic reactions controlling the distribution of cements and the stability of framework grains in sandstones generally can be explained by thermocatalytic sulfate reduction. The determinative aspects of this process are the type of organics present in the system, the sulfate/organic ratio, and the presence or absence of iron. In addition to this information, if a time-temperature profile and kinetics for the redox reaction of interest are available, the process and resultant mineral reactions can be modeled.« less

Microbial processes and factors controlling their activities in alkaline lakes of the Mongolian plateau

NASA Astrophysics Data System (ADS)

Namsaraev, Zorigto B.; Zaitseva, Svetlana V.; Gorlenko, Vladimir M.; Kozyreva, Ludmila P.; Namsaraev, Bair B.

2015-11-01

A striking feature of the Mongolian plateau is the wide range of air temperatures during a year, -30 to 30°C. High summer temperatures, atmospheric weathering and the arid climate lead to formation of numerous alkaline soda lakes that are covered by ice during 6-7 months per year. During the study period, the lakes had pH values between 8.1 to 10.4 and salinity between 1.8 and 360 g/L. According to chemical composition, the lakes belong to sodium carbonate, sodium chloride-carbonate and sodium sulfate-carbonate types. This paper presents the data on the water chemical composition, results of the determination of the rates of microbial processes in microbial mats and sediments in the lakes studied, and the results of a Principal Component Analysis of environmental variables and microbial activity data. Temperature was the most important factor that influenced both chemical composition and microbial activity. pH and salinity are also important factors for the microbial processes. Dark CO2 fixation is impacted mostly by salinity and the chemical composition of the lake water. Total photosynthesis and sulfate-reduction are impacted mostly by pH. Photosynthesis is the dominant process of primary production, but the highest rate (386 mg C/(L•d)) determined in the lakes studied were 2-3 times lower than in microbial mats of lakes located in tropical zones. This can be explained by the relatively short warm period that lasts only 3-4 months per year. The highest measured rate of dark CO2 assimilation (59.8 mg C/(L•d)) was much lower than photosynthesis. The highest rate of sulfate reduction was 60 mg S/(L•d), while that of methanogenesis was 75.6 μL CN4/(L•d) in the alkaline lakes of Mongolian plateau. The rate of organic matter consumption during sulfate reduction was 3-4 orders of magnitude higher than that associated with methanogenesis.

The pH and pCO2 dependence of sulfate reduction in shallow-sea hydrothermal CO2 – venting sediments (Milos Island, Greece)

PubMed Central

Bayraktarov, Elisa; Price, Roy E.; Ferdelman, Timothy G.; Finster, Kai

2013-01-01

Microbial sulfate reduction (SR) is a dominant process of organic matter mineralization in sulfate-rich anoxic environments at neutral pH. Recent studies have demonstrated SR in low pH environments, but investigations on the microbial activity at variable pH and CO2 partial pressure are still lacking. In this study, the effect of pH and pCO2 on microbial activity was investigated by incubation experiments with radioactive 35S targeting SR in sediments from the shallow-sea hydrothermal vent system of Milos, Greece, where pH is naturally decreased by CO2 release. Sediments differed in their physicochemical characteristics with distance from the main site of fluid discharge. Adjacent to the vent site (T ~40–75°C, pH ~5), maximal sulfate reduction rates (SRR) were observed between pH 5 and 6. SR in hydrothermally influenced sediments decreased at neutral pH. Sediments unaffected by hydrothermal venting (T ~26°C, pH ~8) expressed the highest SRR between pH 6 and 7. Further experiments investigating the effect of pCO2 on SR revealed a steep decrease in activity when the partial pressure increased from 2 to 3 bar. Findings suggest that sulfate reducing microbial communities associated with hydrothermal vent system are adapted to low pH and high CO2, while communities at control sites required a higher pH for optimal activity. PMID:23658555

The pH and pCO2 dependence of sulfate reduction in shallow-sea hydrothermal CO2 - venting sediments (Milos Island, Greece).

PubMed

Bayraktarov, Elisa; Price, Roy E; Ferdelman, Timothy G; Finster, Kai

2013-01-01

Microbial sulfate reduction (SR) is a dominant process of organic matter mineralization in sulfate-rich anoxic environments at neutral pH. Recent studies have demonstrated SR in low pH environments, but investigations on the microbial activity at variable pH and CO2 partial pressure are still lacking. In this study, the effect of pH and pCO2 on microbial activity was investigated by incubation experiments with radioactive (35)S targeting SR in sediments from the shallow-sea hydrothermal vent system of Milos, Greece, where pH is naturally decreased by CO2 release. Sediments differed in their physicochemical characteristics with distance from the main site of fluid discharge. Adjacent to the vent site (T ~40-75°C, pH ~5), maximal sulfate reduction rates (SRR) were observed between pH 5 and 6. SR in hydrothermally influenced sediments decreased at neutral pH. Sediments unaffected by hydrothermal venting (T ~26°C, pH ~8) expressed the highest SRR between pH 6 and 7. Further experiments investigating the effect of pCO2 on SR revealed a steep decrease in activity when the partial pressure increased from 2 to 3 bar. Findings suggest that sulfate reducing microbial communities associated with hydrothermal vent system are adapted to low pH and high CO2, while communities at control sites required a higher pH for optimal activity.

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

USGS Publications Warehouse

Church, C.D.; Wilkin, R.T.; Alpers, Charles N.; Rye, R.O.; Blaine, R.B.

2007-01-01

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2-3 ??? heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. ?? 2007 Church et al; licensee BioMed Central Ltd.

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

PubMed Central

Church, Clinton D; Wilkin, Richard T; Alpers, Charles N; Rye, Robert O; McCleskey, R Blaine

2007-01-01

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2–3 ‰ heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. PMID:17956615

Nitrate reduction in sulfate-reducing bacteria.

PubMed

Marietou, Angeliki

2016-08-01

Sulfate-reducing bacteria (SRBs) gain their energy by coupling the oxidation of organic substrate to the reduction of sulfate to sulfide. Several SRBs are able to use alternative terminal electron acceptors to sulfate such as nitrate. Nitrate-reducing SRBs have been isolated from a diverse range of environments. In order to be able to understand the significance of nitrate reduction in SRBs, we need to examine the ecology and physiology of the nitrate-reducing SRB isolates. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Changes in organic matter biodegradatility influencing sulfate reduction in an aquifer contaminated by landfill leachate

USGS Publications Warehouse

Harris, Steve H.; Istok, Jonathan D.; Suflita, Joseph M.

2006-01-01

In situ experiments were conducted to measure sulfate reduction rates and identify rate-limiting factors in a shallow, alluvial aquifer contaminated with municipal landfill leachate. Single-well, push–pull tests conducted in a well adjacent to the landfill with >8 mM dissolved organic carbon (DOC) exhibited a sulfate reduction rate of 3.2 μmol SO4−2 (L sediment)−1 day−1, a value in close agreement with laboratory-derived estimates. Identical tests conducted in wells located 90 m downgradient where DOC levels remained high (>3 mM) showed no detectable sulfate consumption, and laboratory assays confirmed this observation. However, the rates of sulfate reduction in sediment samples obtained from this site were three times larger when they were amended with filter-sterilized groundwater from the upgradient location. The effect of various amendments on sulfate reduction rates was further examined in laboratory incubations using sediment collected from the downgradient site amended with 35S sulfate. Unamended sediments showed only weak conversion of the tracer to 35S sulfide (5 to 7 cpm/cm2), whereas the addition of Desulfovibrio cells increased 35S sulfide production to 44 cpm/cm2. However, the application of heat-killed Desulfovibrio had a similar stimulatory effect, as did a lactate amendment. Collectively, these findings indicate that the lack of measurable sulfate reduction at the downgradient site was not due to the absence of the necessary metabolic potential, the presence of lower sulfate concentration, or the quantity of electron donor, but by its biodegradability. The findings also indicate that field bioaugmentation attempts should be interpreted with caution.

Influence of co-substrate on textile wastewater treatment and microbial community changes in the anaerobic biological sulfate reduction process.

PubMed

Rasool, Kashif; Mahmoud, Khaled A; Lee, Dae Sung

2015-12-15

This study investigated the anaerobic treatment of sulfate-rich synthetic textile wastewater in three sulfidogenic sequential batch reactors (SBRs). The experimental protocol was designed to examine the effect of three different co-substrates (lactate, glucose, and ethanol) and their concentrations on wastewater treatment performance. Sulfate reduction and dye degradation were improved when lactate and ethanol were used as electron donors, as compared with glucose. Moreover, under co-substrate limited concentrations, color, sulfate, and chemical oxygen demand (COD) removal efficiencies were declined. By reducing co-substrate COD gradually from 3000 to 500 mg/L, color removal efficiencies were decreased from 98.23% to 78.46%, 63.37%, and 69.10%, whereas, sulfate removal efficiencies were decreased from 98.42%, 82.35%, and 87.0%, to 30.27%, 21.50%, and 10.13%, for lactate, glucose, and ethanol fed reactors, respectively. Fourier transform infrared spectroscopy (FTIR) and total aromatic amine analysis revealed lactate to be a potential co-substrate for further biodegradation of intermediate metabolites formed after dye degradation. Pyrosequencing analysis showed that microbial community structure was significantly affected by the co-substrate. The reactor with lactate as co-substrate showed the highest relative abundance of sulfate reducing bacteria (SRBs), followed by ethanol, whereas the glucose-fed reactor showed the lowest relative abundance of SRB. Copyright © 2015 Elsevier B.V. All rights reserved.

δ34S and δ18O of dissolved sulfate as biotic tracer of biogeochemical influences on arsenic mobilization in groundwater in the Hetao Plain, Inner Mongolia, China.

PubMed

Li, M D; Wang, Y X; Li, P; Deng, Y M; Xie, X J

2014-12-01

Environmental isotopology of sulfur and oxygen of dissolved sulfate in groundwater was conducted in the Hetao Plain, northwestern China, aiming to better understand the processes controlling arsenic mobilization in arsenic-rich aqueous systems. A total of 22 groundwater samples were collected from domestic wells in the Hetao Plain. Arsenic concentrations ranged from 11.0 to 388 μg/L. The δ(34)S-SO4 and δ(18)O-SO4 values of dissolved sulfate covered a range from +1.48 to +22.4‰ and +8.17‰ to +14.8‰ in groundwater, respectively. The wide range of δ(34)S-SO4 values reflected either an input of different sources of sulfate, such as gypsum dissolution and fertilizer application, or a modification from biogeochemical process of bacterial sulfate reduction. The positive correlation between δ(34)S-SO4 and arsenic concentrations suggested that bacteria mediated processes played an important role in the mobilization of arsenic. The δ(18)O-SO4 values correlated non-linearly with δ(34)S-SO4, but within a relatively narrow range (+8.17 to +14.8‰), implying that complexities inherent in the sulfate-oxygen (O-SO4(2-)) origins, for instance, water-derived oxygen (O-H2O), molecular oxygen (O-O2) and isotope exchanging with dissolved oxides, are accounted for oxygen isotope composition of dissolved sulfate in groundwater in the Hetao Plain.

Assessment of the performance of SMFCs in the bioremediation of PAHs in contaminated marine sediments under different redox conditions and analysis of the associated microbial communities.

PubMed

Hamdan, Hamdan Z; Salam, Darine A; Hari, Ananda Rao; Semerjian, Lucy; Saikaly, Pascal

2017-01-01

The biodegradation of naphthalene, 2-methylnaphthalene and phenanthrene was evaluated in marine sediment microbial fuel cells (SMFCs) under different biodegradation conditions, including sulfate reduction as a major biodegradation pathway, employment of anode as terminal electron acceptor (TEA) under inhibited sulfate reducing bacteria activity, and combined sulfate and anode usage as electron acceptors. A significant removal of naphthalene and 2-methylnaphthalene was observed at early stages of incubation in all treatments and was attributed to their high volatility. In the case of phenanthrene, a significant removal (93.83±1.68%) was measured in the closed circuit SMFCs with the anode acting as the main TEA and under combined anode and sulfate reduction conditions (88.51±1.3%). A much lower removal (40.37±3.24%) was achieved in the open circuit SMFCs operating with sulfate reduction as a major biodegradation pathway. Analysis of the anodic bacterial community using 16S rRNA gene pyrosequencing revealed the enrichment of genera with potential exoelectrogenic capability, namely Geoalkalibacter and Desulfuromonas, on the anode of the closed circuit SMFCs under inhibited SRB activity, while they were not detected on the anode of open circuit SMFCs. These results demonstrate the role of the anode in enhancing PAHs biodegradation in contaminated marine sediments and suggest a higher system efficiency in the absence of competition between microbial redox processes (under SRB inhibition), namely due to the anode enrichment with exoelectrogenic bacteria, which is a more energetically favorable mechanism for PAHs oxidation than sulfate. Copyright © 2016. Published by Elsevier B.V.

Rapid Sediment Accumulation Results in High Methane Effluxes from Coastal Sediments

PubMed Central

Lenstra, Wytze; Jong, Dirk; Meysman, Filip J. R.; Sapart, Célia J.; van der Veen, Carina; Röckmann, Thomas; Gonzalez, Santiago; Slomp, Caroline P.

2016-01-01

Globally, the methane (CH4) efflux from the ocean to the atmosphere is small, despite high rates of CH4 production in continental shelf and slope environments. This low efflux results from the biological removal of CH4 through anaerobic oxidation with sulfate in marine sediments. In some settings, however, pore water CH4 is found throughout the sulfate-bearing zone, indicating an apparently inefficient oxidation barrier for CH4. Here we demonstrate that rapid sediment accumulation can explain this limited capacity for CH4 removal in coastal sediments. In a saline coastal reservoir (Lake Grevelingen, The Netherlands), we observed high diffusive CH4 effluxes from the sediment into the overlying water column (0.2–0.8 mol m-2 yr-1) during multiple years. Linear pore water CH4 profiles and the absence of an isotopic enrichment commonly associated with CH4 oxidation in a zone with high rates of sulfate reduction (50–170 nmol cm-3 d-1) both suggest that CH4 is bypassing the zone of sulfate reduction. We propose that the rapid sediment accumulation at this site (~ 13 cm yr-1) reduces the residence time of the CH4 oxidizing microorganisms in the sulfate/methane transition zone (< 5 years), thus making it difficult for these slow growing methanotrophic communities to build-up sufficient biomass to efficiently remove pore water CH4. In addition, our results indicate that the high input of organic matter (~ 91 mol C m-2 yr-1) allows for the co-occurrence of different dissimilatory respiration processes, such as (acetotrophic) methanogenesis and sulfate reduction in the surface sediments by providing abundant substrate. We conclude that anthropogenic eutrophication and rapid sediment accumulation likely increase the release of CH4 from coastal sediments. PMID:27560511

The demonstration of a novel sulfur cycle-based wastewater treatment process: sulfate reduction, autotrophic denitrification, and nitrification integrated (SANI®) biological nitrogen removal process.

PubMed

Lu, Hui; Wu, Di; Jiang, Feng; Ekama, George A; van Loosdrecht, Mark C M; Chen, Guang-Hao

2012-11-01

Saline water supply has been successfully practiced for toilet flushing in Hong Kong since 1950s, which saves 22% of freshwater in Hong Kong. In order to extend the benefits of saline water supply into saline sewage management, we have recently developed a novel biological organics and nitrogen removal process: the Sulfate reduction, Autotrophic denitrification, and Nitrification Integrated (SANI®) process. The key features of this novel process include elimination of oxygen demand in organic matter removal and production of minimal sludge. Following the success of a 500-day lab-scale trial, this study reports a pilot scale evaluation of this novel process treating 10 m(3) /day of 6-mm screened saline sewage in Hong Kong. The SANI® pilot plant consisted of a sulfate reduction up-flow sludge bed (SRUSB) reactor, an anoxic bioreactor for autotrophic denitrification and an aerobic bioreactor for nitrification. The plant was operated at a steady state for 225 days, during which the average removal efficiencies of both chemical oxygen demand (COD) and total suspended solids (TSS) at 87% and no excess sludge was purposefully withdrawn. Furthermore, a tracer test revealed 5% short circuit flow and a 34.6% dead zone in the SRUSB, indicating a good possibility to further optimize the treatment capacity of the process for full-scale application. Compared with conventional biological nitrogen removal processes, the SANI® process reduces 90% of waste sludge, which saves 35% of the energy and reduces 36% of fossil CO(2) emission. The SANI® process not only eliminates the major odor sources originating from primary treatment and subsequent sludge treatment and disposal during secondary saline sewage treatment, but also promotes saline water supply as an economic and sustainable solution for water scarcity and sewage treatment in water-scarce coastal areas. Copyright © 2012 Wiley Periodicals, Inc.

Effect of process variables on the sulfate reduction process in bioreactors treating metal-containing wastewaters: factorial design and response surface analyses.

PubMed

Villa-Gomez, D K; Pakshirajan, K; Maestro, R; Mushi, S; Lens, P N L

2015-07-01

The individual and combined effect of the pH, chemical oxygen demand (COD) and SO4 (2-) concentration, metal to sulfide (M/S(2-)) ratio and hydraulic retention time (HRT) on the biological sulfate reduction (SR) process was evaluated in an inverse fluidized bed reactor by factorial design analysis (FDA) and response surface analysis (RSA). The regression-based model of the FDA described the experimental results well and revealed that the most significant variable affecting the process was the pH. The combined effect of the pH and HRT was barely observable, while the pH and COD concentration positive effect (up to 7 and 3 gCOD/L, respectively) enhanced the SR process. Contrary, the individual COD concentration effect only enhanced the COD removal efficiency, suggesting changes in the microbial pathway. The RSA showed that the M/S(2-) ratio determined whether the inhibition mechanism to the SR process was due to the presence of free metals or precipitated metal sulfides.

Optimization of microbial detoxification for an aquatic mercury-contaminated environment.

PubMed

Figueiredo, Neusa L; Canário, João; Serralheiro, Maria Luísa; Carvalho, Cristina

2017-01-01

Mercury (Hg) reduction performed by microorganisms is well recognized as a biological means for remediation of contaminated environment. Recently, studies demonstrated that Hg-resistant microorganisms of Tagus Estuary are involved in metal reduction processes. In the present study, aerobic microbial community isolated from a highly Hg-contaminated area of Tagus Estuary was used to determine the optimization of the reduction process in conditions such as the contaminated ecosystem. Factorial design methodology was employed to examine the influence of glucose, sulfate, iron, and chloride on Hg reduction. In the presence of several concentrations of these elements, microbial community reduced Hg in a range of 37-61% of the initial 0.1 mg/ml Hg 2+ levels. The response prediction through central composite design showed that the increase of sulfate concentration led to an optimal response in Hg reduction by microbial community, while the rise in chloride levels markedly decreased metal reduction. Iron may exert antagonistic effects depending upon the media composition. These results are useful in understanding the persistence of Hg contamination in Tagus Estuary after inactivation of critical industrial units, as well as data might also be beneficial for development of new bioremediation strategies either in Tagus Estuary and/or in other Hg-contaminated aquatic environments.

Dynamic investigation of the role of the surface sulfates in NO{sub x} reduction and SO{sub 2} oxidation over V{sub 2}O{sub 5}-WO{sub 3}/TiO{sub 2} catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orsenigo, C.; Lietti, L.; Tronconi, E.

1998-06-01

Transient experiments performed over synthesized and commercial V{sub 2}O{sub 5}-WO{sub 3}/TiO{sub 2} catalysts during catalyst conditioning and during step changes of the operating variables (SO{sub 2} inlet concentration and temperature) show that conditioning of the catalyst is required to attain significant and reproducible steady-state data in both the reduction of NO{sub x} and the oxidation of SO{sub 2}. The response time of conditioning for NO{sub x} reduction is of a few hours and that for SO{sub 2} oxidation is of several hours. Fourier transform infrared spectroscopy temperature programmed decomposition, and thermogravimetric measurements showed that catalyst conditioning is associated with amore » slow process of buildup of sulfates: the different characteristic conditioning times observed in the reduction of NO{sub x} and in the oxidation of SO{sub 2} suggest that the buildup of sulfates occurs first at the vanadyl sites and later on at the exposed titania surface. Formation of sulfates at or near the vanadyl sites increases the reactivity in the de-NO{sub x} reaction, possibly due to the increase in the Broensted and Lewis acidity of the catalyst, whereas the titania surface acts as SO{sub 3} acceptor and affects the outlet SO{sub 3} concentration during catalyst conditioning for the SO{sub 2} oxidation reaction. The response time to step changes in SO{sub 2} concentration and temperature is of a few hours in the case of SO{sub 2} oxidation and much shorter in the case of NO{sub x} reduction. The different time responses associated with conditioning and with step changes in the settings of the operating variables have been rationalized in terms of the different extent of perturbation of the sulfate coverage experienced by the catalyst.« less

Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

USGS Publications Warehouse

Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

2014-01-01

The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2–5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3) and a final, or late-stage, TSR reaction in which hydrocarbon oxidation continues at a slower rate via the non-autocatalytic reduction of sulfate by gaseous hydrocarbons.

Removal of chromium from synthetic plating waste by zero-valent iron and sulfate-reducing bacteria.

PubMed

Guha, Saumyen; Bhargava, Puja

2005-01-01

Experiments were conducted to evaluate the potential of zero-valent iron and sulfate-reducing bacteria (SRB) for reduction and removal of chromium from synthetic electroplating waste. The zero-valent iron shows promising results as a reductant of hexavalent chromium (Cr+6) to trivalent chromium (Cr+3), capable of 100% reduction. The required iron concentration was a function of chromium concentration in the waste stream. Removal of Cr+3 by adsorption or precipitation on iron leads to complete removal of chromium from the waste and was a slower process than the reduction of Cr+6. Presence SRB in a completely mixed batch reactor inhibited the reduction of Cr+6. In a fixed-bed column reactor, SRB enhanced chromium removal and showed promising results for the treatment of wastes with low chromium concentrations. It is proposed that, for waste with high chromium concentration, zero-valent iron is an efficient reductant and can be used for reduction of Cr+6. For low chromium concentrations, a SRB augmented zero-valent iron and sand column is capable of removing chromium completely.

Acetate availability and its influence on sustainable bioremediation of Uranium-contaminated groundwater

USGS Publications Warehouse

Williams, K.H.; Long, P.E.; Davis, J.A.; Wilkins, M.J.; N'Guessan, A. L.; Steefel, Carl; Yang, L.; Newcomer, D.; Spane, F.A.; Kerkhof, L.J.; Mcguinness, L.; Dayvault, R.; Lovley, D.R.

2011-01-01

Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126??M).During successive summer experiments - referred to as "Winchester" (2007) and "Big Rusty" (2008) - acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metal reducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM),and the extent to which iron reduction ("Winchester") or sulfate reduction("Big Rusty") was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO2-CO3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI);however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1-0.05 ??M) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during "Big Rusty" was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration "Winchester" experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter-like strains dominated the groundwater community profile during iron reduction, with 13C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to replicate their genome during the period of optimal U(VI) removal. Gene transcript levels during "Big Rusty" were quantified for Geobacter-specific citrate synthase (gltA), with ongoing transcription during sulfate reduction indicating that members of the Geobacteraceae were still active and likely contributing to U(VI) removal. The persistence of reducible Fe(III) in sediments recovered from an area of prolonged (110-day) sulfate reduction is consistent with this conclusion. These results indicate that acetate availability and its ability to sustain the activity of iron- and uranyl-respiring Geobacter strains during sulfate reduction exerts a primary control on optimized U(VI) removal from groundwater at the Rifle IFRC site over extended time scales (>50 days). ?? Taylor & Francis Group, LLC.

Metabolic stratification driven by surface and subsurface interactions in a terrestrial mud volcano.

PubMed

Cheng, Ting-Wen; Chang, Yung-Hsin; Tang, Sen-Lin; Tseng, Ching-Hung; Chiang, Pei-Wen; Chang, Kai-Ti; Sun, Chih-Hsien; Chen, Yue-Gau; Kuo, Hung-Chi; Wang, Chun-Ho; Chu, Pao-Hsuan; Song, Sheng-Rong; Wang, Pei-Ling; Lin, Li-Hung

2012-12-01

Terrestrial mud volcanism represents the prominent surface geological feature, where fluids and hydrocarbons are discharged along deeply rooted structures in tectonically active regimes. Terrestrial mud volcanoes (MVs) directly emit the major gas phase, methane, into the atmosphere, making them important sources of greenhouse gases over geological time. Quantification of methane emission would require detailed insights into the capacity and efficiency of microbial metabolisms either consuming or producing methane in the subsurface, and establishment of the linkage between these methane-related metabolisms and other microbial or abiotic processes. Here we conducted geochemical, microbiological and genetic analyses of sediments, gases, and pore and surface fluids to characterize fluid processes, community assemblages, functions and activities in a methane-emitting MV of southwestern Taiwan. Multiple lines of evidence suggest that aerobic/anaerobic methane oxidation, sulfate reduction and methanogenesis are active and compartmentalized into discrete, stratified niches, resembling those in marine settings. Surface evaporation and oxidation of sulfide minerals are required to account for the enhanced levels of sulfate that fuels subsurface sulfate reduction and anaerobic methanotrophy. Methane flux generated by in situ methanogenesis appears to alter the isotopic compositions and abundances of thermogenic methane migrating from deep sources, and to exceed the capacity of microbial consumption. This metabolic stratification is sustained by chemical disequilibria induced by the mixing between upward, anoxic, methane-rich fluids and downward, oxic, sulfate-rich fluids.

Metabolic stratification driven by surface and subsurface interactions in a terrestrial mud volcano

PubMed Central

Cheng, Ting-Wen; Chang, Yung-Hsin; Tang, Sen-Lin; Tseng, Ching-Hung; Chiang, Pei-Wen; Chang, Kai-Ti; Sun, Chih-Hsien; Chen, Yue-Gau; Kuo, Hung-Chi; Wang, Chun-Ho; Chu, Pao-Hsuan; Song, Sheng-Rong; Wang, Pei-Ling; Lin, Li-Hung

2012-01-01

Terrestrial mud volcanism represents the prominent surface geological feature, where fluids and hydrocarbons are discharged along deeply rooted structures in tectonically active regimes. Terrestrial mud volcanoes (MVs) directly emit the major gas phase, methane, into the atmosphere, making them important sources of greenhouse gases over geological time. Quantification of methane emission would require detailed insights into the capacity and efficiency of microbial metabolisms either consuming or producing methane in the subsurface, and establishment of the linkage between these methane-related metabolisms and other microbial or abiotic processes. Here we conducted geochemical, microbiological and genetic analyses of sediments, gases, and pore and surface fluids to characterize fluid processes, community assemblages, functions and activities in a methane-emitting MV of southwestern Taiwan. Multiple lines of evidence suggest that aerobic/anaerobic methane oxidation, sulfate reduction and methanogenesis are active and compartmentalized into discrete, stratified niches, resembling those in marine settings. Surface evaporation and oxidation of sulfide minerals are required to account for the enhanced levels of sulfate that fuels subsurface sulfate reduction and anaerobic methanotrophy. Methane flux generated by in situ methanogenesis appears to alter the isotopic compositions and abundances of thermogenic methane migrating from deep sources, and to exceed the capacity of microbial consumption. This metabolic stratification is sustained by chemical disequilibria induced by the mixing between upward, anoxic, methane-rich fluids and downward, oxic, sulfate-rich fluids. PMID:22739492

Factors Governing the Germination of Sulfate-Reducing Desulfotomaculum Endospores Involved in Oil Reservoir Souring.

NASA Astrophysics Data System (ADS)

Sherry, A.; Bell, E.; Cueto, G.; Suarez-Suarez, A.; Pilloni, G.; Hubert, C. R.

2015-12-01

Reservoir souring is caused by the activity of sulfate-reducing microorganisms (SRM) in subsurface oil reservoirs, and is often induced by seawater injection during secondary oil recovery. Souring can potentially contribute to corrosion of infrastructure, health and safety hazards to the workforce, and reduction in value by increasing refining costs associated with producing the oil resource. Souring causes annual losses in the billions of dollars to the oil industry. Endospore-forming SRM, such as Desulfotomaculum spp., are often suspected culprits in reservoir souring. Endospores can survive unfavourable conditions for long periods, yet remain poised to germinate and become active if conditions become more favourable. Factors governing endospore germination are poorly understood, but are thought to include availability of nutrients, possibly metabolic by products of other anaerobic bioprocesses, and/or variations in temperature. Most research has focused on aerobic Bacillus spp., with very few studies dedicated to spore germination among anaerobes (order Clostridiales) including the sulfate-reducing Desulfotomaculum found in anoxic subsurface petroleum reservoirs. For Desulfotomaculum spores in deep hot oil reservoirs, cold seawater introduction during secondary oil recovery may create thermal viability zones for sulfate reduction near the injection wellbore. To evaluate these processes, sulfate-containing microcosms were prepared with different marine sediments as a source of spores, and amended with organic substrates in the presence or absence of oil. Incubation at 80°C for six days was followed by a down-shift in temperature to 60°C to mimic cold seawater injection into a hot reservoir. Souring did not occur at 80°C, but commenced within hours at 60°C. Microcosms were monitored for sulfate reduction and organic acids in combination with next generation sequencing of 16S rRNA genes (Ion Torrent, Illumina MiSeq). Through a combination of high-throughput microbial DNA sequencing and geochemical process analyses we show that altered conditions in oil reservoirs during seawater flooding activates dormant Desulfotomaculum endospores, which leads to reservoir souring, and provide insights on the factors governing the germination of endospores in the deep hot biosphere.

Partitioning Effects during Terminal Carbon and Electron Flow in Sediments of a Low-Salinity Meltwater Pond near Bratina Island, McMurdo Ice Shelf, Antarctica

PubMed Central

Mountfort, Douglas O.; Kaspar, Heinrich F.; Downes, Malcolm; Asher, Rodney A.

1999-01-01

A study of anaerobic sediments below cyanobacterial mats of a low-salinity meltwater pond called Orange Pond on the McMurdo Ice Shelf at temperatures simulating those in the summer season (<5°C) revealed that both sulfate reduction and methane production were important terminal anaerobic processes. Addition of [2-14C]acetate to sediment samples resulted in the passage of label mainly to CO2. Acetate addition (0 to 27 mM) had little effect on methanogenesis (a 1.1-fold increase), and while the rate of acetate dissimilation was greater than the rate of methane production (6.4 nmol cm−3 h−1 compared to 2.5 to 6 nmol cm−3 h−1), the portion of methane production attributed to acetate cleavage was <2%. Substantial increases in the methane production rate were observed with H2 (2.4-fold), and H2 uptake was totally accounted for by methane production under physiological conditions. Formate also stimulated methane production (twofold), presumably through H2 release mediated through hydrogen lyase. Addition of sulfate up to 50-fold the natural levels in the sediment (interstitial concentration, ∼0.3 mM) did not substantially inhibit methanogenesis, but the process was inhibited by 50-fold chloride (36 mM). No net rate of methane oxidation was observed when sediments were incubated anaerobically, and denitrification rates were substantially lower than rates for sulfate reduction and methanogenesis. The results indicate that carbon flow from acetate is coupled mainly to sulfate reduction and that methane is largely generated from H2 and CO2 where chloride, but not sulfate, has a modulating role. Rates of methanogenesis at in situ temperatures were four- to fivefold less than maximal rates found at 20°C. PMID:10584008

Green synthesis of gold nanoparticles reduced and stabilized by sodium glutamate and sodium dodecyl sulfate.

PubMed

Cabrera, Gil Felicisimo S; Balbin, Michelle M; Eugenio, Paul John G; Zapanta, Charleo S; Monserate, Juvy J; Salazar, Joel R; Mingala, Claro N

2017-03-18

The Turkevich method has been used for many years in the synthesis of gold nanoparticles. Lately, the use of plant extracts and amino acids has been reported, which is valuable in the field of biotechnology and biomedicine. The AuNPs was synthesized from the reduction of HAuCl4 3H2O by sodium glutamate and stabilized with sodium dodecyl sulfate. The optimum concentrations for sodium glutamate and sodium dodecyl sulfate in the synthesis process were determined. The characteristics of the synthesized AuNPs was analysed through UV-Vis Spectroscopy and SEM. The AuNPs have spherical shape with a mean diameter of approximately 21.62 ± 4.39 nm and is well dispersed. FTIR analysis of the AuNPs reflected that the sulfate head group of sodium dodecyl sulfate is adsorbed at the surface of the AuNPs. Thus, we report herein the synthesis of AuNPs using sodium glutamate and sodium dodecyl sulfate. Copyright © 2017 Elsevier Inc. All rights reserved.

Exploring the potential of anaerobic sulfate reduction process in treating sulfonated diazo dye: Microbial community analysis using bar-coded pyrosequencing.

PubMed

Rasool, Kashif; Shahzad, Asif; Lee, Dae Sung

2016-11-15

Anaerobic decolorization and biotransformation of azo dye was investigated in a sulfate-reducing environment. Batch reactor studies were performed with mixed cultures of anaerobic sulfate-reducing bacteria (SRBs) enriched from anaerobic digester sludge. Complete sulfate and color removal were achieved in batch experiments with different initial dye concentrations (50-2500mg/L) and 1000mg/L of sulfate. Induction of various oxidoreductive enzyme activities such as phenol oxidase, veratryl alcohol oxidase, lignin peroxidase, and azo reductase was studied to understand their involvement in dye metabolism under anoxic environment. The degradation of Cotton Red B was confirmed using high-performance liquid chromatography and gas chromatography-mass spectroscopy. Sulfidogenic sludge demonstrated excellent dye degradation and mineralization ability, producing aniline and 1,4-diamino benzene as metabolites. A barcoded 16S rRNA gene-pyrosequencing approach was used to assess the bacterial diversity in the sludge culture and a phylogenetic tree was constructed for sulfate-reducing bacteria. Copyright © 2016 Elsevier B.V. All rights reserved.

Sulfur isotopic and proteomic profiles of sulfate reducers grown under differential steady-states

NASA Astrophysics Data System (ADS)

Leavitt, W.; Venceslau, S.; Waldbauer, J.; Smith, D. A.; Boidi, F. J.; Bradley, A. S.

2016-12-01

Microbial sulfate reducers (MSR) drive the Earth's biogeochemical sulfur cycle. At the heart of this energy metabolism is a cascade of redox transformations coupling organic carbon and/or hydrogen oxidation to the dissimilatory reduction of sulfate to sulfide. The product sulfide is depleted in the heavier isotopes of sulfur, relative to the reactant sulfate, consistent with a normal kinetic isotope effect. However, the magnitude of the net fractionation during MSR can range over a range of 70 permil, consistent with a multi-step set of reactions. This range in MSR fractionation has been shown to mainly depend on: i) the cell-specific sulfate reduction rate (csSRR), and ii) the ambient sulfate concentration. However, the fractionation under identical conditions differs among strains (Bradley et al. 2016. Geobio), and so must also be mediated by strain-specific processes, such as the nature and quantity of individual proteins involved in sulfate reduction, electron transport, and growth. In recent work we have examined the influence of electron donor, electron acceptor, and co-limitation under controlled steady-state culture conditions in order better inform models of MSR isotope fractionation, and the physiological and isotopic response to differential environmental forcings (e.g. Leavitt et al. (2013) PNAS). Recent models of the fractionation response to MSR rate (c.f. Bradley 2016; Wing & Halevy, 2016) make specific predictions for the responses of the cellular metabolome and proteome. Here we compare the steady-state S-isotopic fractionation and proteome of `fast' versus `slow' grown D. vulgaris, using replicate chemostats under electron donor limitation. We observe clear and statistically robust changes in some key central MSR and C-metabolism enzymes, though a host of the critical energy-transfer enzymes show no statistically discernable change. We discuss these results in light of recent theoretical advances and their relevance to modern and ancient geochemical records.

ARSENIC MOBILIZATION FROM SEDIMENTS IN MICROCOSMS UNDER SULFATE REDUCTION

PubMed Central

Sun, Jing; Quicksall, Andrew N.; Chillrud, Steven N.; Mailloux, Brian J.; Bostick, Benjamin C.

2016-01-01

Arsenic is often assumed to be immobile in sulfidic environments. Here, laboratory-scale microcosms were conducted to investigate whether microbial sulfate reduction could control dissolved arsenic concentrations sufficiently for use in groundwater remediation. Sediments from the Vineland Superfund site and the Coeur d'Alene mining district were amended with different combination of lactate and sulfate and incubated for 30 to 40 days. In general, sulfate reduction in Vineland sediments resulted in transient and incomplete arsenic removal, or arsenic release from sediments. Sulfate reduction in the Coeur d'Alene sediments was more effective at removing arsenic from solution than the Vineland sediments, probably by arsenic substitution and adsorption within iron sulfides. X-ray absorption spectroscopy indicated that the Vineland sediments initially contained abundant reactive ferrihydrite, and underwent extensive sulfur cycling during incubation. As a result, arsenic in the Vineland sediments could not be effectively converted to immobile arsenic-bearing sulfides, but instead a part of the arsenic was probably converted to soluble thioarsenates. These results suggest that coupling between the iron and sulfur redox cycles must be fully understood for in situ arsenic immobilization by sulfate reduction to be successful. PMID:27037658

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Des Marais, David J.

1993-01-01

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works. We infer from the data the various sinks for O2 as well as the sources of carbon for primary production. Although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Oxygenic photosynthesis was the most important process of carbon fixation. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount.

Reconstructing metabolic pathways of a member of the genus Pelotomaculum suggesting its potential to oxidize benzene to carbon dioxide with direct reduction of sulfate.

PubMed

Dong, Xiyang; Dröge, Johannes; von Toerne, Christine; Marozava, Sviatlana; McHardy, Alice C; Meckenstock, Rainer U

2017-03-01

The enrichment culture BPL is able to degrade benzene with sulfate as electron acceptor and is dominated by an organism of the genus Pelotomaculum. Members of Pelotomaculum are usually known to be fermenters, undergoing syntrophy with anaerobic respiring microorganisms or methanogens. By using a metagenomic approach, we reconstructed a high-quality genome (∼2.97 Mbp, 99% completeness) for Pelotomaculum candidate BPL. The proteogenomic data suggested that (1) anaerobic benzene degradation was activated by a yet unknown mechanism for conversion of benzene to benzoyl-CoA; (2) the central benzoyl-CoA degradation pathway involved reductive dearomatization by a class II benzoyl-CoA reductase followed by hydrolytic ring cleavage and modified β-oxidation; (3) the oxidative acetyl-CoA pathway was utilized for complete oxidation to CO2. Interestingly, the genome of Pelotomaculum candidate BPL has all the genes for a complete sulfate reduction pathway including a similar electron transfer mechanism for dissimilatory sulfate reduction as in other Gram-positive sulfate-reducing bacteria. The proteome analysis revealed that the essential enzymes for sulfate reduction were all formed during growth with benzene. Thus, our data indicated that, besides its potential to anaerobically degrade benzene, Pelotomaculum candidate BPL is the first member of the genus that can perform sulfate reduction. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Sulfur and carbon isotope biogeochemistry of a rewetted brackish fen

NASA Astrophysics Data System (ADS)

Koebsch, Franziska; Gehre, Matthias; Winkel, Matthias; Koehler, Stefan; Koch, Marian; Jurasinski, Gerald; Spitzy, Alejandro; Liebner, Susanne; Sachs, Torsten; Schmiedinger, Iris; Kretzschmann, Lisett; Saborowski, Anke; Böttcher, Michael E.

2015-04-01

Coastal wetlands are at the interface between terrestrial freshwater and marine and exhibit very specific biogeochemical conditions. Intermittent sea water intrusion affects metabolic pathways, i. e. anaerobic carbon metabolism is progressively dominated by sulfate reduction with lower contribution of methanogenesis whilst methane production is increasingly shifted from acetoclastic to hydrogenotrophic. Due to expanding anthropogenic impact a large proportion of coastal ecosystems is degraded with severe implications for the biogeochemical processes. We use concentration patterns and stable isotope signatures of water, sulfate, dissolved carbonate, and methane (δ2H, δ13C, δ18O, δ34S) to investigate the S and C metabolic cycle in a rewetted fen close to the southern Baltic Sea border. Such studies are crucial to better predict dynamic ecosystem feedback to global change like organic matter (OM) decomposition or greenhouse gas emissions. Yet, little is known about the metabolic pathways in such environments. The study site is part of the TERENO Observatory "Northeastern German Lowlands' and measurements of methane emissions have run since 2009. High methane fluxes up to 800 mg m-2 hr-1 indicate that methanogenesis is the dominant C metabolism pathway despite of high sulfate concentrations (up to 37 mM). The presented data are part of a comprehensive biogeochemical investigation that we conducted in autumn 2014 and that comprises 4 pore water profiles and sediment samples within a transect of 300-1500 m distance to the Baltic Sea. Depth of organic layers ranged from 25 to 140 cm with high OM contents (up to 90 dwt.%). Sulfate/chloride ratios in the pore waters were lower than in the Baltic Sea for most sites and sediment depths indicated a substantial net sulfate loss. Sulfide concentrations were negligible at the top and increased parallel to the sulfate concentrations with depth to values of up to 0.3 mM. One pore water profiles situated 1150 m from the Baltic Sea coast line exhibited a significant excess of sulfate. Preliminary sulfur isotope analysis of pore water sulfate from a location nearest to this profile revealed an enrichment in 34S (24.9 to 41.8o ) in comparison to Baltic Sea sulfate (21o ). This confirms high degrees of net sulfate reduction. Considering the yet high sulfate concentrations we hypothesize that local processes might supply additional sulfate and that the sulfide produced from sulfate reduction might either be lost by upwards diffusion towards the atmosphere or converted into other S compounds such as pyrite or organic compounds. The isotopic signatures of methane (δ13C: -68 to -57o and δ2H: -133 to -157o respectively) indicated acetoclastic methanogenesis to be the most dominant methane production pathway. However, estimated fractionation factors are comparatively high (1.050-1.065). Enrichment of heavy 13C in methane at the top of the sediment was either caused by methane oxidation or variation in substrate availability (e. g. due to peat degradation). The interpretation of our data in the light of further results will provide deeper insights into metabolic pathways and possible interactions between both coupled element cycles for coastal ecosystems.

Comparison of heterogeneous photolytic reduction of Hg(II) in the coal fly ashes and synthetic aerosols

NASA Astrophysics Data System (ADS)

Tong, Yindong; Eichhorst, Terry; Olson, Michael R.; Rutter, Andrew P.; Shafer, Martin M.; Wang, Xuejun; Schauer, James J.

2014-03-01

In this study, we examined the heterogeneous reduction of Hg(II) on the coal fly ash samples and synthetic aerosols under different light conditions in a controlled laboratory reactor. Three types of coal fly ashes were studied: a high carbon fly ash from a stoker boiler, a low carbon/low sulfate fly ash from a pulverized coal combustor burning low sulfur coal, and a high sulfate fly ash from a pulverized coal combustor burning high sulfur coal. The rate of Hg(II) reduction on the three diverse fly ash samples was found to be relatively fast with an average half-life of 1.6 h under clear sky atmospheric conditions (under the irradiance of 1000 W/m2). The reduction rate in the low sulfate/low carbon fly ash was approximately 1.5 times faster than with the other coal fly ash samples. Synthetic aerosols made of carbon black and levoglucosan produced Hg(II) reduction rates similar to coal fly ashes. However, aerosols composed of adipic acid resulted in reduction rates that were 3-5 times faster. The sensitivity of adipic acid reduction to light source wavelength was found to be greater than for the coal fly ash and other synthetic aerosols. Aerosols made from the water extracts of coal fly ash samples produced reduction rates equal to or slightly higher than with the native fly ash suggesting that the soluble components of fly ash play a significant role in the reduction mechanism. The measured reduction rates are likely important in the chemical processing of mercury in power plant plumes and potentially in the atmosphere and should be considered for incorporation in atmospheric transport models that are used to understand the fate of atmospheric mercury.

Impact of Organic Carbon Electron Donors on Microbial Community Development under Iron- and Sulfate-Reducing Conditions

DOE PAGES

Kwon, Man Jae; O’Loughlin, Edward J.; Boyanov, Maxim I.; ...

2016-01-22

Although iron- and sulfate-reducing bacteria in subsurface environments have crucial roles in biogeochemical cycling of C, Fe, and S, how specific electron donors impact the compositional structure and activity of native iron- and/or sulfate-reducing communities is largely unknown. To understand this better, we created bicarbonate-buffered batch systems in duplicate with three different electron donors (acetate, lactate, or glucose) paired with ferrihydrite and sulfate as the electron acceptors and inoculated them with subsurface sediment as the microbial inoculum. Sulfate and ferrihydrite reduction occurred simultaneously and were faster with lactate than with acetate. 16S rRNA-based sequence analysis of the communities over timemore » revealed that Desulfotomaculum was the major driver for sulfate reduction coupled with propionate oxidation in lactate-amended incubations. The reduction of sulfate resulted in sulfide production and subsequent abiotic reduction of ferrihydrite. In contrast, glucose promoted faster reduction of ferrihydrite, but without reduction of sulfate. Interestingly, the glucose-amended incubations led to two different biogeochemical trajectories among replicate bottles that resulted in distinct coloration (white and brown). The two outcomes in geochemical evolution might be due to the stochastic evolution of the microbial communities or subtle differences in the initial composition of the fermenting microbial community and its development via the use of different glucose fermentation pathways available within the community. Synchrotron-based x-ray analysis indicated that siderite and amorphous Fe(II) were formed in the replicate bottles with glucose, while ferrous sulfide and vivianite were formed with lactate or acetate. As a result, these data sets reveal that use of different C utilization pathways projects significant changes in microbial community composition over time that uniquely impact both the geochemistry and mineralogy of subsurface environments.« less

Impact of Organic Carbon Electron Donors on Microbial Community Development under Iron- and Sulfate-Reducing Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwon, Man Jae; O’Loughlin, Edward J.; Boyanov, Maxim I.

Although iron- and sulfate-reducing bacteria in subsurface environments have crucial roles in biogeochemical cycling of C, Fe, and S, how specific electron donors impact the compositional structure and activity of native iron- and/or sulfate-reducing communities is largely unknown. To understand this better, we created bicarbonate-buffered batch systems in duplicate with three different electron donors (acetate, lactate, or glucose) paired with ferrihydrite and sulfate as the electron acceptors and inoculated them with subsurface sediment as the microbial inoculum. Sulfate and ferrihydrite reduction occurred simultaneously and were faster with lactate than with acetate. 16S rRNA-based sequence analysis of the communities over timemore » revealed that Desulfotomaculum was the major driver for sulfate reduction coupled with propionate oxidation in lactate-amended incubations. The reduction of sulfate resulted in sulfide production and subsequent abiotic reduction of ferrihydrite. In contrast, glucose promoted faster reduction of ferrihydrite, but without reduction of sulfate. Interestingly, the glucose-amended incubations led to two different biogeochemical trajectories among replicate bottles that resulted in distinct coloration (white and brown). The two outcomes in geochemical evolution might be due to the stochastic evolution of the microbial communities or subtle differences in the initial composition of the fermenting microbial community and its development via the use of different glucose fermentation pathways available within the community. Synchrotron-based x-ray analysis indicated that siderite and amorphous Fe(II) were formed in the replicate bottles with glucose, while ferrous sulfide and vivianite were formed with lactate or acetate. As a result, these data sets reveal that use of different C utilization pathways projects significant changes in microbial community composition over time that uniquely impact both the geochemistry and mineralogy of subsurface environments.« less

Impact of Organic Carbon Electron Donors on Microbial Community Development under Iron- and Sulfate-Reducing Conditions.

PubMed

Kwon, Man Jae; O'Loughlin, Edward J; Boyanov, Maxim I; Brulc, Jennifer M; Johnston, Eric R; Kemner, Kenneth M; Antonopoulos, Dionysios A

2016-01-01

Although iron- and sulfate-reducing bacteria in subsurface environments have crucial roles in biogeochemical cycling of C, Fe, and S, how specific electron donors impact the compositional structure and activity of native iron- and/or sulfate-reducing communities is largely unknown. To understand this better, we created bicarbonate-buffered batch systems in duplicate with three different electron donors (acetate, lactate, or glucose) paired with ferrihydrite and sulfate as the electron acceptors and inoculated them with subsurface sediment as the microbial inoculum. Sulfate and ferrihydrite reduction occurred simultaneously and were faster with lactate than with acetate. 16S rRNA-based sequence analysis of the communities over time revealed that Desulfotomaculum was the major driver for sulfate reduction coupled with propionate oxidation in lactate-amended incubations. The reduction of sulfate resulted in sulfide production and subsequent abiotic reduction of ferrihydrite. In contrast, glucose promoted faster reduction of ferrihydrite, but without reduction of sulfate. Interestingly, the glucose-amended incubations led to two different biogeochemical trajectories among replicate bottles that resulted in distinct coloration (white and brown). The two outcomes in geochemical evolution might be due to the stochastic evolution of the microbial communities or subtle differences in the initial composition of the fermenting microbial community and its development via the use of different glucose fermentation pathways available within the community. Synchrotron-based x-ray analysis indicated that siderite and amorphous Fe(II) were formed in the replicate bottles with glucose, while ferrous sulfide and vivianite were formed with lactate or acetate. These data sets reveal that use of different C utilization pathways projects significant changes in microbial community composition over time that uniquely impact both the geochemistry and mineralogy of subsurface environments.

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

NASA Astrophysics Data System (ADS)

Canfield, Donald E.; Des Marais, David J.

1993-08-01

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works located in Guerrero Negro, Baja California Sur, Mexico. Included in the budget are measured rates of O 2 production, sulfate reduction, and elemental exchange across the mat/brine interface, day and night, at various temperatures and times of the year. We infer from this data the various sinks for O 2, as well as the sources of carbon for primary production. To summarize, although seasonal variability exists, a major percentage of the O 2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O 2 that diffused into the mat was used to oxidize sulfide, with O 2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O 2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Also, oxygenic photosynthesis was the most important process of carbon fixation, although anoxygenic photosynthesis may have been important at low light levels during some times of the year. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount. These mats are thus closely coupled systems where rapid rates of photosynthesis both require and fuel rapid rates of heterotrophic carbon oxidation.

Optimization of the operation of packed bed bioreactor to improve the sulfate and metal removal from acid mine drainage.

PubMed

Dev, Subhabrata; Roy, Shantonu; Bhattacharya, Jayanta

2017-09-15

The present study discusses the potentiality of using anaerobic Packed Bed Bioreactor (PBR) for the treatment of acid mine drainage (AMD). The multiple process parameters such as pH, hydraulic retention time (HRT), concentration of marine waste extract (MWE), total organic carbon (TOC) and sulfate were optimized together using Taguchi design. The order of influence of the parameters towards biological sulfate reduction was found to be pH > MWE > sulfate > HRT > TOC. At optimized conditions (pH - 7, 20% (v/v) MWE, 1500 mg/L sulfate, 48 h HRT and 2300 mg/L TOC), 98.3% and 95% sulfate at a rate of 769.7 mg/L/d. and 732.1 mg/L/d. was removed from the AMD collected from coal and metal mine, respectively. Efficiency of metal removal (Fe, Cu, Zn, Mg and Ni) was in the range of 94-98%. The levels of contaminants in the treated effluent were below the minimum permissible limits of industrial discharge as proposed by Bureau of Indian Standards (IS 2490:1981). The present study establishes the optimized conditions for PBR operation to completely remove sulfate and metal removal from AMD at high rate. The study also creates the future scope to develop an efficient treatment process for sulfate and metal-rich mine wastewater in a large scale. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfate Reduction and Sulfide Biomineralization By Deep-Sea Hydrothermal Vent Microorganisms

NASA Astrophysics Data System (ADS)

Picard, A.; Gartman, A.; Clarke, D. R.; Girguis, P. R.

2014-12-01

Deep-sea hydrothermal vents are characterized by steep temperature and chemical gradients and moderate pressures. At these sites, mesophilic sulfate-reducing bacteria thrive, however their significance for the formation of sulfide minerals is unknown. In this study we investigated sulfate reduction and sulfide biomineralization by the deep-sea bacterium Desulfovibrio hydrothermalis isolated from a deep-sea vent chimney at the Grandbonum vent site (13°N, East Pacific Rise, 2600 m water depth) [1]. Sulfate reduction rates were determined as a function of pressure and temperature. Biomineralization of sulfide minerals in the presence of various metal concentrations was characterized using light and electron microscopy and optical spectroscopy. We seek to better understand the significance of biological sulfate reduction in deep-sea hydrothermal environments, to characterize the steps in sulfide mineral nucleation and growth, and identify the interactions between cells and minerals. [1] D. Alazard, S. Dukan, A. Urios, F. Verhe, N. Bouabida, F. Morel, P. Thomas, J.L. Garcia and B. Ollivier, Desulfovibrio hydrothermalis sp. nov., a novel sulfate-reducing bacterium isolated from hydrothermal vents, Int. J. Syst. Evol. Microbiol., 53 (2003) 173-178.

Bio-desulfurization and denitrification by anaerobic-anoxic process for the treatment of wastewater from flue gas washing.

PubMed

Song, Ziyu; Zhou, Xuemei; Li, Yuguang; Yang, Maohua; Xing, Jianmin

2013-01-01

For amine-based carbon dioxide capture, nitrogen oxides and sulfur oxides were the main pollutants that had a negative effect on the regeneration of solvent. Before carbon dioxide capture, the sulfur oxides in flue gas should be removed by the method of calcium salt, and then washed by alkaline solution to eliminate the residual nitrogen oxides and sulfur oxides. The washing wastewater containing sulfate and nitrate needs to be treated. In this study, a novel anaerobic-anoxic process was built up for the treatment of this washing wastewater. Nitrate was reduced to nitrogen by denitrifying bacteria. Sulfate was firstly reduced to sulfide by sulfate reducing bacteria, and then selectively oxidized to element sulfur by sulfide oxidizing bacteria. The treated liquid could be reused as absorption after the adjustment of pH value. The performances of this bioprocess were investigated under various pH values and S/N ratios. It was found that the optimal pH value of influent was 6.0, the percentages of denitrification and sulfate reducing could reach 90 and 89%, respectively. Seventy-six percent of sulfate was transformed into element sulfur. Nitrate significantly had a negative effect on sulfate reduction above 10 mM. As 20 mM nitrate, the sulfate reducing percentage would drop to 67%. These results showed that the anaerobic-anoxic process was feasible for the treatment of flue gas washing wastewater. It would be prospectively applied to other wastewater with the higher ratio of SO4(2-)/NO3(-).

Sulfide‐ and nitrite‐dependent nitric oxide production in the intestinal tract

PubMed Central

Vermeiren, Joan; Van de Wiele, Tom; Van Nieuwenhuyse, Glynn; Boeckx, Pascal; Verstraete, Willy; Boon, Nico

2012-01-01

Summary In the gut ecosystem, nitric oxide (NO) has been described to have damaging effects on the energy metabolism of colonocytes. Described mechanisms of NO production are microbial reduction of nitrate via nitrite to NO and conversion of l‐arginine by NO synthase. The aim of this study was to investigate whether dietary compounds can stimulate the production of NO by representative cultures of the human intestinal microbiota and whether this correlates to other processes in the intestinal tract. We have found that the addition of a reduced sulfur compound, i.e. cysteine, contributed to NO formation. This increase was ascribed to higher sulfide concentrations generated from cysteine that in turn promoted the chemical conversion of nitrite to NO. The NO release from nitrite was of the order of 4‰ at most. Overall, it was shown that two independent biological processes contribute to the chemical formation of NO in the intestinal tract: (i) the production of sulfide by fermentation of sulfur containing amino acids or reduction of sulfate by sulfate reducing bacteria, and (ii) the reduction of nitrate to nitrite. Our results indicate that dietary thiol compounds in combination with nitrate may contribute to colonocytes damaging processes by promoting NO formation. PMID:22129449

A large column analog experiment of stable isotope variations during reactive transport: I. A comprehensive model of sulfur cycling and δ34S fractionation

NASA Astrophysics Data System (ADS)

Druhan, Jennifer L.; Steefel, Carl I.; Conrad, Mark E.; DePaolo, Donald J.

2014-01-01

This study demonstrates a mechanistic incorporation of the stable isotopes of sulfur within the CrunchFlow reactive transport code to model the range of microbially-mediated redox processes affecting kinetic isotope fractionation. Previous numerical models of microbially mediated sulfate reduction using Monod-type rate expressions have lacked rigorous coupling of individual sulfur isotopologue rates, with the result that they cannot accurately simulate sulfur isotope fractionation over a wide range of substrate concentrations using a constant fractionation factor. Here, we derive a modified version of the dual-Monod or Michaelis-Menten formulation (Maggi and Riley, 2009, 2010) that successfully captures the behavior of the 32S and 34S isotopes over a broad range from high sulfate and organic carbon availability to substrate limitation using a constant fractionation factor. The new model developments are used to simulate a large-scale column study designed to replicate field scale conditions of an organic carbon (acetate) amended biostimulation experiment at the Old Rifle site in western Colorado. Results demonstrate an initial period of iron reduction that transitions to sulfate reduction, in agreement with field-scale behavior observed at the Old Rifle site. At the height of sulfate reduction, effluent sulfate concentrations decreased to 0.5 mM from an influent value of 8.8 mM over the 100 cm flow path, and thus were enriched in sulfate δ34S from 6.3‰ to 39.5‰. The reactive transport model accurately reproduced the measured enrichment in δ34S of both the reactant (sulfate) and product (sulfide) species of the reduction reaction using a single fractionation factor of 0.987 obtained independently from field-scale measurements. The model also accurately simulated the accumulation and δ34S signature of solid phase elemental sulfur over the duration of the experiment, providing a new tool to predict the isotopic signatures associated with reduced mineral pools. To our knowledge, this is the first rigorous treatment of sulfur isotope fractionation subject to Monod kinetics in a mechanistic reactive transport model that considers the isotopic spatial distribution of both dissolved and solid phase sulfur species during microbially-mediated sulfate reduction. describe the design and results of the large-scale column experiment; demonstrate incorporation of the stable isotopes of sulfur in a dual-Monod kinetic expression such that fractionation is accurately modeled at both high and low substrate availability; verify accurate simulation of the chemical and isotopic gradients in reactant and product sulfur species using a kinetic fractionation factor obtained from field-scale analysis (Druhan et al., 2012); utilize the model to predict the final δ34S values of secondary sulfur minerals accumulated in the sediment over the course of the experiment. The development of rigorous isotope-specific Monod-type rate expressions are presented here in application to sulfur cycling during amended biostimulation, but are readily applicable to a variety of stable isotope systems associated with both steady state and transient biogenic redox environments. In other words, the association of this model with a uranium remediation experiment does not limit its applicability to more general redox systems. Furthermore, the ability of this model treatment to predict the isotopic composition of secondary minerals accumulated as a result of fractionating processes (item 4) offers an important means of interpreting solid phase isotopic compositions and tracking long-term stability of precipitates.

Desulfohalophilus alkaliarsenatis gen. nov., sp. nov., an extremely halophilic sulfate- and arsenate-respiring bacterium from Searles Lake, California

USGS Publications Warehouse

Blum, Jodi Switzer; Kulp, Thomas R.; Han, Sukkyun; Lanoil, Brian; Saltikov, Chad W.; Stolz, John F.; Miller, Laurence G.; Oremland, Ronald S.

2012-01-01

A haloalkaliphilic sulfate-respiring bacterium, strain SLSR-1, was isolated from a lactate-fed stable enrichment culture originally obtained from the extreme environment of Searles Lake, California. The isolate proved capable of growth via sulfate-reduction over a broad range of salinities (125–330 g/L), although growth was slowest at salt-saturation. Strain SLSR-1 was also capable of growth via dissimilatory arsenate-reduction and displayed an even broader range of salinity tolerance (50–330 g/L) when grown under these conditions. Strain SLSR-1 could also grow via dissimilatory nitrate reduction to ammonia. Growth experiments in the presence of high borate concentrations indicated a greater sensitivity of sulfate-reduction than arsenate-respiration to this naturally abundant anion in Searles Lake. Strain SLSR-1 contained genes involved in both sulfate-reduction (dsrAB) and arsenate respiration (arrA). Amplicons of 16S rRNA gene sequences obtained from DNA extracted from Searles Lake sediment revealed the presence of close relatives of strain SLSR-1 as part of the flora of this ecosystem despite the fact that sulfate-reduction activity could not be detected in situ. We conclude that strain SLSR-1 can only achieve growth via arsenate-reduction under the current chemical conditions prevalent at Searles Lake. Strain SLSR-1 is a deltaproteobacterium in the family Desulfohalobiacea of anaerobic, haloalkaliphilic bacteria, for which we propose the name Desulfohalophilus alkaliarsenatis gen. nov., sp. nov.

Volumetric determination of uranium titanous sulfate as reductant before oxidimetric titration

USGS Publications Warehouse

Wahlberg, J.S.; Skinner, D.L.; Rader, L.F.

1957-01-01

Need for a more rapid volumetric method for the routine determination of uranium in uranium-rich materials has led to the development of a method that uses titanous sulfate as a reductant before oxidimetric titration. Separation of the hydrogen sulfide group is not necessary. Interfering elements precipitated by cupferron are removed by automatic filtrations made simultaneously rather than by the longer chloroform extraction method. Uranium is reduced from VI to IV by addition of an excess of titanous sulfate solution, cupric ion serving as an indicator by forming red metallic copper when reduction is complete. The copper is reoxidized by addition of mercuric perchlorate. The reduced uranium is then determined by addition of excess ferric sulfate and titration with ceric sulfate. The method has proved to be rapid, accurate, and economical.

Pathways of organic carbon oxidation in three continental margin sediments

NASA Technical Reports Server (NTRS)

Canfield, D. E.; Jorgensen, B. B.; Fossing, H.; Glud, R.; Gundersen, J.; Ramsing, N. B.; Thamdrup, B.; Hansen, J. W.; Nielsen, L. P.; Hall, P. O.

1993-01-01

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

Reduction of uranium by Desulfovibrio desulfuricans

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1992-01-01

The possibility that sulfate-reducing microorganisms contribute to U(VI) reduction in sedimentary environments was investigated. U(VI) was reduced to U(IV) when washed cells of sulfate-grown Desulfovibrio desulfuricans were suspended in a bicarbonate buffer with lactate or H2 as the electron donor. There was no U(VI) reduction in the absence of an electron donor or when the cells were killed by heat prior to the incubation. The rates of U(VI) reduction were comparable to those in respiratory Fe(III)-reducing microorganisms. Azide or prior exposure of the cells to air did not affect the ability of D. desulfuricans to reduce U(VI). Attempts to grow D. desulfuricans with U(VI) as the electron acceptor were unsuccessful. U(VI) reduction resulted in the extracellular precipitation of the U(IV) mineral uraninite. The presence of sulfate had no effect on the rate of U(VI) reduction. Sulfate and U(VI) were reduced simultaneously. Enzymatic reduction of U(VI) by D. desulfuricans was much faster than nonenzymatic reduction of U(VI) by sulfide, even when cells of D. desulfuricans were added to provide a potential catalytic surface for the nonenzymatic reaction. The results indicate that enzymatic U(VI) reduction by sulfate-reducing microorganisms may be responsible for the accumulation of U(IV) in sulfidogenic environments. Furthermore, since the reduction of U(VI) to U(IV) precipitates uranium from solution, D. desulfuricans might be a useful organisms for recovering uranium from contaminated waters and waste streams.

Extremely high sulfate reduction, sediment oxygen demand and benthic nutrient flux associated with a large-scale artificial dyke and its implication to benthic-pelagic coupling in the Yeongsan River estuary, Yellow Sea.

PubMed

Kim, Sung-Han; Lee, Jae Seong; Hyun, Jung-Ho

2017-07-15

We investigated environmental impact of large-scale dyke on the sediment geochemistry, sulfate reduction rates (SRRs), sediment oxygen demand (SOD) and potential contribution of benthic nutrient flux (BNF) to primary production in the Yeongsan River estuary, Yellow Sea. The sediment near the dyke (YE1) with high organic carbon (C org ) content (>4%, dry wt.) was characterized by extremely high SOD (327mmolm -2 d -1 ) and SRRs (91-140mmolm -2 d -1 ). The sulfate reduction accounted for 73% of C org oxidation, and was responsible for strikingly high concentrations of NH 4 + (7.7mM), PO 4 3- (67μM) and HS - (487μM) in pore water. The BNF at YE1 accounted for approximately 200% of N and P required for primary production in the water column. The results present one of the most extreme cases that the construction of an artificial dyke may have profound impacts on the biogeochemical and ecological processes in coastal ecosystems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation Processes and Impacts of Reactive and Nonreactive Minerals in Permeable Reactive Barriers

EPA Science Inventory

Mineral precipitates in zero-valent iron PRBs can be classified by formation processes into three groups: 1) those that result from changes in chemical conditions (i.e., changes in pH, e.g., calcite); 2) those that are a consequence of microbial activity (i.e., sulfate reduction,...

FORMATION PROCESSES AND CONSEQUENCES OF REACTIVE AND NON-REACTIVE MINERAL PRECIPITATES IN PERMEABLE REACTIVE BARRIERS

EPA Science Inventory

Mineral precipitates in zero-valent iron PRBs can be classified by formation processes into three groups: 1) those that result from changes in chemical conditions (i.e., change in pH, e.g., calcite); 2) those that are a consequence of microbial activity (i.e., sulfate reduction, ...

Artificial electron acceptors decouple archaeal methane oxidation from sulfate reduction.

PubMed

Scheller, Silvan; Yu, Hang; Chadwick, Grayson L; McGlynn, Shawn E; Orphan, Victoria J

2016-02-12

The oxidation of methane with sulfate is an important microbial metabolism in the global carbon cycle. In marine methane seeps, this process is mediated by consortia of anaerobic methanotrophic archaea (ANME) that live in syntrophy with sulfate-reducing bacteria (SRB). The underlying interdependencies within this uncultured symbiotic partnership are poorly understood. We used a combination of rate measurements and single-cell stable isotope probing to demonstrate that ANME in deep-sea sediments can be catabolically and anabolically decoupled from their syntrophic SRB partners using soluble artificial oxidants. The ANME still sustain high rates of methane oxidation in the absence of sulfate as the terminal oxidant, lending support to the hypothesis that interspecies extracellular electron transfer is the syntrophic mechanism for the anaerobic oxidation of methane. Copyright © 2016, American Association for the Advancement of Science.

Dynamic characteristics of sulfur, iron and phosphorus in coastal polluted sediments, north China.

PubMed

Sun, Qiyao; Sheng, Yanqing; Yang, Jian; Di Bonito, Marcello; Mortimer, Robert J G

2016-12-01

The cycling of sulfur (S), iron (Fe) and phosphorus (P) in sediments and pore water can impact the water quality of overlying water. In a heavily polluted river estuary (Yantai, China), vertical profiles of fluxes of dissolved sulfide, Fe 2+ and dissolved reactive phosphorus (DRP) in sediment pore water were investigated by the Diffusive Gradients in Thin films technique (DGT). Vertical fluxes of S, Fe, P in intertidal sediment showed the availability of DRP increased while the sulfide decreased with depth in surface sediment, indicating that sulfide accumulation could enhance P release in anoxic sediment. In sites with contrasting salinity, the relative dominance of iron and sulfate reduction was different, with iron reduction dominant over sulfate reduction in the upper sediment at an intertidal site but the reverse true in a freshwater site, with the other process dominating at depth in each case. Phosphate release was largely controlled by iron reduction. Copyright © 2016 Elsevier Ltd. All rights reserved.

Microbial community functional structure in response to micro-aerobic conditions in sulfate-reducing sulfur-producing bioreactor.

PubMed

Yu, Hao; Chen, Chuan; Ma, Jincai; Xu, Xijun; Fan, Ronggui; Wang, Aijie

2014-05-01

Limited oxygen supply to anaerobic wastewater treatment systems had been demonstrated as an effective strategy to improve elemental sulfur (S(0)) recovery, coupling sulfate reduction and sulfide oxidation. However, little is known about the impact of dissolved oxygen (DO) on the microbial functional structures in these systems. We used a high throughput tool (GeoChip) to evaluate the microbial community structures in a biological desulfurization reactor under micro-aerobic conditions (DO: 0.02-0.33 mg/L). The results indicated that the microbial community functional compositions and structures were dramatically altered with elevated DO levels. The abundances of dsrA/B genes involved in sulfate reduction processes significantly decreased (p < 0.05, LSD test) at relatively high DO concentration (DO: 0.33 mg/L). The abundances of sox and fccA/B genes involved in sulfur/sulfide oxidation processes significantly increased (p < 0.05, LSD test) in low DO concentration conditions (DO: 0.09 mg/L) and then gradually decreased with continuously elevated DO levels. Their abundances coincided with the change of sulfate removal efficiencies and elemental sulfur (S(0)) conversion efficiencies in the bioreactor. In addition, the abundance of carbon degradation genes increased with the raising of DO levels, showing that the heterotrophic microorganisms (e.g., fermentative microorganisms) were thriving under micro-aerobic condition. This study provides new insights into the impacts of micro-aerobic conditions on the microbial functional structure of sulfate-reducing sulfur-producing bioreactors, and revealed the potential linkage between functional microbial communities and reactor performance. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Sulfide Generated by Sulfate Reduction is a Primary Controller of the Occurrence of Wild Rice (Zizania palustris) in Shallow Aquatic Ecosystems

NASA Astrophysics Data System (ADS)

Myrbo, A.; Swain, E. B.; Engstrom, D. R.; Coleman Wasik, J.; Brenner, J.; Dykhuizen Shore, M.; Peters, E. B.; Blaha, G.

2017-11-01

Field observations suggest that surface water sulfate concentrations control the distribution of wild rice, an aquatic grass (Zizania palustris). However, hydroponic studies show that sulfate is not toxic to wild rice at even unrealistically high concentrations. To determine how sulfate might directly or indirectly affect wild rice, potential wild rice habitat was characterized for 64 chemical and physical variables in over 100 sites spanning a relatively steep climatic and geological gradient in Minnesota. Habitat suitability was assessed by comparing the occurrence of wild rice with the field variables, through binary logistic regression. This analysis demonstrated that sulfide in sediment pore water, generated by the microbial reduction of sulfate that diffuses or advects into the sediment, is the primary control of wild rice occurrence. Water temperature and water transparency independently control the suitability of habitat for wild rice. In addition to generating phytotoxic sulfide, sulfate reduction also supports anaerobic decomposition of organic matter, releasing nutrients that can compound the harm of direct sulfide toxicity. These results are important because they show that increases in sulfate loading to surface water can have multiple negative consequences for ecosystems, even though sulfate itself is relatively benign.

Kinetics of sulfate reduction and sulfide precipitation rates in sediments of a bar-built estuary (Pescadero, California).

PubMed

Richards, Chandra M; Pallud, Céline

2016-05-01

The bar-built Pescadero Estuary in Northern California is a major fish rearing habitat, though recently threatened by near-annual fish kill events, which occur when the estuary transitions from closed to open state. The direct and indirect effects of hydrogen sulfide are suspected to play a role in these mortalities, but the spatial variability of hydrogen sulfide production and its link to fish kills remains poorly understood. Using flow-through reactors containing intact littoral sediment slices, we measured potential sulfate reduction rates, kinetic parameters of microbial sulfate reduction (Rmax, the maximum sulfate reduction rate, and Km, the half-saturation constant for sulfate), potential sulfide precipitation rates, and potential hydrogen sulfide export rates to water at four sites in the closed and open states. At all sites, the Michaelis-Menten kinetic rate equation adequately describes the utilization of sulfate by the complex resident microbial communities. We estimate that 94-96% of hydrogen sulfide produced through sulfate reduction precipitates in the sediment and that only 4-6% is exported to water, suggesting that elevated sulfide concentrations in water, which would affect fish through toxicity and oxygen consumption, cannot be responsible for fish deaths. However, the indirect effects of sulfide precipitates, which chemically deplete, contaminate, and acidify the water column during sediment re-suspension and re-oxidation in the transition from closed to open state, can be implicated in fish mortalities at Pescadero Estuary. Published by Elsevier Ltd.

Microbial Response to Experimentally Controlled Redox Transitions at the Sediment Water Interface.

PubMed

Frindte, Katharina; Allgaier, Martin; Grossart, Hans-Peter; Eckert, Werner

2015-01-01

The sediment-water interface of freshwater lakes is characterized by sharp chemical gradients, shaped by the interplay between physical, chemical and microbial processes. As dissolved oxygen is depleted in the uppermost sediment, the availability of alternative electron acceptors, e.g. nitrate and sulfate, becomes the limiting factor. We performed a time series experiment in a mesocosm to simulate the transition from aerobic to anaerobic conditions at the sediment-water interface. Our goal was to identify changes in the microbial activity due to redox transitions induced by successive depletion of available electron acceptors. Monitoring critical hydrochemical parameters in the overlying water in conjunction with a new sampling strategy for sediment bacteria enabled us to correlate redox changes in the water to shifts in the active microbial community and the expression of functional genes representing specific redox-dependent microbial processes. Our results show that during several transitions from oxic-heterotrophic condition to sulfate-reducing condition, nitrate-availability and the on-set of sulfate reduction strongly affected the corresponding functional gene expression. There was evidence of anaerobic methane oxidation with NOx. DGGE analysis revealed redox-related changes in microbial activity and expression of functional genes involved in sulfate and nitrite reduction, whereas methanogenesis and methanotrophy showed only minor changes during redox transitions. The combination of high-frequency chemical measurements and molecular methods provide new insights into the temporal dynamics of the interplay between microbial activity and specific redox transitions at the sediment-water interface.

Desulfobacter psychrotolerans sp. nov., a new psychrotolerant sulfate-reducing bacterium and descriptions of its physiological response to temperature changes.

PubMed

Tarpgaard, Irene H; Boetius, Antje; Finster, Kai

2006-01-01

A psychrotrolerant acetate-oxidizing sulfate-reducing bacterium (strain akvb(T)) was isolated from sediment from the northern part of The North Sea with annual temperature fluctuations between 8 and 14 degrees C. Of the various substrates tested, strain akvb(T) grew exclusively by the oxidation of acetate coupled to the reduction of sulfate. The cells were motile, thick rods with round ends and grew in dense aggregates. Strain akvb(T) grew at temperatures ranging from -3.6 to 26.3 degrees C. Optimal growth was observed at 20 degrees C. The highest cell specific sulfate reduction rate of 6.2 fmol cell(-1) d(-1) determined by the (35)SO(2-)(40) method was measured at 26 degrees C. The temperature range of short-term sulfate reduction rates exceeded the temperature range of growth by 5 degrees C. The Arrhenius relationship for the temperature dependence of growth and sulfate reduction was linear, with two distinct slopes below the optimum temperatures of both processes. The critical temperature was 6.4 degrees C. The highest growth yield (4.3-4.5 g dry weight mol(-1) acetate) was determined at temperatures between 5 and 15 degrees C. The cellular fatty acid composition was determined with cultures grown at 4 and 20 degrees C, respectively. The relative proportion of cellular unsaturated fatty acids (e.g. 16:1omega7c) was higher in cells grown at 4 degrees C than in cells grown at 20 degrees C. The physiological responses to temperature changes showed that strain akvb(T) was well adapted to the temperature regime of the environment from which it was isolated. Phylogenetic analysis showed that strain akvb(T) is closest related to Desulfobacter hydrogenophilus, with a 16S rRNA gene sequence similarity of 98.6%. DNA-DNA-hybridization showed a similarity of 32% between D. hydrogenophilus and strain akvb(T). Based on phenotypic and DNA-based characteristics we propose that strain akvb(T) is a member of a new species, Desulfobacter psychrotolerans sp. nov.

Effect of increasing dietary fiber on plasma levels of colon-derived solutes in hemodialysis patients.

PubMed

Sirich, Tammy L; Plummer, Natalie S; Gardner, Christopher D; Hostetter, Thomas H; Meyer, Timothy W

2014-09-05

Numerous uremic solutes are derived from the action of colon microbes. Two such solutes, indoxyl sulfate and p-cresol sulfate, have been associated with adverse outcomes in renal failure. This study tested whether increasing dietary fiber in the form of resistant starch would lower the plasma levels of these solutes in patients on hemodialysis. Fifty-six patients on maintenance hemodialysis were randomly assigned to receive supplements containing resistant starch (n=28) or control starch (n=28) daily for 6 weeks in a study conducted between October 2010 and May 2013. Of these, 40 patients (20 in each group) completed the study and were included in the final analysis. Plasma indoxyl sulfate and p-cresol sulfate levels were measured at baseline and week 6. Increasing dietary fiber for 6 weeks significantly reduced the unbound, free plasma level of indoxyl sulfate (median -29% [25th percentile, 75th percentile, -56, -12] for fiber versus -0.4% [-20, 34] for control, P=0.02). The reduction in free plasma levels of indoxyl sulfate was accompanied by a reduction in free plasma levels of p-cresol sulfate (r=0.81, P<0.001). However, the reduction of p-cresol sulfate levels was of lesser magnitude and did not achieve significance (median -28% [-46, 5] for fiber versus 4% [-28, 36] for control, P=0.05). Increasing dietary fiber in hemodialysis patients may reduce the plasma levels of the colon-derived solutes indoxyl sulfate and possibly p-cresol sulfate without the need to intensify dialysis treatments. Further studies are required to determine whether such reduction provides clinical benefits. Copyright © 2014 by the American Society of Nephrology.

Freshwater wetland sediments support substantial rates of anaerobic oxidation of methane (AOM)

NASA Astrophysics Data System (ADS)

Segarra, K. E.; Samarkin, V.; Schubotz, F.; Yoshinaga, M. Y.; Hinrichs, K.; Joye, S. B.

2012-12-01

Freshwater wetlands are characterized by high rates of methanogenesis and are the single largest source of atmospheric methane. Anaerobic oxidation of methane (AOM), a previously underappreciated process in these systems, may be an important component in freshwater methane budgets. Here we report some of the first direct measurements of AOM in wetland sediments. We examined seasonal methane cycling within three freshwater wetlands (two peat wetlands and one tidal, freshwater creekbank) along the eastern coast of the US. Rates of AOM were high (up to 286 nmol per cubic cm per day) and varied on a seasonal basis. Despite low sulfate concentrations, rates of sulfate reduction were sufficient to support all the observed AOM activity, though rates of these two processes were not correlated. This study highlights the importance of AOM in freshwater sediments, where this process, in conjunction with sulfate reduction, may control emissions of methane to the atmosphere through competitive interactions with methanogens and the consumption of large fractions of the methane produced from acetate and hydrogen. The zone of maximum AOM activity was marked by enriched stable carbon isotopic signatures (δ13C) of methane and depleted signatures of DIC. However, the δ13C of archaeal and bacterial lipids were not indicative of methanotrophy. Studies that evaluate the role of AOM in wetlands using lipid and isotope-based approaches may therefore underestimate its importance.

Insight into the molecular mechanism of the sulfur oxidation process by reverse sulfite reductase (rSiR) from sulfur oxidizer Allochromatium vinosum.

PubMed

Ghosh, Semanti; Bagchi, Angshuman

2018-04-26

Sulfur metabolism is one of the oldest known biochemical processes. Chemotrophic or phototrophic proteobacteria, through the dissimilatory pathway, use sulfate, sulfide, sulfite, thiosulfate or elementary sulfur by either reductive or oxidative mechanisms. During anoxygenic photosynthesis, anaerobic sulfur oxidizer Allochromatium vinosum forms sulfur globules that are further oxidized by dsr operon. One of the key redox enzymes in reductive or oxidative sulfur metabolic pathways is the DsrAB protein complex. However, there are practically no reports to elucidate the molecular mechanism of the sulfur oxidation process by the DsrAB protein complex from sulfur oxidizer Allochromatium vinosum. In the present context, we tried to analyze the structural details of the DsrAB protein complex from sulfur oxidizer Allochromatium vinosum by molecular dynamics simulations. The molecular dynamics simulation results revealed the various types of molecular interactions between DsrA and DsrB proteins during the formation of DsrAB protein complex. We, for the first time, predicted the mode of binding interactions between the co-factor and DsrAB protein complex from Allochromatium vinosum. We also compared the binding interfaces of DsrAB from sulfur oxidizer Allochromatium vinosum and sulfate reducer Desulfovibrio vulgaris. This study is the first to provide a comparative aspect of binding modes of sulfur oxidizer Allochromatium vinosum and sulfate reducer Desulfovibrio vulgaris.

Processes controlling the fate of chloroethenes emanating from DNAPL aged sources in river-aquifer contexts.

PubMed

Puigserver, Diana; Cortés, Amparo; Viladevall, Manuel; Nogueras, Xènia; Parker, Beth L; Carmona, José M

2014-11-01

This work dealt with the physical and biogeochemical processes that favored the natural attenuation of chloroethene plumes of aged sources located close to influent rivers in the presence of co-contaminants, such as nitrate and sulfate. Two working hypotheses were proposed: i) Reductive dechlorination is increased in areas where the river-aquifer relationship results in the groundwater dilution of electron acceptors, the reduction potential of which exceeds that of specific chloroethenes; ii) zones where silts predominate or where textural changes occur are zones in which biodegradation preferentially takes place. A field site on a Quaternary alluvial aquifer at Torelló, Catalonia (Spain) was selected to validate these hypotheses. This aquifer is adjacent to an influent river, and its redox conditions favor reductive dechlorination. The main findings showed that the low concentrations of nitrate and sulfate due to dilution caused by the input of surface water diminish the competition for electrons between microorganisms that reduce co-contaminants and chloroethenes. Under these conditions, the most bioavailable electron acceptors were PCE and metabolites, which meant that their biodegradation was favored. This led to the possibility of devising remediation strategies based on bioenhancing natural attenuation. The artificial recharge with water that is low in nitrates and sulfates may favor dechlorinating microorganisms if the redox conditions in the mixing water are sufficiently maintained as reducing and if there are nutrients, electron donors and carbon sources necessary for these microorganisms. Copyright © 2014 Elsevier B.V. All rights reserved.

Immobilization of cobalt by sulfate-reducing bacteria in subsurface sediments

USGS Publications Warehouse

Krumholz, Lee R.; Elias, Dwayne A.; Suflita, Joseph M.

2003-01-01

We investigated the impact of sulfate-reduction on immobilization of metals in subsurface aquifers. Co 2+ was used as a model for heavy metals. Factors limiting sulfate-reduction dependent Co 2+ immobilization were tested on pure cultures of sulfate-reducing bacteria, and in sediment columns from a landfill leachate contaminated aquifer. In the presence of 1 mM Co 2+ , the growth of pure cultures of sulfate-reducing bacteria was not impacted. Cultures of Desulfovibrio desulfuricans, Desulfotomaculum gibsoniae , and Desulfomicrobium hypogeia removed greater than 99.99% of the soluble Co 2+ when CoCl 2 was used with no chelators. The above cultures and Desulfoarcula baarsi removed 98-99.94% of the soluble Co(II) when the metal was complexed with the model ligand nitrilotriacetate (Co-NTA). Factors controlling the rate of sulfate-reduction based Co 2+ precipitation were investigated in sediment-cobalt mixtures. Several electron donors were tested and all but toluene accelerated soluble Co 2+ loss. Ethanol and formate showed the greatest stimulation. All complex nitrogen sources tested slowed and decreased the extent of Co 2+ removal from solution relative to formate-amended sediment incubations. A range of pH values were tested (6.35-7.81), with the more alkaline incubations exhibiting the largest precipitation of Co 2+ . The immobilization of Co 2+ in sediments was also investigated with cores to monitor the flow of Co 2+ through undisturbed sediments. An increase in the amount of Co 2+ immobilized as CoS was observed as sulfate reduction activity was stimulated in flow through columns. Both pure culture and sediment incubation data indicate that stimulation of sulfate reduction is a viable strategy in the immobilization of contaminating metals in subsurface systems.

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium

USGS Publications Warehouse

Liu, D.; Dong, H.; Bishop, M.E.; Zhang, Jiahua; Wang, Hongfang; Xie, S.; Wang, Shaoming; Huang, L.; Eberl, D.D.

2012-01-01

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. ?? 2011 Blackwell Publishing Ltd.

Simultaneous chromate and sulfate removal by Streptomyces sp. MC1. Changes in intracellular protein profile induced by Cr(VI).

PubMed

Bonilla, José Oscar; Callegari, Eduardo Alberto; Delfini, Claudio Daniel; Estevez, María Cristina; Villegas, Liliana Beatriz

2016-11-01

The purpose of this study was to investigate the influence of increasing sulfate concentrations on chromium removal, to evaluate the effect of the presence of Cr(VI) on sulfate removal by Streptomyces sp. MC1 and to analyze the differential protein expression profile in the presence of this metal for the identification of proteins repressed or overexpressed. In the presence of Cr(VI) but in the absence of sulfate ions, bacterial growth was negligible, showing the Cr(VI) toxicity for this bacterium. However, the sulfate presence stimulated bacterium growth and Cr(VI) removal, regardless of its concentrations. Streptomyces sp. MC1 showed ability to remove chromium and sulfate simultaneously. Also, the sulfate presence favored the decrease of total chromium concentration from supernatants reaching a decrease of 50% at 48 h. In presence of chromium, seven proteins were down-expressed and showed homology to proteins involved in protein biosynthesis, energy production and free radicals detoxification while two proteins involved in oxidation-reduction processes identified as dihydrolipoamide dehydrogenase and S-adenosyl-l-methionine synthase were overexpressed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methane related changes in prokaryotic activity along geochemical profiles in sediments of Lake Kinneret (Israel)

NASA Astrophysics Data System (ADS)

Bar Or, I.; Ben-Dov, E.; Kushmaro, A.; Eckert, W.; Sivan, O.

2014-06-01

Microbial methane oxidation process (methanotrophy) is the primary control on the emission of the greenhouse gas methane (CH4) to the atmosphere. In terrestrial environments, aerobic methanotrophic bacteria are mainly responsible for oxidizing the methane. In marine sediments the coupling of the anaerobic oxidation of methane (AOM) with sulfate reduction, often by a consortium of anaerobic methanotrophic archaea (ANME) and sulfate reducing bacteria, was found to consume almost all the upward diffusing methane. Recently, we showed geochemical evidence for AOM driven by iron reduction in Lake Kinneret (LK) (Israel) deep sediments and suggested that this process can be an important global methane sink. The goal of the present study was to link the geochemical gradients found in the porewater (chemical and isotope profiles) with possible changes in microbial community structure. Specifically, we examined the possible shift in the microbial community in the deep iron-driven AOM zone and its similarity to known sulfate driven AOM populations. Screening of archaeal 16S rRNA gene sequences revealed Thaumarchaeota and Euryarchaeota as the dominant phyla in the sediment. Thaumarchaeota, which belongs to the family of copper containing membrane-bound monooxgenases, increased with depth while Euryarchaeota decreased. This may indicate the involvement of Thaumarchaeota, which were discovered to be ammonia oxidizers but whose activity could also be linked to methane, in AOM in the deep sediment. ANMEs sequences were not found in the clone libraries, suggesting that iron-driven AOM is not through sulfate. Bacterial 16S rRNA sequences displayed shifts in community diversity with depth. Proteobacteria and Chloroflexi increased with depth, which could be connected with their different dissimilatory anaerobic processes. The observed changes in microbial community structure suggest possible direct and indirect mechanisms for iron-driven AOM in deep sediments.

Zero valent iron simultaneously enhances methane production and sulfate reduction in anaerobic granular sludge reactors.

PubMed

Liu, Yiwen; Zhang, Yaobin; Ni, Bing-Jie

2015-05-15

Zero valent iron (ZVI) packed anaerobic granular sludge reactors have been developed for improved anaerobic wastewater treatment. In this work, a mathematical model is developed to describe the enhanced methane production and sulfate reduction in anaerobic granular sludge reactors with the addition of ZVI. The model is successfully calibrated and validated using long-term experimental data sets from two independent ZVI-enhanced anaerobic granular sludge reactors with different operational conditions. The model satisfactorily describes the chemical oxygen demand (COD) removal, sulfate reduction and methane production data from both systems. Results show ZVI directly promotes propionate degradation and methanogenesis to enhance methane production. Simultaneously, ZVI alleviates the inhibition of un-dissociated H2S on acetogens, methanogens and sulfate reducing bacteria (SRB) through buffering pH (Fe(0) + 2H(+) = Fe(2+) + H2) and iron sulfide precipitation, which improve the sulfate reduction capacity, especially under deterioration conditions. In addition, the enhancement of ZVI on methane production and sulfate reduction occurs mainly at relatively low COD/ [Formula: see text] ratio (e.g., 2-4.5) rather than high COD/ [Formula: see text] ratio (e.g., 16.7) compared to the reactor without ZVI addition. The model proposed in this work is expected to provide support for further development of a more efficient ZVI-based anaerobic granular system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Acetate concentrations and oxidation in salt marsh sediments

NASA Technical Reports Server (NTRS)

1992-01-01

Acetate concentrations and rates of acetate oxidation and sulfate reduction were measured in S. alterniflora sediments in New Hampshire and Massachusetts. Pore water extracted from cores by squeezing or centrifugation contained in greater than 0.1 mM acetate and, in some instances, greater than 1.0 mM. Pore water sampled nondestructively contained much less acetate, often less than 0.01 mM. Acetate was associated with roots, and concentrations varied with changes in plant physiology. Acetate turnover was very low whether whole core or slurry incubations were used. Radiotracers injected directly into soils yielded rates of sulfate reduction and acetate oxidation not significantly different from core incubation techniques. Regardless of incubation method, acetate oxidation did not account for a substantial percentage of sulfate reduction. These results differ markedly from data for unvegetated coastal sediments where acetate levels are low, oxidation rate constants are high, and acetate oxication rates greatly exceed rates of sulfate reduction. The discrepancy between rates of acetate oxidation and sulfate reduction in these marsh soils may be due either to the utilization of substrates other than acetate by sulfate reducers or artifacts associated with measurements of organic utilization by rhizosphere bacteria. Care must be taken when interpreting data from salt marsh sediments since the release of material from roots during coring may affect the concentrations of certain compounds as well as influencing results obtained when sediment incubations are employed.

Analysis of Biogeochemistry of Acid-Mine Drainage at Rowe, Massachusetts

NASA Astrophysics Data System (ADS)

Ahlfeld, D. P.; Yuretich, R.; Ergas, S.; Nusslein, K.; Feldman, A.

2003-12-01

Acid waters rich in iron and sulfate can support a wide variety of microorganisms that catalyze the oxidation-reduction reactions of these bioactive elements, exemplified by acid-mine drainage (AMD). In order to study the biogeochemistry of natural attenuation a field site has been established at Davis Mine, an abandoned pyrite mine in rural Rowe Massachusetts. This site is of particular interest because of the apparent dynamic equilibrium that has restricted the extent of the AMD in this area since the mine was closed nearly 100 years ago. Initial evidence suggests that sulfate reduction is occurring at the fringes of the site. Multi-level monitoring wells and surface water sampling points have been installed. Soil samples collected from the drilled wells are being used to provide inoculums for cultivating bacteria and identifying DNA. Preliminary data indicate a restricted lens of impacted groundwater that moves rapidly through the mine tailings and shallow bedrock fractures, but is contained by ambient groundwater from uncontaminated recharge areas. Sulfate reduction has been documented at the margins of the acid-generating area, and this has been reproduced in laboratory experiments. Current research is now examining the processes of Fe(III) and SO4 reduction and the roles of acidophilic and acid-tolerant anaerobic microorganisms. K12 teachers are part of the research teams and the effects of research experiences on their higher-level understanding of science are being evaluated.

A Demonstration of Bacterial Reduction of Inorganic Sulfate.

ERIC Educational Resources Information Center

Kinard, W. Frank

1979-01-01

This experiment demonstrates the reduction of inorganic sulfate to sulfide in the pore water of estuarine muds. Procedures involve the incubation of mud samples for varying amounts of time followed by gravimetric determination. (Author/SA)

Impact of sulfation and desulfation on NO x reduction using Cu-chabazite SCR catalysts

DOE PAGES

Brookshear, Daniel William; Nam, Jeong -Gil; Nguyen, Ke; ...

2015-06-05

This bench reactor study investigates the impact of gaseous sulfur on the NO x reduction activity of Cu-chabazite SCR (Cu-CHA) catalysts at SO 2 concentrations representative of marine diesel engine exhaust. After two hours of 500 ppm SO 2 exposure at 250 and 400 °C in the simulated diesel exhaust gases, the NO x reduction activity of the sulfated Cu-CHA SCR catalysts is severely degraded at evaluation temperatures below 250 °C; however, above 250 °C the impact of sulfur exposure is minimal. EPMA shows that sulfur is located throughout the washcoat and along the entire length of the sulfated samples.more » Interestingly, BET measurements reveal that the sulfated samples have a 20% decrease in surface area. Moreover, the sulfated samples show a decrease in NO x/nitrate absorption during NO exposure in a DRIFTS reactor which suggests that Cu sites in the catalyst are blocked by the presence of sulfur. SO 2 exposure also results in an increase in NH 3 storage capacity, possibly due to the formation of ammonium sulfate species in the sulfated samples. In all cases, lean thermal treatments as low as 500 °C reverse the effects of sulfur exposure and restore the NO x reduction activity of the Cu-CHA catalyst to that of the fresh condition.« less

Microbial links between sulfate reduction and metal retention in uranium- and heavy metal-contaminated soil.

PubMed

Sitte, Jana; Akob, Denise M; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E; Scheinost, Andreas C; Büchel, Georg; Küsel, Kirsten

2010-05-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the (35)SO(4)(2-) radiotracer method, was restricted to reduced soil horizons with rates of < or =142 +/- 20 nmol cm(-3) day(-1). Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that approximately 80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [(13)C]acetate- and [(13)C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined < or =100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching < or =1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems.

Microbial Links between Sulfate Reduction and Metal Retention in Uranium- and Heavy Metal-Contaminated Soil▿

PubMed Central

Sitte, Jana; Akob, Denise M.; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E.; Scheinost, Andreas C.; Büchel, Georg; Küsel, Kirsten

2010-01-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the 35SO42− radiotracer method, was restricted to reduced soil horizons with rates of ≤142 ± 20 nmol cm−3 day−1. Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that ∼80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [13C]acetate- and [13C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined ≤100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching ≤1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems. PMID:20363796

Anaerobic Benzene Degradation in Petroleum-Contaminated Aquifer Sediments after Inoculation with a Benzene-Oxidizing Enrichment

PubMed Central

Weiner, Jonathan M.; Lovley, Derek R.

1998-01-01

Sediments from the sulfate-reduction zone of a petroleum-contaminated aquifer, in which benzene persisted, were inoculated with a benzene-oxidizing, sulfate-reducing enrichment from aquatic sediments. Benzene was degraded, with apparent growth of the benzene-degrading population over time. These results suggest that the lack of benzene degradation in the sulfate-reduction zones of some aquifers may result from the failure of the appropriate benzene-degrading sulfate reducers to colonize the aquifers rather than from environmental conditions that are adverse for anaerobic benzene degradation. PMID:9464422

Rock magnetic properties in the sulfate reduction zone in IODP 350 Hole 1437B, Izu Bonin rear arc: preliminary results

NASA Astrophysics Data System (ADS)

Musgrave, R. J.; Kars, M. A. C.; Kodama, K.

2014-12-01

During the northern Spring 2014 (April-May), IODP Expedition 350 drilled a 1806.5 m deep hole at Site U1437 in the Izu-Bonin rear arc, in order to understand, among other objectives, the compositional evolution of the arc since the Miocene and track the missing half of the subduction factory. The good recovery of mostly fine grained sediments at this site enables a high resolution paleomagnetic and rock magnetic study. Particularly, variations in magnetic properties and mineralogy are well documented. The onboard magnetostratigraphy established from the study of the archive halves highlighted remagnetized intervals that produced "ghost" repetitions of geomagnetic reversals ~10's meters below their actual stratigraphic position in specific intervals. Onboard paleo- and rock magnetic analyses showed that remagnetization is probably due to a chemical remanence carried by iron sulfides (putatively identified as greigite). The rock magnetic parameters, SIRM/k and the S-ratio are consistent with the presence of ferromagnetic iron sulfides in Site U1437. A mixture of iron oxides and iron sulfides was found within the sulfate reduction zone, which was identified by onboard pore water analyses at ~50-60 meters below sea floor (mbsf) by a minimum in sulfate (~5 mM) coupled with a maximum in alkalinity. Below 50 mbsf, the sulfate content increases up to ~29 mM at ~460 mbsf. The particular downhole profile of the sulfate content in Site U1437 is probably triggered by fluid circulation. Evolution of sulfate content, pyritization process and fluid circulation are closely linked. Onshore research is focusing on further downhole characterization of the iron sulfides including their abundance, grain size and composition. Routine magnetic properties (NRM, magnetic susceptibility) and rock magnetic analyses at high resolution (every ~20-50 cm), including hysteresis properties and low temperature magnetic measurements, have been conducted on about 400 discrete samples in the first 200 m of Hole 1437B (Cores 1H to 30X). As suggested by the onboard data, hysteresis measurements showed the occurrence of both single domain-pseudo single domain iron oxides and iron sulfides in the sulfate reduction zone. Preliminary results will be compared with the geochemical data.

Effects of Iron and Nitrogen Limitation on Sulfur Isotope Fractionation during Microbial Sulfate Reduction

PubMed Central

Ono, Shuhei; Bosak, Tanja

2012-01-01

Sulfate-reducing microbes utilize sulfate as an electron acceptor and produce sulfide that is depleted in heavy isotopes of sulfur relative to sulfate. Thus, the distribution of sulfur isotopes in sediments can trace microbial sulfate reduction (MSR), and it also has the potential to reflect the physiology of sulfate-reducing microbes. This study investigates the relationship between the availability of iron and reduced nitrogen and the magnitude of S-isotope fractionation during MSR by a marine sulfate-reducing bacterium, DMSS-1, a Desulfovibrio species, isolated from salt marsh in Cape Cod, MA. Submicromolar levels of iron increase sulfur isotope fractionation by about 50% relative to iron-replete cultures of DMSS-1. Iron-limited cultures also exhibit decreased cytochrome c-to-total protein ratios and cell-specific sulfate reduction rates (csSRR), implying changes in the electron transport chain that couples carbon and sulfur metabolisms. When DMSS-1 fixes nitrogen in ammonium-deficient medium, it also produces larger fractionation, but it occurs at faster csSRRs than in the ammonium-replete control cultures. The energy and reducing power required for nitrogen fixation may be responsible for the reverse trend between S-isotope fractionation and csSRR in this case. Iron deficiency and nitrogen fixation by sulfate-reducing microbes may lead to the large observed S-isotope effects in some euxinic basins and various anoxic sediments. PMID:23001667

Transient exposure to oxygen or nitrate reveals ecophysiology of fermentative and sulfate-reducing benthic microbial populations.

PubMed

Saad, Sainab; Bhatnagar, Srijak; Tegetmeyer, Halina E; Geelhoed, Jeanine S; Strous, Marc; Ruff, S Emil

2017-12-01

For the anaerobic remineralization of organic matter in marine sediments, sulfate reduction coupled to fermentation plays a key role. Here, we enriched sulfate-reducing/fermentative communities from intertidal sediments under defined conditions in continuous culture. We transiently exposed the cultures to oxygen or nitrate twice daily and investigated the community response. Chemical measurements, provisional genomes and transcriptomic profiles revealed trophic networks of microbial populations. Sulfate reducers coexisted with facultative nitrate reducers or aerobes enabling the community to adjust to nitrate or oxygen pulses. Exposure to oxygen and nitrate impacted the community structure, but did not suppress fermentation or sulfate reduction as community functions, highlighting their stability under dynamic conditions. The most abundant sulfate reducer in all cultures, related to Desulfotignum balticum, appeared to have coupled both acetate- and hydrogen oxidation to sulfate reduction. We describe a novel representative of the widespread uncultured candidate phylum Fermentibacteria (formerly candidate division Hyd24-12). For this strictly anaerobic, obligate fermentative bacterium, we propose the name ' U Sabulitectum silens' and identify it as a partner of sulfate reducers in marine sediments. Overall, we provide insights into the function of fermentative, as well as sulfate-reducing microbial communities and their adaptation to a dynamic environment. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Temperature effects on the fractionation of multiple sulfur isotopes by Thermodesulfobacterium and Desulfovibrio strains

NASA Astrophysics Data System (ADS)

Wang, P.; Sun, C.; Ono, S.; Lin, L.

2012-12-01

Microbial dissimilatory sulfate reduction is one of the major mechanisms driving anaerobic mineralization of organic matter in global ocean. While sulfate-reducing prokaryotes are well known to fractionate sulfur isotopes during dissimilatory sulfate reduction, unraveling the isotopic compositions of sulfur-bearing minerals preserved in sedimentary records could provide invaluable constraints on the evolution of seawater chemistry and metabolic pathways. Variations in the sulfur isotope fractionations are partly due to inherent differences among species and also affected by environmental conditions. The isotope fractionations caused by microbial sulfate reduction have been interpreted to be a sequence of enzyme-catalyzed isotope fractionation steps. Therefore, the fractionation factor depends on (1) the sulfate flux into and out of the cell, and (2) the flux of sulfur transformation between the internal pools. Whether the multiple sulfur isotope effect could be quantitatively predicted using such a metabolic flux model would provide insights into the cellular machinery catalyzing with sulfate reduction. This study examined the multiple sulfur isotope fractionation patterns associated with a thermophilic Thermodesulfobacterium-related strain and a mesophilic Desulfovibrio gigas over a wide temperature range. The Thermodesulfobacterium-related strain grew between 34 and 79°C with an optimal temperature at 72°C and the highest cell-specific sulfate reduction rate at 77°C. The 34ɛ values ranged between 8.2 and 31.6‰ with a maximum at 68°C. The D. gigas grew between 10 and 45 °C with an optimal temperature at 30°C and the highest cell-specific sulfate reduction rate at 41°C. The 34ɛ values ranged between 10.3 and 29.7‰ with higher magnitude at both lower and higher temperatures. The results of multiple sulfur isotope measurements expand the previously reported range and cannot be described by a solution field of the metabolic flux model, which calculates the Δ33S and 34ɛ values assuming equilibrium fractionation among internal steps. Either larger isotope effects or kinetic fractionation has to be considered in the metabolic flux model to explain the multiple sulfur isotope effect produced by these two strains. Overall, the metabolic flux model warrants further revision and further studies regarding physiological responses to growth conditions may probably offer a linkage between multiple sulfur isotope effects and environmental factors for microbial dissimilatory sulfate reduction.

Chemical and Isotopic Characterization of Waters in Rio Tinto, Spain, Shows Possible Origin of the Blueberry Haematite Nodules in Meridiani Planum, Mars

NASA Astrophysics Data System (ADS)

Coleman, M. L.; Hubbard, C. G.; Mielke, R. E.; Black, S.

2005-12-01

Meridiani Planum sediments formed in an acid environment and include jarosite and other evaporitic sulfate minerals. Nodular spheroidal concretions appear to have grown in situ and are predominantly hematite. The source of the Rio Tinto, S. Spain, drains an area of extensive sulfide mineralization and is dominated by acid mine drainage processes. The system is not a Mars analog but potentially similar processes of sulfide oxidation produce sulfate rich waters which feed into the river and precipitate a large range of evaporitic sulfates including jarosite. Iron oxide minerals associated with the evaporites are either dispersed or bedded but not nodular. The water compositions appear to be mixtures of a few discreet end-members: the two most significant occur in undiluted form as inputs to the river and are relevant to many such systems. They both have all sulfur totally oxidized as sulfate. The first is a bright red water, pH ~1.5, Fe/S 0.5 and 23 g/L iron which is greater than 95% Fe3+. Its sulfate oxygen isotope composition is +2‰SMOW and about +7‰, relative to the water O isotope composition. These data indicate pyrite oxidation by Fe3+ with O in sulfate coming mainly from water. The second end-member is a pale green water, pH ~0.7, Fe/S 0.7, 50 g/L iron present mainly as Fe2+ and O isotope composition of sulfate about +6‰SMOW , about +12.5‰ relative to the water O value. Oxygen in sulfate comes mainly from atmospheric oxygen resulting from pyrite oxidation by molecular oxygen dissolved in water. Although the Rio Tinto system reactions probably are microbiologically mediated (relevant genera have been identified there) similar processes could occur abiotically but more slowly. Meridiani Planum sediments and nodules can be described by a plausible set of similar end-member processes. The primary source of sulfate is oxidation of sulfides present in basalt (pyrite, FeS2 or pyrrhotite, FeS) and weathering would have produced oxidized sulfate rich solutions at low pH. Ground water migration could produce evaporitic ponds where various bedded sulfate mineral sediments could form. The intergranular pore-spaces would be water filled. Most terrestrial spheroidal nodular concretions form by radial diffusion in pore-water of a chemical component of a very different oxidation state from that of the surrounding water. A nodular concretion is most usually formed by the reaction of the diffusive component with others in the pore-water. There are two main possible reaction sets for formation of the Blueberries that are consistent with all current data. 1. Local concentrations of organic matter (pre-biotic or biotic) formed reduction spots in which a small amount of Fe3+ either in solution or from evaporite mineral salts, was reduced to Fe2+ and then diffused radially to form an iron oxide nodule by reaction with inwardly diffusing dissolved oxygen. 2. Similar local concentrations of organic matter could also have engendered sulfate reduction and consequent outward diffusion of dissolved sulfide reacted with iron in solution to produce an iron sulfide nodule, subsequently oxidized in situ to hematite (maybe via goethite). Our current work is successfully identifying chemical and stable isotopic characteristics for both microbial and abiotic modes of all relevant reactions.

Sulfur-oxidizing autotrophic and mixotrophic denitrification processes for drinking water treatment: elimination of excess sulfate production and alkalinity requirement.

PubMed

Sahinkaya, Erkan; Dursun, Nesrin

2012-09-01

This study evaluated the elimination of alkalinity need and excess sulfate generation of sulfur-based autotrophic denitrification process by stimulating simultaneous autotrophic and heterotrophic (mixotrophic) denitrification process in a column bioreactor by methanol supplementation. Also, denitrification performances of sulfur-based autotrophic and mixotrophic processes were compared. In autotrophic process, acidity produced by denitrifying sulfur-oxidizing bacteria was neutralized by the external NaHCO(3) supplementation. After stimulating mixotrophic denitrification process, the alkalinity need of the autotrophic process was satisfied by the alkalinity produced by heterotrophic denitrifiers. Decreasing and lastly eliminating the external alkalinity supplementation did not adversely affect the process performance. Complete denitrification of 75 mg L(-1) NO(3)-N under mixotrophic conditions at 4 h hydraulic retention time was achieved without external alkalinity supplementation and with effluent sulfate concentration lower than the drinking water guideline value of 250 mg L(-1). The denitrification rate of mixotrophic process (0.45 g NO(3)-N L(-1) d(-1)) was higher than that of autotrophic one (0.3 g NO(3)-N L(-1) d(-1)). Batch studies showed that the sulfur-based autotrophic nitrate reduction rate increased with increasing initial nitrate concentration and transient accumulation of nitrite was observed. Copyright © 2012 Elsevier Ltd. All rights reserved.

Characterization of U(VI) reduction in contaminated sediments with slow-degrading electron donor source

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Zhang, G.; Mehlhorn, T.; Lowe, K.; Earles, J.; Phillips, J.; Kelly, S. D.; Boyanov, M.; Kemner, K. M.; Schadt, C.; Criddle, C. S.; Jardine, P. M.; Brooks, S. C.

2011-12-01

In order to select sustainable, high efficiency and cost effective electron donor source, oleate and emulsified vegetable oil (EVO) were tested uranium (VI) reduction in comparison with ethanol in microcosms using uranium contaminated sediments and groundwater from the US DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site. The effect of initial sulfate concentration on U(VI) reduction was also tested. Both oleate and EVO were effective electron donor sources for U(VI) reduction. Accumulation of acetate as a major product and the removal of aqueous U(VI) were observed and were associated with sulfate reduction. Both oleate and EVO supported U(VI) reduction but at slower rates with a comparable but slightly lower extent of reduction than ethanol. X-ray absorption near-edge spectroscopy (XANES) analysis confirmed reduction of U(VI) to U(IV). The extent of U(VI) reduction in solid phase was negatively influenced by aqueous calcium concentration. The majority of electrons of the three substrates were consumed by sulfate reduction, Fe(III) reduction, and methanogenesis. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 versus 5 mM), likely due to U(VI) desorption from the solid phase. At the higher initial sulfate concentration more U(VI) was reduced and fewer electrons were used in methanogenesis. Analysis of bacterial and archeal populations using 16S rRNA gene libraries showed a significant increase in Deltaproteobacteria after biostimulation. The microbial community structures developed with oleate and EVO were significantly distinct from those developed with ethanol. Bacteria similar to Desulforegula spp. was predominant for oleate and EVO degradation but were not observed in ethanol-amended microcosms. Known U(VI)-reducing bacteria in the microcosms amended with the three electron donor sources included iron(III) reducing Geobacter spp. but in lower abundances than sulfate-reducing Desulfovibrio spp. The test results were used for the design a field test by one-time injection of EVO to the subsurface for U(VI) reduction in Area 2 of the ORIFRC site.

Mechanistic modeling of biocorrosion caused by biofilms of sulfate reducing bacteria and acid producing bacteria.

PubMed

Xu, Dake; Li, Yingchao; Gu, Tingyue

2016-08-01

Biocorrosion is also known as microbiologically influenced corrosion (MIC). Most anaerobic MIC cases can be classified into two major types. Type I MIC involves non-oxygen oxidants such as sulfate and nitrate that require biocatalysis for their reduction in the cytoplasm of microbes such as sulfate reducing bacteria (SRB) and nitrate reducing bacteria (NRB). This means that the extracellular electrons from the oxidation of metal such as iron must be transported across cell walls into the cytoplasm. Type II MIC involves oxidants such as protons that are secreted by microbes such as acid producing bacteria (APB). The biofilms in this case supply the locally high concentrations of oxidants that are corrosive without biocatalysis. This work describes a mechanistic model that is based on the biocatalytic cathodic sulfate reduction (BCSR) theory. The model utilizes charge transfer and mass transfer concepts to describe the SRB biocorrosion process. The model also includes a mechanism to describe APB attack based on the local acidic pH at a pit bottom. A pitting prediction software package has been created based on the mechanisms. It predicts long-term pitting rates and worst-case scenarios after calibration using SRB short-term pit depth data. Various parameters can be investigated through computer simulation. Copyright © 2016 Elsevier B.V. All rights reserved.

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium.

PubMed

Liu, D; Dong, H; Bishop, M E; Zhang, J; Wang, H; Xie, S; Wang, S; Huang, L; Eberl, D D

2012-03-01

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. © 2011 Blackwell Publishing Ltd.

Characterization of sulfate-reducing granular sludge in the SANI(®) process.

PubMed

Hao, Tianwei; Wei, Li; Lu, Hui; Chui, Hokwong; Mackey, Hamish R; van Loosdrecht, Mark C M; Chen, Guanghao

2013-12-01

Hong Kong practices seawater toilet flushing covering 80% of the population. A sulfur cycle-based biological nitrogen removal process, the Sulfate reduction, Autotrophic denitrification and Nitrification Integrated (SANI(®)) process, had been developed to close the loop between the hybrid water supply and saline sewage treatment. To enhance this novel process, granulation of a Sulfate-Reducing Up-flow Sludge Bed (SRUSB) reactor has recently been conducted for organic removal and provision of electron donors (sulfide) for subsequent autotrophic denitrification, with a view to minimizing footprint and maximizing operation resilience. This further study was focused on the biological and physicochemical characteristics of the granular sulfate-reducing sludge. A lab-scale SRUSB reactor seeded with anaerobic digester sludge was operated with synthetic saline sewage for 368 days. At 1 h nominal hydraulic retention time (HRT) and 6.4 kg COD/m(3)-d organic loading rate, the SRUSB reactor achieved 90% COD and 75% sulfate removal efficiencies. Granular sludge was observed within 30 days, and became stable after 4 months of operation with diameters of 400-500 μm, SVI5 of 30 ml/g, and extracellular polymeric substances of 23 mg carbohydrate/g VSS. Fluorescence in situ hybridization (FISH) analysis revealed that the granules were enriched with abundant sulfate-reducing bacteria (SRB) as compared with the seeding sludge. Pyrosequencing analysis of the 16S rRNA gene in the sulfate-reducing granules on day 90 indicated that the microbial community consisted of a diverse SRB genera, namely Desulfobulbus (18.1%), Desulfobacter (13.6%), Desulfomicrobium (5.6%), Desulfosarcina (0.73%) and Desulfovibrio (0.6%), accounting for 38.6% of total operational taxonomic units at genera level, with no methanogens detected. The microbial population and physicochemical properties of the granules well explained the excellent performance of the granular SRUSB reactor. Copyright © 2013 Elsevier Ltd. All rights reserved.

OBSERVABLE INDICATORS OF THE SENSITIVITY OF PM 2.5 NITRATE TO EMISSION REDUCTIONS, PART II: SENSITIVITY TO ERRORS IN TOTAL AMMONIA AND TOTAL NITRATE OF THE CMAQ-PREDICTED NONLINEAR EFFECT OF SO 2 EMISSION REDUCTIONS

EPA Science Inventory

The inorganic aerosol system of sulfate, nitrate, and ammonium can respond nonlinearly to changes in precursor sulfur dioxide (SO₂) emissions. The potential increase in nitrate, when sulfate is reduced and the associated ammonia is released, can negate the sulfate mass...

Relative contributions of mercury bioavailability and microbial growth rate on net methylmercury production by anaerobic mixed cultures

DOE PAGES

Kucharzyk, Katarzyna H.; Deshusses, Marc A.; Porter, Kaitlyn A.; ...

2015-01-01

Net production of methylmercury correlated with sulfate reduction rates in cultures exposed to dissolved Hg, but was insensitive to sulfate reduction rates for cultures exposed to nanoparticulate HgS.

Hydrochemical assessment of freshening saline groundwater using multiple end-members mixing modeling: A study of Red River delta aquifer, Vietnam

NASA Astrophysics Data System (ADS)

Kim, Ji-Hyun; Kim, Kyoung-Ho; Thao, Nguyen Thi; Batsaikhan, Bayartungalag; Yun, Seong-Taek

2017-06-01

In this study, we evaluated the water quality status (especially, salinity problems) and hydrogeochemical processes of an alluvial aquifer in a floodplain of the Red River delta, Vietnam, based on the hydrochemical and isotopic data of groundwater samples (n = 23) from the Kien Xuong district of the Thai Binh province. Following the historical inundation by paleo-seawater during coastal progradation, the aquifer has been undergone progressive freshening and land reclamation to enable settlements and farming. The hydrochemical data of water samples showed a broad hydrochemical change, from Na-Cl through Na-HCO3 to Ca-HCO3 types, suggesting that groundwater was overall evolved through the freshening process accompanying cation exchange. The principal component analysis (PCA) of the hydrochemical data indicates the occurrence of three major hydrogeochemical processes occurring in an aquifer, namely: 1) progressive freshening of remaining paleo-seawater, 2) water-rock interaction (i.e., dissolution of silicates), and 3) redox process including sulfate reduction, as indicated by heavy sulfur and oxygen isotope compositions of sulfate. To quantitatively assess the hydrogeochemical processes, the end-member mixing analysis (EMMA) and the forward mixing modeling using PHREEQC code were conducted. The EMMA results show that the hydrochemical model with the two-dimensional mixing space composed of PC 1 and PC 2 best explains the mixing in the study area; therefore, we consider that the groundwater chemistry mainly evolved by mixing among three end-members (i.e., paleo-seawater, infiltrating rain, and the K-rich groundwater). The distinct depletion of sulfate in groundwater, likely due to bacterial sulfate reduction, can also be explained by EMMA. The evaluation of mass balances using geochemical modeling supports the explanation that the freshening process accompanying direct cation exchange occurs through mixing among three end-members involving the K-rich groundwater. This study shows that the multiple end-members mixing model is useful to more successfully assess complex hydrogeochemical processes occurring in a salinized aquifer under freshening, as compared to the conventional interpretation using the theoretical mixing line based on only two end-members (i.e., seawater and rainwater).

Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.

PubMed

Egger, Matthias; Rasigraf, Olivia; Sapart, Célia J; Jilbert, Tom; Jetten, Mike S M; Röckmann, Thomas; van der Veen, Carina; Bândă, Narcisa; Kartal, Boran; Ettwig, Katharina F; Slomp, Caroline P

2015-01-06

Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Impacts of an ethanol-blended fuel release on groundwater and fate of produced methane: Simulation of field observations

NASA Astrophysics Data System (ADS)

Rasa, Ehsan; Bekins, Barbara A.; Mackay, Douglas M.; de Sieyes, Nicholas R.; Wilson, John T.; Feris, Kevin P.; Wood, Isaac A.; Scow, Kate M.

2013-08-01

In a field experiment at Vandenberg Air Force Base (VAFB) designed to mimic the impact of a small-volume release of E10 (10% ethanol and 90% conventional gasoline), two plumes were created by injecting extracted groundwater spiked with benzene, toluene, and o-xylene, abbreviated BToX (no-ethanol lane) and BToX plus ethanol (with-ethanol lane) for 283 days. We developed a reactive transport model to understand processes controlling the fate of ethanol and BToX. The model was calibrated to the extensive field data set and accounted for concentrations of sulfate, iron, acetate, and methane along with iron-reducing bacteria, sulfate-reducing bacteria, fermentative bacteria, and methanogenic archaea. The benzene plume was about 4.5 times longer in the with-ethanol lane than in the no-ethanol lane. Matching this different behavior in the two lanes required inhibiting benzene degradation in the presence of ethanol. Inclusion of iron reduction with negligible growth of iron reducers was required to reproduce the observed constant degradation rate of benzene. Modeling suggested that vertical dispersion and diffusion of sulfate from an adjacent aquitard were important sources of sulfate in the aquifer. Matching of methane data required incorporating initial fermentation of ethanol to acetate, methane loss by outgassing, and methane oxidation coupled to sulfate and iron reduction. Simulation of microbial growth using dual Monod kinetics, and including inhibition by more favorable electron acceptors, generally resulted in reasonable yields for microbial growth of 0.01-0.05.

Impacts of an ethanol-blended fuel release on groundwater and fate of produced methane: simulation of field observations

USGS Publications Warehouse

Rasa, Ehsan; Bekins, Barbara A.; Mackay, Douglas M.; de Sieyes, Nicholas R.; Wilson, John T.; Feris, Kevin P.; Wood, Isaac A.; Scow, Kate M.

2013-01-01

In a field experiment at Vandenberg Air Force Base (VAFB) designed to mimic the impact of a small-volume release of E10 (10% ethanol and 90% conventional gasoline), two plumes were created by injecting extracted groundwater spiked with benzene, toluene, and o-xylene, abbreviated BToX (No-Ethanol Lane) and BToX plus ethanol (With-Ethanol Lane) for 283 days. We developed a reactive transport model to understand processes controlling the fate of ethanol and BToX. The model was calibrated to the extensive field dataset and accounted for concentrations of sulfate, iron, acetate, and methane along with iron-reducing bacteria, sulfate-reducing bacteria, fermentative bacteria, and methanogenic archaea. The benzene plume was about 4.5 times longer in the With-Ethanol Lane than in the No-Ethanol Lane. Matching this different behavior in the two lanes required inhibiting benzene degradation in the presence of ethanol. Inclusion of iron reduction with negligible growth of iron-reducers was required to reproduce the observed constant degradation rate of benzene. Modeling suggested that vertical dispersion and diffusion of sulfate from an adjacent aquitard were important sources of sulfate in the aquifer. Matching of methane data required incorporating initial fermentation of ethanol to acetate, methane loss by outgassing, and methane oxidation coupled to sulfate and iron reduction. Simulation of microbial growth using dual Monod kinetics, and including inhibition by more favorable electron acceptors, generally resulted in reasonable yields for microbial growth of 0.01-0.05.

Sulfur transformations at the hydrogen sulfide/oxygen interface in stratified waters and in cyanobacterial mats

NASA Technical Reports Server (NTRS)

Cohen, Y.

1985-01-01

Stratified water bodies allow the development of several microbial plates along the water column. The microbial plates develop in relation to nutrient availability, light penetration, and the distribution of oxygen and sulfide. Sulfide is initially produced in the sediment by sulfate-reducing bacteria. It diffuses along the water column creating a zone of hydrogen sulfide/oxygen interface. In the chemocline of Solar Lake oxygen and sulfide coexist in a 0 to 10 cm layer that moves up and down during a diurnal cycle. The microbial plate at the chemocline is exposed to oxygen and hydrogen sulfide, alternating on a diurnal basis. The cyanobacteria occupying the interface switch from anoxygenic photosynthesis in the morning to oxygenic photosynthesis during the rest of the day which results in a temporal build up of elemental sulfur during the day and disappears at night due to both oxidation to thiosulfate and sulfate by thiobacilli, and reduction to hydrogen sulfide by Desulfuromonas sp. and anaerobically respiring cyanobacteria. Sulfate reduction was enhanced in the light at the surface of the cyanobacterial mats. Microsulfate reduction measurements showed enhanced activity of sulfate reduction even under high oxygen concentrations of 300 to 800 micrometer. Apparent aerobic SO sub 4 reduction activity is explained by the co-occurrence of H sub 2. The physiology of this apparent sulfate reduction activity is studied.

Selenate reduction to elemental selenium by anaerobic bacteria in sediments and culture: biogeochemical significance of a novel, sulfate-independent respiration

USGS Publications Warehouse

Oremland, Ronald S.; Hollibaugh, James T.; Maest, Ann S.; Presser, Theresa S.; Miller, Laurence G.; Culbertson, Charles W.

1989-01-01

Interstitial water profiles of SeO42−, SeO32−, SO42−, and Cl− in anoxic sediments indicated removal of the seleno-oxyanions by a near-surface process unrelated to sulfate reduction. In sediment slurry experiments, a complete reductive removal of SeO42− occurred under anaerobic conditions, was more rapid with H2 or acetate, and was inhibited by O2, NO3−, MnO2, or autoclaving but not by SO42− or FeOOH. Oxidation of acetate in sediments could be coupled to selenate but not to molybdate. Reduction of selenate to elemental selenium was determined to be the mechanism for loss from solution. Selenate reduction was inhibited by tungstate and chromate but not by molybdate. A small quantity of the elemental selenium precipitated into sediments from solution could be resolublized by oxidation with either nitrate or FeOOH, but not with MnO2. A bacterium isolated from estuarine sediments demonstrated selenate-dependent growth on acetate, forming elemental selenium and carbon dioxide as respiratory end products. These results indicate that dissimilatory selenate reduction to elemental selenium is the major sink for selenium oxyanions in anoxic sediments. In addition, they suggest application as a treatment process for removing selenium oxyanions from wastewaters and also offer an explanation for the presence of selenite in oxic waters.

Bacterially mediated removal of phosphorus and cycling of nitrate and sulfate in the waste stream of a "zero-discharge" recirculating mariculture system.

PubMed

Krom, M D; Ben David, A; Ingall, E D; Benning, L G; Clerici, S; Bottrell, S; Davies, C; Potts, N J; Mortimer, R J G; van Rijn, J

2014-06-01

Simultaneous removal of nitrogen and phosphorus by microbial biofilters has been used in a variety of water treatment systems including treatment systems in aquaculture. In this study, phosphorus, nitrate and sulfate cycling in the anaerobic loop of a zero-discharge, recirculating mariculture system was investigated using detailed geochemical measurements in the sludge layer of the digestion basin. High concentrations of nitrate and sulfate, circulating in the overlying water (∼15 mM), were removed by microbial respiration in the sludge resulting in a sulfide accumulation of up to 3 mM. Modelling of the observed S and O isotopic ratios in the surface sludge suggested that, with time, major respiration processes shifted from heterotrophic nitrate and sulfate reduction to autotrophic nitrate reduction. The much higher inorganic P content of the sludge relative to the fish feces is attributed to conversion of organic P to authigenic apatite. This conclusion is supported by: (a) X-ray diffraction analyses, which pointed to an accumulation of a calcium phosphate mineral phase that was different from P phases found in the feces, (b) the calculation that the pore waters of the sludge were highly oversaturated with respect to hydroxyapatite (saturation index = 4.87) and (c) there was a decrease in phosphate (and in the Ca/Na molar ratio) in the pore waters simultaneous with an increase in ammonia showing there had to be an additional P removal process at the same time as the heterotrophic breakdown of organic matter. Copyright © 2014 Elsevier Ltd. All rights reserved.

Enhanced Sulfate Reduction and Carbon Sequestration in Sediments Underlying the Core of the Arabian Sea Oxygen Minimum Zone

NASA Astrophysics Data System (ADS)

Fernandes, S. Q.; Mazumdar, A.; Peketi, A.; Bhattacharya, S.; Carvalho, M.; Da Silva, R.; Roy, R.; Mapder, T.; Roy, C.; Banik, S. K.; Ghosh, W.

2017-12-01

The oxygen minimum zone (OMZ) of the Arabian Sea in the northern Indian Ocean is one of the three major global sites of open ocean denitrification. The functionally anoxic water column between 150 to 1200 mbsl plays host to unique biogeochemical processes and organism interactions. Little is known, however, about the consequence of the low dissolved oxygen on the underlying sedimentary biogeochemical processes. Here we present, for the first time, a comprehensive investigation of sediment biogeochemistry of the Arabian Sea OMZ by coupling pore fluid analyses with microbial diversity data in eight sediment cores collected across a transect off the west coast of India in the Eastern Arabian Sea. We observed that in sediments underlying the core of the OMZ, high organic carbon sequestration coincides with a high diversity of all bacteria (the majority of which are complex organic matter hydrolyzers) and sulfate reducing bacteria (simple organic compound utilizers). Depth-integrated sulfate reduction rate also intensifies in this territory. These biogeochemical features, together with the detected shallowing of the sulfate-methane interface and buildup of pore-water sulfide, are all reflective of heightened carbon-sulfur cycling in the sediments underlying the OMZ core. Our data suggests that the sediment biogeochemistry of the OMZ is sensitive to minute changes in bottom water dissolved oxygen, and is dictated by the potential abundance and bioavailability of complex to simple carbon compounds which can stimulate a cascade of geomicrobial activities pertaining to the carbon-sulfur cycle. Our findings hold implications in benthic ecology and sediment diagenesis.

Sulfur Isotope Effects of Dissimilatory Sulfite Reductase

PubMed Central

Leavitt, William D.; Bradley, Alexander S.; Santos, André A.; Pereira, Inês A. C.; Johnston, David T.

2015-01-01

The precise interpretation of environmental sulfur isotope records requires a quantitative understanding of the biochemical controls on sulfur isotope fractionation by the principle isotope-fractionating process within the S cycle, microbial sulfate reduction (MSR). Here we provide the only direct observation of the major (34S/32S) and minor (33S/32S, 36S/32S) sulfur isotope fractionations imparted by a central enzyme in the energy metabolism of sulfate reducers, dissimilatory sulfite reductase (DsrAB). Results from in vitro sulfite reduction experiments allow us to calculate the in vitro DsrAB isotope effect in 34S/32S (hereafter, 34εDsrAB) to be 15.3 ± 2‰, 2σ. The accompanying minor isotope effect in 33S, described as 33λDsrAB, is calculated to be 0.5150 ± 0.0012, 2σ. These observations facilitate a rigorous evaluation of the isotopic fractionation associated with the dissimilatory MSR pathway, as well as of the environmental variables that govern the overall magnitude of fractionation by natural communities of sulfate reducers. The isotope effect induced by DsrAB upon sulfite reduction is a factor of 0.3–0.6 times prior indirect estimates, which have ranged from 25 to 53‰ in 34εDsrAB. The minor isotope fractionation observed from DsrAB is consistent with a kinetic or equilibrium effect. Our in vitro constraints on the magnitude of 34εDsrAB is similar to the median value of experimental observations compiled from all known published work, where 34εr−p = 16.1‰ (r–p indicates reactant vs. product, n = 648). This value closely matches those of MSR operating at high sulfate reduction rates in both laboratory chemostat experiments (34εSO4−H2S =  17.3 ± 1.5‰, 2σ) and in modern marine sediments (34εSO4−H2S =  17.3 ± 3.8‰). Targeting the direct isotopic consequences of a specific enzymatic processes is a fundamental step toward a biochemical foundation for reinterpreting the biogeochemical and geobiological sulfur isotope records in modern and ancient environments. PMID:26733949

Sulfur and Methylmercury in the Florida Everglades - the Biogeochemical Connection

NASA Astrophysics Data System (ADS)

Orem, W. H.; Gilmour, C. C.; Krabbenhoft, D. P.; Aiken, G.

2011-12-01

Methylmercury (MeHg) is a serious environmental problem in aquatic ecosystems worldwide because of its toxicity and tendency to bioaccumulate. The Everglades receives some of the highest levels of atmospheric mercury deposition and has some of the highest levels of MeHg in fish in the USA, posing a threat to pisciverous wildlife and people through fish consumption. USGS studies show that a combination of biogeochemical factors make the Everglades especially susceptible to MeHg production and bioaccumulation: (1) vast wetland area with anoxic soils supporting anaerobic microbial activity, (2) high rates of atmospheric mercury deposition, (3) high levels of dissolved organic carbon (DOC) that complexes and stabilizes mercury in solution for transport to sites of methylation, and (4) high sulfate loading in surface water that drives microbial sulfate reduction and mercury methylation. The high levels of sulfate in the Everglades represent an unnatural condition. Background sulfate levels are estimated to be <1 mg/L, but about 60% of the Everglades has surface water sulfate concentrations exceeding background. Highly sulfate-enriched marshes in the northern Everglades have average sulfate levels of 60 mg/L. Sulfate loading to the Everglades is principally a result of land and water management in south Florida. The highest concentrations of sulfate, averaging 60-70 mg/L, are in canal water in the Everglades Agricultural Area (EAA). Geochemical data and a preliminary sulfur mass balance for the EAA are consistent with sulfur currently used in agriculture, and sulfur released by oxidation of organic EAA soils (including legacy agricultural applications and natural sulfur) as the primary sources of sulfate enrichment to the canals and ecosystem. Sulfate loading increases microbial sulfate reduction and MeHg production in soils. The relationship between sulfate loading and MeHg production, however, is complex. Sulfate levels up to about 20-30 mg/L increase mercury methylation, but buildup of sulfide from microbial sulfate reduction begins to inhibit mercury methylation above this range. Sulfate from the EAA canals has primarily impacted the northern Everglades nearest the EAA, but recent evidence shows sulfate loading extending about 80 km further south into Everglades National Park. Current restoration plans to restore to deliver more water south to Everglades National Park may increase overall sulfur loads to the southern part of the ecosystem. A comprehensive Everglades restoration strategy should include reduction of sulfur loads as a goal because of the many detrimental impacts of sulfate on the ecosystem. Monitoring data show that the ecosystem response to changes in sulfate levels is rapid, and strategies for reducing sulfate loading may be effective in the near-term. A multifaceted approach employing best management practices for sulfur in agriculture, agricultural practices that minimize soil oxidation, and changes to stormwater treatment areas that increase sulfate retention, could help reduce sulfate loads to the Everglades, with resulting benefits.

A potential role for chondroitin sulfate/dermatan sulfate in arm regeneration in Amphiura filiformis.

PubMed

Ramachandra, Rashmi; Namburi, Ramesh B; Dupont, Sam T; Ortega-Martinez, Olga; van Kuppevelt, Toin H; Lindahl, Ulf; Spillmann, Dorothe

2017-05-01

Glycosaminoglycans (GAGs), such as chondroitin sulfate (CS) and dermatan sulfate (DS) from various vertebrate and invertebrate sources are known to be involved in diverse cellular mechanisms during repair and regenerative processes. Recently, we have identified CS/DS as the major GAG in the brittlestar Amphiura filiformis, with high proportions of di- and tri-O-sulfated disaccharide units. As this echinoderm is known for its exceptional regeneration capacity, we aimed to explore the role of these GAG chains during A. filiformis arm regeneration. Analysis of CS/DS chains during the regeneration process revealed an increase in the proportion of the tri-O-sulfated disaccharides. Conversely, treatment of A. filiformis with sodium chlorate, a potent inhibitor of sulfation reactions in GAG biosynthesis, resulted in a significant reduction in arm growth rates with total inhibition at concentrations higher than 5 mM. Differentiation was less impacted by sodium chlorate exposure or even slightly increased at 1-2 mM. Based on the structural changes observed during arm regeneration we identified chondroitin synthase, chondroitin-4-O-sulfotransferase 2 and dermatan-4-O-sulfotransferase as candidate genes and sought to correlate their expression with the expression of the A. filiformis orthologue of bone morphogenetic factors, AfBMP2/4. Quantitative amplification by real-time PCR indicated increased expression of chondroitin synthase and chondroitin-4-O-sulfotransferase 2, with a corresponding increase in AfBMP2/4 during regeneration relative to nonregenerating controls. Our findings suggest that proper sulfation of GAGs is important for A. filiformis arm regeneration and that these molecules may participate in mechanisms controlling cell proliferation. © The Author 2017. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Coastal eutrophication thresholds: a matter of sediment microbial processes.

PubMed

Lehtoranta, Jouni; Ekholm, Petri; Pitkänen, Heikki

2009-09-01

In marine sediments, the major anaerobic mineralization processes are Fe(III) oxide reduction and sulfate reduction. In this article, we propose that the two alternative microbial mineralization pathways in sediments exert decisively different impacts on aquatic ecosystems. In systems where iron reduction dominates in the recently deposited sediment layers, the fraction of Fe(III) oxides that is dissolved to Fe(II) upon reduction will ultimately be transported to the oxic layer, where it will be reoxidized. Phosphorus, which is released from Fe(III) oxides and decomposing organic matter from the sediment, will be largely trapped by this newly formed Fe(III) oxide layer. Consequently, there are low concentrations of phosphorus in near-bottom and productive water layers and primary production tends to be limited by phosphorus (State 1). By contrast, in systems where sulfate reduction dominates, Fe(III) oxides are reduced by sulfides. This chemical reduction leads to the formation and permanent burial of iron as solid iron sulfides that are unable to capture phosphorus. In addition, the cycling of iron is blocked, and phosphorus is released to overlying water. Owing to the enrichment of phosphorus in water, the nitrogen : phosphorus ratio is lowered and nitrogen tends to limit algal growth, giving an advantage to nitrogen-fixing blue-green algae (State 2). A major factor causing a shift from State 1 to State 2 is an increase in the flux of labile organic carbon to the bottom sediments; upon accelerating eutrophication a critical point will be reached when the availability of Fe(III) oxides in sediments will be exhausted and sulfate reduction will become dominant. Because the reserves of Fe(III) oxides are replenished only slowly, reversal to State 1 may markedly exceed the time needed to reduce the flux of organic carbon to the sediment. A key factor affecting the sensitivity of a coastal system to such a regime shift is formed by the hydrodynamic alterations that decrease the transport of O2 to the near-bottom water, e.g., due to variations in salinity and temperature stratification.

Bedded Barite Deposits from Sonora (nw Mexico): a Paleozoic Analog for Modern Cold Seeps

NASA Astrophysics Data System (ADS)

Canet, C.; Anadón, P.; González-Partida, E.; Alfonso, P.; Rajabi, A.; Pérez-Segura, E.; Alba-Aldave, L. A.

2013-05-01

The Mazatán barite deposits represent an outstanding example of Paleozoic bedded barite, a poorly understood type of mineral deposit of major economic interest. The largest barite bodies of Mazatán are hosted within an Upper Carboniferous flysch succession, which formed part of an accretionary wedge related to the subduction of the Rheic Ocean beneath Gondwana. As well, a few barite occurrences are hosted in Upper Devonian, pre-orogenic turbidites. A variety of mineralized structures is displayed by barite, including: septaria nodules, enterolitic structures, rosettes and debris-flow conglomerates. Barite is accompanied by chalcedony, pyrite (framboids) and berthierine. Gas-rich fluid inclusions in barite were analyzed by Raman spectroscopy and methane was identified, suggesting the occurrence of light hydrocarbons in the environment within which barite precipitated. 13C-depleted carbonates (δ13C: -24.3 to -18.8‰) were found in the barite deposits; they formed through anaerobic oxidation of methane coupled to sulfate reduction, and yield negative δ18O values (-11.9 to -5.2‰) reflecting the isotopic composition of Devonian-Carboniferous seawater. Methane-derived carbonates occur in modern hydrocarbon seeps and have been reported from Mesozoic and Cenozoic seep sediments, but they have never before been described in Paleozoic bedded barite deposits. δ34S of barite varies from +17.6 to +64.1‰, with the lowest values overlapping the range for coeval seawater sulfate; this distribution indicates a process of sulfate reduction. Barite precipitation can be explained by mixing of methane- and barium-rich fluids with pore-water (seawater) containing sulfate residual from microbial reduction. Two analyses from barite gave an 87Sr/86Sr within and slightly above the range for seawater at the time of deposition, with 0.708130 and 0.708588, which would preclude the involvement of hydrothermal fluids in the mineralization process.

Microbial mats in the Black Sea that anaerobically oxidise methane

NASA Astrophysics Data System (ADS)

Nauhaus, K.; Knittel, K.; Krüger, M.; Boetius, A.; Michaelis, W.; Widdel, F.

2003-04-01

Reef-forming microbial mats were recovered from methane seeps in anoxic waters of the northwestern Black Sea (BS) shelf. The microbial mats consist mainly of archaea (ANME-1 cluster) and sulfate-reducing bacteria (Desulfosarcina/Desulfococcus group). Laboratory incubations with homogenized subsamples of the mats revealed their ability for the anaerobic oxidation of methane (AOM). The phylogentic relationship of the sulfate reducing partner is the same as in the AOM consortia studied in sediment samples from a methane hydrate area (Hydrate Ridge (HR), Oregon, USA (1,2)). The archaeal partner however belongs to a different cluster than in the HR samples (ANME-2). Methane oxidation is coupled to sulfate reduction in a 1:1 stoichiometry. Elevated methane partial pressures (0.1 to 1.1 MPa) increased the sulfate reduction rates in the Black Sea samples only two-fold in contrast to 5-fold in HR samples. The optimal temperature for the BS samples is between 10 and 25^oC. In both samples AOM was not taking place if typical inhibitors for sulfate-reduction or methanogenesis were added, thus indicating a syntrophic relationship between the partner organisms. The intermediate that is exchanged between the methane oxidizing archaea and the sulfate-reducing bacterium is still unknown. Additions of the possible intermediates (Acetate, Formate, Hydrogen) did not result in higher sulfate reduction rates in the absence of methane. (1) Boetius, A. et al. (2000) A marine microbial consortium apparently mediating anaerobic oxidation of methane. Nature. 407: 623--626 (2) Nauhaus, K., Boetius, A., Krüger, M., Widdel, F. (2002) In vitro demonstration of anaerobic oxidation of methane coupled to sulphate reduction in sediment from a marine gas hydrate area. Environ. Microbiol. 4 (5): 296--305

Transcriptome analysis of the sulfate deficiency response in the marine microalga Emiliania huxleyi.

PubMed

Bochenek, Michal; Etherington, Graham J; Koprivova, Anna; Mugford, Sam T; Bell, Thomas G; Malin, Gill; Kopriva, Stanislav

2013-08-01

The response to sulfate deficiency of plants and freshwater green algae has been extensively analysed by system biology approaches. By contrast, seawater sulfate concentration is high and very little is known about the sulfur metabolism of marine organisms. Here, we used a combination of metabolite analysis and transcriptomics to analyse the response of the marine microalga Emiliania huxleyi as it acclimated to sulfate limitation. Lowering sulfate availability in artificial seawater from 25 to 5 mM resulted in significant reduction in growth and intracellular concentrations of dimethylsulfoniopropionate and glutathione. Sulfate-limited E. huxleyi cells showed increased sulfate uptake but sulfate reduction to sulfite did not seem to be regulated. Sulfate limitation in E. huxleyi affected expression of 1718 genes. The vast majority of these genes were upregulated, including genes involved in carbohydrate and lipid metabolism, and genes involved in the general stress response. The acclimation response of E. huxleyi to sulfate deficiency shows several similarities to the well-described responses of Arabidopsis and Chlamydomonas, but also has many unique features. This dataset shows that even though E. huxleyi is adapted to constitutively high sulfate concentration, it retains the ability to re-program its gene expression in response to reduced sulfate availability. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

Sulfate Aerosol in the Arctic: Source Attribution and Radiative Forcing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Yang; Wang, Hailong; Smith, Steven J.

Source attributions of Arctic sulfate and its direct radiative effect for 2010–2014 are quantified in this study using the Community Earth System Model (CESM) equipped with an explicit sulfur source-tagging technique. Regions that have high emissions and/or are near/within the Arctic present relatively large contributions to Arctic sulfate burden, with the largest contribution from sources in East Asia (27%). East Asia and South Asia together have the largest contributions to Arctic sulfate concentrations at 9–12 km, whereas sources within or near the Arctic account largely below 2 km. For remote sources with strong emissions, their contributions to Arctic sulfate burdenmore » are primarily driven by meteorology, while contributions of sources within or near the Arctic are dominated by their emission strength. The sulfate direct radiative effect (DRE) is –0.080 W m-2 at the Arctic surface, offsetting the net warming effect from the combination of in-snow heating and DRE cooling from black carbon. East Asia, Arctic local and Russia/Belarus/Ukraine sources contribute –0.017, –0.016 and –0.014 W m-2, respectively, to Arctic sulfate DRE. A 20% reduction in anthropogenic SO2 emissions leads to a net increase of +0.013 W m-2 forcing at the Arctic surface. These results indicate that a joint reduction in BC emissions could prevent possible Arctic warming from future reductions in SO2 emissions. Sulfate DRE efficiency calculations suggest that short transport pathways together with meteorology favoring long sulfate lifetimes make certain sources more efficient in influencing the Arctic sulfate DRE.« less

Transcriptional analysis of sulfate reducing and chemolithoautotrophic sulfur oxidizing bacteria in the deep subseafloor.

PubMed

Orsi, William D; Barker Jørgensen, Bo; Biddle, Jennifer F

2016-08-01

Sulfate reducing bacteria (SRB) oxidize a significant proportion of subseafloor organic carbon, but their metabolic activities and subsistence mechanisms are poorly understood. Here, we report in depth phylogenetic and metabolic analyses of SRB transcripts in the Peru Margin subseafloor and interpret these results in the context of sulfate reduction activity in the sediment. Relative abundance of overall SRB gene transcripts declines strongly whereas relative abundance of ribosomal protein transcripts from sulfate reducing δ-Proteobacteria peak at 90 m below seafloor (mbsf) within a deep sulfate methane transition zone. This coincides with isotopically heavy δ(34) S values of pore water sulfate (70‰), indicating active subseafloor microbial sulfate reduction. Within the shallow sulfate reduction zone (0-5 mbsf), a transcript encoding the beta subunit of dissimilatory sulfite reductase (dsrB) was related to Desulfitobacterium dehalogenans and environmental sequences from Aarhus Bay (Denmark). At 159 mbsf we discovered a transcript encoding the reversely operating dissimilatory sulfite reductase α-subunit (rdsrA), with basal phylogenetic relation to the chemolithoautotrophic SUP05 Group II clade. A diversity of SRB transcripts involved in cellular maintenance point toward potential subsistence mechanisms under low-energy over long time periods, and provide a detailed new picture of SRB activities underlying sulfur cycling in the deep subseafloor. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Biogeochemical Signals from Deep Microbial Life in Terrestrial Crust

PubMed Central

Fukuda, Akari; Komatsu, Daisuke D.; Hirota, Akinari; Watanabe, Katsuaki; Togo, Yoko; Morikawa, Noritoshi; Hagiwara, Hiroki; Aosai, Daisuke; Iwatsuki, Teruki; Tsunogai, Urumu; Nagao, Seiya; Ito, Kazumasa; Mizuno, Takashi

2014-01-01

In contrast to the deep subseafloor biosphere, a volumetrically vast and stable habitat for microbial life in the terrestrial crust remains poorly explored. For the long-term sustainability of a crustal biome, high-energy fluxes derived from hydrothermal circulation and water radiolysis in uranium-enriched rocks are seemingly essential. However, the crustal habitability depending on a low supply of energy is unknown. We present multi-isotopic evidence of microbially mediated sulfate reduction in a granitic aquifer, a representative of the terrestrial crust habitat. Deep meteoric groundwater was collected from underground boreholes drilled into Cretaceous Toki granite (central Japan). A large sulfur isotopic fractionation of 20–60‰ diagnostic to microbial sulfate reduction is associated with the investigated groundwater containing sulfate below 0.2 mM. In contrast, a small carbon isotopic fractionation (<30‰) is not indicative of methanogenesis. Except for 2011, the concentrations of H2 ranged mostly from 1 to 5 nM, which is also consistent with an aquifer where a terminal electron accepting process is dominantly controlled by ongoing sulfate reduction. High isotopic ratios of mantle-derived 3He relative to radiogenic 4He in groundwater and the flux of H2 along adjacent faults suggest that, in addition to low concentrations of organic matter (<70 µM), H2 from deeper sources might partly fuel metabolic activities. Our results demonstrate that the deep biosphere in the terrestrial crust is metabolically active and playing a crucial role in the formation of reducing groundwater even under low-energy fluxes. PMID:25517230

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

NASA Astrophysics Data System (ADS)

Dale, A. W.; Regnier, P.; Knab, N. J.; Jørgensen, B. B.; Van Cappellen, P.

2008-06-01

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol-1, which is within the range reported in the literature for anaerobic processes.

Performance of CSTR-EGSB-SBR system for treating sulfate-rich cellulosic ethanol wastewater and microbial community analysis.

PubMed

Shan, Lili; Zhang, Zhaohan; Yu, Yanling; Ambuchi, John Justo; Feng, Yujie

2017-06-01

Performance and microbial community composition were evaluated in a two-phase anaerobic and aerobic system treating sulfate-rich cellulosic ethanol wastewater (CEW). The system was operated at five different chemical oxygen demand (COD)/SO 4 2- ratios (63.8, 26.3, 17.8, 13.7, and 10.7). Stable performance was obtained for total COD removal efficiency (94.5%), sulfate removal (89.3%), and methane production rate (11.5 L/day) at an organic loading rate of 32.4 kg COD/(m 3 ·day). The acidogenic reactor made a positive contribution to net VFAs production (2318.1 mg/L) and sulfate removal (60.9%). Acidogenic bacteria (Megasphaera, Parabacteroides, unclassified Ruminococcaceae spp., and Prevotella) and sulfate-reducing bacteria (Butyrivibrio, Megasphaera) were rich in the acidogenic reactor. In the methanogenic reactor, high diversity of microorganisms corresponded with a COD removal contribution of 83.2%. Moreover, methanogens (Methanosaeta) were predominant, suggesting that these organisms played an important role in the acetotrophic methanogenesis pathway. The dominant aerobic bacteria (Truepera) appeared to have been responsible for the COD removal of the SBR. These results indicate that dividing the sulfate reduction process could effectively minimize sulfide toxicity, which is important for the successful operation of system treating sulfate-rich CEW.

Erosion of functional independence early in the evolution of a microbial mutualism

PubMed Central

Hillesland, Kristina L.; Lim, Sujung; Flowers, Jason J.; Turkarslan, Serdar; Pinel, Nicolas; Zane, Grant M.; Elliott, Nicholas; Qin, Yujia; Wu, Liyou; Baliga, Nitin S.; Zhou, Jizhong; Wall, Judy D.; Stahl, David A.

2014-01-01

Many species have evolved to function as specialized mutualists, often to the detriment of their ability to survive independently. However, there are few, if any, well-controlled observations of the evolutionary processes underlying the genesis of new mutualisms. Here, we show that within the first 1,000 generations of initiating independent syntrophic interactions between a sulfate reducer (Desulfovibrio vulgaris) and a hydrogenotrophic methanogen (Methanococcus maripaludis), D. vulgaris frequently lost the capacity to grow by sulfate respiration, thus losing the primary physiological attribute of the genus. The loss of sulfate respiration was a consequence of mutations in one or more of three key genes in the pathway for sulfate respiration, required for sulfate activation (sat) and sulfate reduction to sulfite (apsA or apsB). Because loss-of-function mutations arose rapidly and independently in replicated experiments, and because these mutations were correlated with enhanced growth rate and productivity, gene loss could be attributed to natural selection, even though these mutations should significantly restrict the independence of the evolved D. vulgaris. Together, these data present an empirical demonstration that specialization for a mutualistic interaction can evolve by natural selection shortly after its origin. They also demonstrate that a sulfate-reducing bacterium can readily evolve to become a specialized syntroph, a situation that may have often occurred in nature. PMID:25267659

Formate, acetate, and propionate as substrates for sulfate reduction in sub-arctic sediments of Southwest Greenland

PubMed Central

Glombitza, Clemens; Jaussi, Marion; Røy, Hans; Seidenkrantz, Marit-Solveig; Lomstein, Bente A.; Jørgensen, Bo B.

2015-01-01

Volatile fatty acids (VFAs) are key intermediates in the anaerobic mineralization of organic matter in marine sediments. We studied the role of VFAs in the carbon and energy turnover in the sulfate reduction zone of sediments from the sub-arctic Godthåbsfjord (SW Greenland) and the adjacent continental shelf in the NE Labrador Sea. VFA porewater concentrations were measured by a new two-dimensional ion chromatography-mass spectrometry method that enabled the direct analysis of VFAs without sample pretreatment. VFA concentrations were low and surprisingly constant (4–6 μmol L−1 for formate and acetate, and 0.5 μmol L−1 for propionate) throughout the sulfate reduction zone. Hence, VFAs are turned over while maintaining a stable concentration that is suggested to be under a strong microbial control. Estimated mean diffusion times of acetate between neighboring cells were <1 s, whereas VFA turnover times increased from several hours at the sediment surface to several years at the bottom of the sulfate reduction zone. Thus, diffusion was not limiting the VFA turnover. Despite constant VFA concentrations, the Gibbs energies (ΔGr) of VFA-dependent sulfate reduction decreased downcore, from −28 to −16 kJ (mol formate)−1, −68 to −31 kJ (mol acetate)−1, and −124 to −65 kJ (mol propionate)−1. Thus, ΔGr is apparently not determining the in-situ VFA concentrations directly. However, at the bottom of the sulfate zone of the shelf station, acetoclastic sulfate reduction might operate at its energetic limit at ~ −30 kJ (mol acetate)−1. It is not clear what controls VFA concentrations in the porewater but cell physiological constraints such as energetic costs of VFA activation or uptake could be important. We suggest that such constraints control the substrate turnover and result in a minimum ΔGr that depends on cell physiology and is different for individual substrates. PMID:26379631

Sulfur isotopic constraints from a single enzyme on the cellular to global sulfur cycles

NASA Astrophysics Data System (ADS)

Sim, M. S.; Adkins, J. F.; Sessions, A. L.; Orphan, V. J.; McGlynn, S.

2017-12-01

Since first reported more than a half century ago, sulfur isotope fractionation between sulfate and sulfide has been used as a diagnostic indicator of microbial sulfate reduction, giving added dimensions to the microbial ecological and geochemical studies of the sulfur cycle. A wide range of fractionation has attracted particular attention because it may serve as a potential indicator of environmental or physiological variables such as substrate concentrations or specific respiration rates. In theory, the magnitude of isotope fractionation depends upon the sulfur isotope effect imparted by the involved enzymes and the relative rate of each enzymatic reaction. The former defines the possible range of fractionation quantitatively, while the latter responds to environmental stimuli, providing an underlying rationale for the varying fractionations. The experimental efforts so far have concentrated largely on the latter, the factors affecting the size of fractionation. Recently, however, the direct assessment of intracellular processes emerges as a promising means for the quantitative analysis of microbial sulfur isotope fractionation as a function of environmental or physiological variables. Here, we experimentally determined for the first time the sulfur isotope fractionation during APS reduction, the first reductive step in the dissimilatory sulfate reduction pathway, using the enzyme purified from Desulfovibrio vulgaris Miyazaki. APS reductase carried out the one-step, two-electron reduction of APS to sulfite, without the production of other metabolic intermediates. Nearly identical isotope effects were obtained at two different temperatures, while the rate of APS reduction more than quadrupled with a temperature increase from 20 to 32°C. When placed in context of the linear network model for microbial sulfur isotope fractionation, our finding could provide a new, semi-quantitative constraint on the sulfur cycle at levels from cellular to global.

Impact of anaerobic oxidation of methane on the geochemical cycle of redox-sensitive elements at cold-seep sites of the northern South China Sea

NASA Astrophysics Data System (ADS)

Hu, Yu; Feng, Dong; Liang, Qianyong; Xia, Zhen; Chen, Linying; Chen, Duofu

2015-12-01

Cold hydrocarbon seepage is a frequently observed phenomenon along continental margins worldwide. However, little is known about the impact of seeping fluids on the geochemical cycle of redox-sensitive elements. Pore waters from four gravity cores (D-8, D-5, D-7, and D-F) collected from cold-seep sites of the northern South China Sea were analyzed for SO42-, Mg2+, Ca2+, Sr2+, dissolved inorganic carbon (DIC), δ13CDIC, dissolved Fe, Mn, and trace elements (e.g. Mo, U). The sulfate concentration-depth profiles, δ13CDIC values and (ΔDIC+ΔCa2++ΔMg2+)/ΔSO42- ratios suggest that organoclastic sulfate reduction (OSR) is the dominant process in D-8 core. Besides OSR, anaerobic oxidation of methane (AOM) is partially responsible for depletion of sulfate at D-5 and D-7 cores. The sulfate consumption at D-F core is predominantly caused by AOM. The depth of sulfate-methane interface (SMI) and methane diffusive flux of D-F core are calculated to be ~7 m and 0.035 mol m-2 yr-1, respectively. The relatively shallow SMI and high methane flux at D-F core suggest the activity of gas seepage in this region. The concentrations of dissolved uranium (U) were inferred to decrease significantly within the iron reduction zone. It seems that AOM has limited influence on the U geochemical cycling. In contrast, a good correlation between the consumption of sulfate and the removal of molybdenum (Mo) suggests that AOM has a significantly influence on the geochemical cycle of Mo at cold seeps. Accordingly, cold seep environments may serve as an important potential sink in the marine geochemical cycle of Mo.

Bacterial dissimilatory reduction of arsenic(V) to arsenic(III) in anoxic sediments

USGS Publications Warehouse

Dowdle, P.R.; Laverman, A.M.; Oremland, R.S.

1996-01-01

Incubation of anoxic salt marsh sediment slurries with 10 mM As(V) resulted in the disappearance over time of the As(V) in conjunction with its recovery as As(III). No As(V) reduction to As(III) occurred in heat- sterilized or formalin-killed controls or in live sediments incubated in air. The rate of As(V) reduction in slurries was enhanced by addition of the electron donor lactate, H2, or glucose, whereas the respiratory inhibitor/uncoupler dinitrophenol, rotenone, or 2-heptyl-4-hydroxyquinoline N-oxide blocked As(V) reduction. As(V) reduction was also inhibited by tungstate but not by molybdate, sulfate, or phosphate. Nitrate inhibited As(V) reduction by its action as a preferred respiratory electron acceptor rather than as a structural analog of As(V). Nitrate-respiring sediments could reduce As(V) to As(III) once all the nitrate was removed. Chloramphenicol blocked the reduction of As(V) to As(III) in nitrate- respiring sediments, suggesting that nitrate and arsenate were reduced by separate enzyme systems. Oxidation of [2-14C]acetate to 14CO2 by salt marsh and freshwater sediments was coupled to As(V). Collectively, these results show that reduction of As(V) in sediments proceeds by a dissimilatory process. Bacterial sulfate reduction was completely inhibited by As(V) as well as by As(III).

Bio-reduction of N-nitrosodimethylamine (NDMA) using a hydrogen-based membrane biofilm reactor.

PubMed

Chung, Jinwook; Ahn, Chang-Hoon; Chen, Zhuo; Rittmann, Bruce E

2008-01-01

N-Nitrosodimethylamine (NDMA) is a disinfection by-product shown to be carcinogenic, mutagenic, and teratogenic. A feasible detoxification pathway for NDMA is a three-step bio-reduction that leads to ammonia and dimethylamine. This study examines the bio-reduction of NDMA in a H2-based membrane biofilm reactor (MBfR) that also is active in nitrate and sulfate reductions. In particular, the study investigates the effects of H2 availability and the relative loadings of NDMA, nitrate, and sulfate, which potentially are competing electron acceptors. The results demonstrate that NDMA was bio-reduced to a major extent (i.e., at least 96%) in a H2-based MBfR in which the electron-equivalent fluxes from H2 oxidation were dominated by nitrate and sulfate reductions. NDMA reduction kinetics responded to NDMA concentration, H2 pressure, and the presence of competing acceptors. The most important factor controlling NDMA-reduction kinetics was the H2 availability, controlled primarily by the H2 pressure, and secondarily by competition from nitrate reduction.

High Magnetic Susceptibility in a Highly Saline Sulfate-Rich Aquifer Undergoing Biodegradation of Hydrocarbon Results from Sulfate Reduction.

NASA Astrophysics Data System (ADS)

Atekwana, E. A.; Enright, A.; Ntarlagiannis, D.; Slater, L. D.; Bernier, R.; Beaver, C. L.; Rossbach, S.

2016-12-01

We investigated the chemical and stable carbon isotope composition of groundwater in a highly saline aquifer contaminated with hydrocarbon. Our aim to evaluate hydrocarbon degradation and to constrain the geochemical conditions that generated high anomalous magnetic susceptibility (MS) signatures observed at the water table interface. The occurrence of high MS in the water table fluctuating zone has been attributed to microbial iron reduction, suggesting the use of MS as a proxy for iron cycling. The highly saline aquifer had total dissolved solids concentrations of 3.7 to 29.3 g/L and sulfate concentrations of 787 to 37,100 mg/L. We compared our results for groundwater locations with high hydrocarbon contamination (total petroleum hydrocarbon (TPH) >10 mg/L), at lightly contaminated (TPH <10 mg/L) and locations with no contaminations. Our results for the terminal electron acceptors (TEAs) dissolved oxygen (DO), nitrate (NO3-), dissolved iron (Fe2+) , dissolved manganese (Mn2+), sulfate (SO42-) and methane (CH4) suggest a chemically heterogeneous aquifer, probably controlled by heterogeneous distribution of TEAs and contamination (type of hydrocarbon, phase and age of contamination). The concentrations of dissolved inorganic carbon (DIC) ranged from 67 to 648 mg C/L and the stable carbon isotope (δ13CDIC) ranged from -30.0‰ to 1.0 ‰ and DIC-δ13CDIC modeling indicates that the carbon in the DIC is derived primarily from hydrocarbon degradation. The concentrations of Fe2+ in the aquifer ranged from 0.1 to 55.8 mg/L, but was mostly low, averaging 2.7+10.9 mg/L. Given the low Fe2+ [AE1] in the aqueous phase and the high MS at contaminated locations, we suggest that the high MS observed does not arise from iron reduction but rather from sulfate reduction. Sulfate reduction produces H2S which reacts with Fe2+ to produce ferrous sulfide (Fe2+S) or the mixed valence greigite (Fe2+Fe3+2S4). We conclude that in highly saline aquifers with high concentrations of sulfate and contaminated with hydrocarbon, dominance of sulfate reduction as the TEA is responsible for iron cycling and therefore the high MS associated with biodegradation. [AE1]What about sulfate concentrations? And the range in salinity? You need to add these values to the bastrcat

Apparent Minimum Free Energy Requirements for Methanogenic Archaea and Sulfate-Reducing Bacteria in an Anoxic Marine Sediment

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Alperin, Marc J.; Albert, Daniel B.; Martens, Christopher S.; DeVincenzi, Don (Technical Monitor)

2000-01-01

Among the most fundamental constraints governing the distribution of microorganisms in the environment is the availability of chemical energy at biologically useful levels. To assess the minimum free energy yield that can support microbial metabolism in situ, we examined the thermodynamics of H2-consuming processes in anoxic sediments from Cape Lookout Bight, NC, USA. Depth distributions of H2 partial pressure, along with a suite of relevant concentration data, were determined in sediment cores collected in November (at 14.5 C) and August (at 27 C) and used to calculate free energy yields for methanogenesis and sulfate reduction. At both times of year, and for both processes, free energy yields gradually decreased (became less negative) with depth before reaching an apparent asymptote. Sulfate reducing bacteria exhibited an asymptote of -19.1 +/- 1.7 kj(mol SO4(2-)(sup -1) while methanogenic archaea were apparently supported by energy yields as small as -10.6 +/- 0.7 kj(mol CH4)(sup -1).

Drought stress in maize causes differential acclimation responses of glutathione and sulfur metabolism in leaves and roots.

PubMed

Ahmad, Nisar; Malagoli, Mario; Wirtz, Markus; Hell, Ruediger

2016-11-09

Drought is the most important environmental stress that limits crop yield in a global warming world. Despite the compelling evidence of an important role of oxidized and reduced sulfur-containing compounds during the response of plants to drought stress (e.g. sulfate for stomata closure or glutathione for scavenging of reactive oxygen species), the assimilatory sulfate reduction pathway is almost not investigated at the molecular or at the whole plant level during drought. In the present study, we elucidated the role of assimilatory sulfate reduction in roots and leaves of the staple crop maize after application of drought stress. The time-resolved dynamics of the adaption processes to the stress was analyzed in a physiological relevant situation -when prolonged drought caused significant oxidation stress but root growth should be maintained. The allocation of sulfate was significantly shifted to the roots upon drought and allowed for significant increase of thiols derived from sulfate assimilation in roots. This enabled roots to produce biomass, while leaf growth was stopped. Accumulation of harmful reactive oxygen species caused oxidation of the glutathione pool and decreased glutathione levels in leaves. Surprisingly, flux analysis using [ 35 S]-sulfate demonstrated a significant down-regulation of sulfate assimilation and cysteine synthesis in leaves due to the substantial decrease of serine acetyltransferase activity. The insufficient cysteine supply caused depletion of glutathione pool in spite of significant transcriptional induction of glutathione synthesis limiting GSH1. Furthermore, drought impinges on transcription of membrane-localized sulfate transport systems in leaves and roots, which provides a potential molecular mechanism for the reallocation of sulfur upon prolonged water withdrawal. The study demonstrated a significant and organ-specific impact of drought upon sulfate assimilation. The sulfur metabolism related alterations at the transcriptional, metabolic and enzyme activity level are consistent with a promotion of root growth to search for water at the expense of leaf growth. The results provide evidence for the importance of antagonistic regulation of sulfur metabolism in leaves and roots to enable successful drought stress response at the whole plant level.

40 CFR 415.222 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... SOURCE CATEGORY Titanium Dioxide Production Subcategory § 415.222 Effluent limitations guidelines... point source subject to this subpart and producing titanium dioxide by the sulfate process must achieve... application of the best practicable control technology currently available (BPT): Subpart V—Titanium Dioxide...

40 CFR 415.222 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... SOURCE CATEGORY Titanium Dioxide Production Subcategory § 415.222 Effluent limitations guidelines... point source subject to this subpart and producing titanium dioxide by the sulfate process must achieve... application of the best practicable control technology currently available (BPT): Subpart V—Titanium Dioxide...

40 CFR 415.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... CATEGORY Titanium Dioxide Production Subcategory § 415.223 Effluent limitations guidelines representing the... to this subpart and producing titanium dioxide by the sulfate process must achieve the following..., any existing point source subject to this subpart and producing titanium dioxide by the chloride...

40 CFR 415.222 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... SOURCE CATEGORY Titanium Dioxide Production Subcategory § 415.222 Effluent limitations guidelines... point source subject to this subpart and producing titanium dioxide by the sulfate process must achieve... application of the best practicable control technology currently available (BPT): Subpart V—Titanium Dioxide...

40 CFR 415.222 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... SOURCE CATEGORY Titanium Dioxide Production Subcategory § 415.222 Effluent limitations guidelines... point source subject to this subpart and producing titanium dioxide by the sulfate process must achieve... application of the best practicable control technology currently available (BPT): Subpart V—Titanium Dioxide...

40 CFR 415.222 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... SOURCE CATEGORY Titanium Dioxide Production Subcategory § 415.222 Effluent limitations guidelines... point source subject to this subpart and producing titanium dioxide by the sulfate process must achieve... application of the best practicable control technology currently available (BPT): Subpart V—Titanium Dioxide...

40 CFR 415.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... CATEGORY Titanium Dioxide Production Subcategory § 415.223 Effluent limitations guidelines representing the... to this subpart and producing titanium dioxide by the sulfate process must achieve the following..., any existing point source subject to this subpart and producing titanium dioxide by the chloride...

40 CFR 418.12 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS FERTILIZER MANUFACTURING POINT SOURCE CATEGORY... waters. (b) Process wastewater pollutants from a calcium sulfate storage pile runoff facility operated... a surge capacity equal to the runoff from the 10-year, 24-hour rainfall event may be discharged...

40 CFR 418.12 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS FERTILIZER MANUFACTURING POINT SOURCE CATEGORY... waters. (b) Process wastewater pollutants from a calcium sulfate storage pile runoff facility operated... a surge capacity equal to the runoff from the 10-year, 24-hour rainfall event may be discharged...

40 CFR 418.12 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS FERTILIZER MANUFACTURING POINT SOURCE CATEGORY... waters. (b) Process wastewater pollutants from a calcium sulfate storage pile runoff facility operated... a surge capacity equal to the runoff from the 10-year, 24-hour rainfall event may be discharged...

METHANOGENESIS AND SULFATE REDUCTION IN CHEMOSTATS: II. MODEL DEVELOPMENT AND VERIFICATION

EPA Science Inventory

A comprehensive dynamic model is presented that simulates methanogenesis and sulfate reduction in a continuously stirred tank reactor (CSTR). This model incorporates the complex chemistry of anaerobic systems. A salient feature of the model is its ability to predict the effluent ...

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

NASA Astrophysics Data System (ADS)

Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

2010-02-01

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II) (aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III) (s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

Arsenic Repartitioning during Biogenic Sulfidization and Transformation of Ferrihydrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kocar, B.; Borch, T; Fendorf, S

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within themore » zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II){sub (aq)} concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III){sub (s)} depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.« less

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within themore » zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yung, M. M.; Cheah, S.; Magrini-Bair, K.

Sulfur K-edge XANES identified transformation of sulfides to sulfates during combined steam and air regeneration on a Ni/Mg/K/Al2O3 catalyst used to condition biomass-derived syngas. This catalyst was tested over multiple reaction/regeneration/reduction cycles. Postreaction catalysts showed the presence of sulfides on H2S-poisoned sites. Although H2S was observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst, and a transformation from sulfides to sulfates was observed. Following the oxidative regeneration, the subsequent H2 reduction led to a partial reduction of sulfates back to sulfides, indicating the difficulty and sensitivity in achieving complete sulfur removal during regeneration for biomass-conditioning catalysts.

Iron Reduction and Carbonate Precipitation by Shewanella oneidensis

NASA Astrophysics Data System (ADS)

Zeng, Z.; Tice, M. M.

2011-12-01

This study is to contribute to better understanding of how Archean microbes induced carbonate diagenesis in mats and stromatolites. Previous studies showed sulfate reduction, a common promoter of carbonate precipitation in modern mats[1], is likely to have been less effective in Archean mats in marine fluids lower in sulfate[2]. Alternatively, iron reduction produces far more alkalinity per unit carbon respired than sulfate reduction. Therefore, we hypothesize iron reduction can promote much more carbonate precipitation than sulfate reduction. Our study might also have some relevance to banded iron formation on which microbial iron reduction played a potential role[3]. To test our hypothesis, Shewanella oneidensis MR-1, a dissimilatory iron reducing bacterium will be cultured anaerobically (79%N2, 20%CO2 and 1%H2) in basal medium to trigger iron reduction. Lactate will be used as electron donor, and the electron acceptor will be fresh ferrihydrite. Culture medium will be added with various metal ions, such as Ca2+ and Mg2+, to obtain potential carbonate precipitate. Escherichia coli (with fumarate added as an electron acceptor) will be used to provide a comparison to live but non-iron- reduction cells. After 20 days incubation, precipitate will be collected, washed and identified by X-ray diffraction (XRD). Besides, iron reduction rate (ferrozine assay)[4], PH and amount of precipitate (carbonate and oxidize fractions)[5] will be measured over time to well understand how S. oneidensis drives carbonate precipitation.

Constraining pathways of microbial mediation for carbonate concretions of the Miocene Monterey Formation using carbonate-associated sulfate

NASA Astrophysics Data System (ADS)

Loyd, Sean J.; Berelson, William M.; Lyons, Timothy W.; Hammond, Douglas E.; Corsetti, Frank A.

2012-02-01

Carbonate concretions can form as a result of organic matter degradation within sediments. However, the ability to determine specific processes and timing relationships to particular concretions has remained elusive. Previously employed proxies (e.g., carbon and oxygen isotopes) cannot uniquely distinguish among diagenetic alkalinity sources generated by microbial oxidation of organic matter using oxygen, nitrate, metal oxides, and sulfate as electron acceptors, in addition to degradation by thermal decarboxylation. Here, we employ concentrations of carbonate-associated sulfate (CAS) and δ 34S CAS (along with more traditional approaches) to determine the specific nature of concretion authigenesis within the Miocene Monterey Formation. Integrated geochemical analyses reveal that at least three specific organo-diagenetic reaction pathways can be tied to concretion formation and that these reactions are largely sample-site specific. One calcitic concretion from the Phosphatic Shale Member at Naples Beach yields δ 34S CAS values near Miocene seawater sulfate (˜+22‰ VCDT), abundant CAS (ca. 1000 ppm), depleted δ 13C carb (˜-11‰ VPDB), and very low concentrations of Fe (ca. 700 ppm) and Mn (ca. 15 ppm)—characteristics most consistent with shallow formation in association with organic matter degradation by nitrate, iron-oxides and/or minor sulfate reduction. Cemented concretionary layers of the Phosphatic Shale Member at Shell Beach display elevated δ 34S CAS (up to ˜+37‰), CAS concentrations of ˜600 ppm, mildly depleted δ 13C carb (˜-6‰), moderate amounts of Mn (ca. 250 ppm), and relatively low Fe (ca. 1700 ppm), indicative of formation in sediments dominated by sulfate reduction. Finally, concretions within a siliceous host at Montaña de Oro and Naples Beach show minimal CAS concentrations, positive δ 13C values, and the highest concentrations of Fe (ca. 11,300 ppm) and Mn (ca. 440 ppm), consistent with formation in sediments experiencing methanogenesis in a highly reducing environment. This study highlights the promise in combining CAS analysis with more traditional techniques to differentiate among diagenetic reactions as preserved in the geologic record and shows potential for unraveling subsurface biospheric processes in ancient samples with a high degree of specificity.

Sulfate-reducing mixed communities with the ability to generate bioelectricity and degrade textile diazo dye in microbial fuel cells.

PubMed

Miran, Waheed; Jang, Jiseon; Nawaz, Mohsin; Shahzad, Asif; Lee, Dae Sung

2018-06-15

The biotreatment of recalcitrant wastes in microbial fuel cells (MFCs) rather than chemical, physical, and advanced oxidation processes is a low-cost and eco-friendly process. In this study, sulfate-reducing mixed communities in MFC anodic chamber were employed for simultaneous electricity generation, dye degradation, and sulfate reduction. A power generation of 258 ± 10 mW/m 2 was achieved under stable operating conditions in the presence of electroactive sulfate-reducing bacteria (SRB). The SRBs dominant anodic chambers result in dye, chemical oxygen demand (COD), and sulfate removal of greater than 85% at an initial COD (as lactate)/SO 4 2- mass ratio of 2.0 and dye concentration of 100 mg/L. The effects of the COD/SO 4 2- ratio (5.0:1.0-0.5:1.0) and initial diazo dye concentration (100-1000 mg/L) were studied to evaluate and optimize the MFC performance. Illumina Miseq technology for bacterial community analysis showed that Proteobacteria (89.4%), Deltaproteobacteria (52.7%), and Desulfovibrio (48.2%) were most dominant at phylum, class, and genus levels, respectively, at the MFC anode. Integration of anaerobic SRB culture in MFC bioanode for recalcitrant chemical removal and bioenergy generation may lead to feasible option than the currently used technologies in terms of overall pollutant treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Oxygen Reduction Reaction on PtCo Nanocatalyst: (Bi)sulfate Anion Poisoning

NASA Astrophysics Data System (ADS)

Liu, Jie; Huang, Yan

2018-05-01

Pt alloy electrocatalysts are susceptible to anion adsorption in the working environment of fuel cells. In this work, the unavoidable bisulfate and sulfate ((bi)sulfate) poisoning of the oxygen reduction reaction (ORR) on a common PtCo nanocatalyst was studied by the rotating disk electrode (RDE) technique, for the first time to the best of our knowledge. The specific activity decreases linearly with the logarithm of (bi)sulfate concentration under various high potentials. This demonstrates that the (bi)sulfate adsorption does not affect the free energy of ORR activation at a given potential. Moreover, it is speculated that these two conditions, the adsorption of one O2 molecule onto two Pt sites and this adsorption as a rate-determining step of ORR reaction, are unlikely to exist simultaneously.

Treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron.

PubMed

Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, James A

2016-05-05

This study assessed the bioremediation of acid rock drainage (ARD) in flow-through columns testing zero-valent iron (ZVI) for the first time as the sole exogenous electron donor to drive sulfate-reducing bacteria in permeable reactive barriers. Columns containing ZVI, limestone or a mixture of both materials were inoculated with an anaerobic mixed culture and fed a synthetic ARD containing sulfuric acid and heavy metals (initially copper, and later also cadmium and lead). ZVI significantly enhanced sulfate reduction and the heavy metals were extensively removed (>99.7%). Solid-phase analyses showed that heavy metals were precipitated with biogenic sulfide in the columns packed with ZVI. Excess sulfide was sequestered by iron, preventing the discharge of dissolved sulfide. In the absence of ZVI, heavy metals were also significantly removed (>99.8%) due to precipitation with hydroxide and carbonate ions released from the limestone. Vertical-profiles of heavy metals in the columns packing, at the end of the experiment, demonstrated that the ZVI columns still had excess capacity to remove heavy metals, while the capacity of the limestone control column was approaching saturation. The ZVI provided conditions that enhanced sulfate reduction and generated alkalinity. Collectively, the results demonstrate an innovative passive ARD remediation process using ZVI as sole electron-donor. Copyright © 2016 Elsevier B.V. All rights reserved.

Microbial Community Composition and Functional Capacity in a Terrestrial Ferruginous, Sulfate-Depleted Mud Volcano

PubMed Central

Tu, Tzu-Hsuan; Wu, Li-Wei; Lin, Yu-Shih; Imachi, Hiroyuki; Lin, Li-Hung; Wang, Pei-Ling

2017-01-01

Terrestrial mud volcanoes (MVs) are an important natural source of methane emission. The role of microbial processes in methane cycling and organic transformation in such environments remains largely unexplored. In this study, we aim to uncover functional potentials and community assemblages across geochemical transitions in a ferruginous, sulfate-depleted MV of eastern Taiwan. Geochemical profiles combined with 16S rRNA gene abundances indicated that anaerobic oxidation of methane (AOM) mediated by ANME-2a group coincided with iron/manganese reduction by Desulfuromonadales at shallow depths deprived of sulfate. The activity of AOM was stimulated either by methane alone or by methane and a range of electron acceptors, such as sulfate, ferrihydrite, and artificial humic acid. Metagenomic analyses revealed that functional genes for AOM and metal reduction were more abundant at shallow intervals. In particular, genes encoding pili expression and electron transport through multi-heme cytochromes were prevalent, suggesting potential intercellular interactions for electron transport involved in AOM. For comparison, genes responsible for methanogenesis and degradation of chitin and plant-derived molecules were more abundant at depth. The gene distribution combined with the enhanced proportions of 16S rRNA genes related to methanogens and heterotrophs, and geochemical characteristics suggest that particulate organic matter was degraded into various organic entities that could further fuel in situ methanogenesis. Finally, genes responsible for aerobic methane oxidation were more abundant in the bubbling pool and near-surface sediments. These methane oxidizers account for the ultimate attenuation of methane discharge into the atmosphere. Overall, our results demonstrated that various community members were compartmentalized into stratified niches along geochemical gradients. These community members form a metabolic network that cascades the carbon transformation from the upstream degradation of recalcitrant organic carbon with fermentative production of labile organic entities and methane to downstream methane oxidation and metal reduction near the surface. Such a metabolic architecture enables effective methane removal under ferruginous, sulfate-depleted conditions in terrestrial MVs. PMID:29163423

Microbial Community Composition and Functional Capacity in a Terrestrial Ferruginous, Sulfate-Depleted Mud Volcano.

PubMed

Tu, Tzu-Hsuan; Wu, Li-Wei; Lin, Yu-Shih; Imachi, Hiroyuki; Lin, Li-Hung; Wang, Pei-Ling

2017-01-01

Terrestrial mud volcanoes (MVs) are an important natural source of methane emission. The role of microbial processes in methane cycling and organic transformation in such environments remains largely unexplored. In this study, we aim to uncover functional potentials and community assemblages across geochemical transitions in a ferruginous, sulfate-depleted MV of eastern Taiwan. Geochemical profiles combined with 16S rRNA gene abundances indicated that anaerobic oxidation of methane (AOM) mediated by ANME-2a group coincided with iron/manganese reduction by Desulfuromonadales at shallow depths deprived of sulfate. The activity of AOM was stimulated either by methane alone or by methane and a range of electron acceptors, such as sulfate, ferrihydrite, and artificial humic acid. Metagenomic analyses revealed that functional genes for AOM and metal reduction were more abundant at shallow intervals. In particular, genes encoding pili expression and electron transport through multi-heme cytochromes were prevalent, suggesting potential intercellular interactions for electron transport involved in AOM. For comparison, genes responsible for methanogenesis and degradation of chitin and plant-derived molecules were more abundant at depth. The gene distribution combined with the enhanced proportions of 16S rRNA genes related to methanogens and heterotrophs, and geochemical characteristics suggest that particulate organic matter was degraded into various organic entities that could further fuel in situ methanogenesis. Finally, genes responsible for aerobic methane oxidation were more abundant in the bubbling pool and near-surface sediments. These methane oxidizers account for the ultimate attenuation of methane discharge into the atmosphere. Overall, our results demonstrated that various community members were compartmentalized into stratified niches along geochemical gradients. These community members form a metabolic network that cascades the carbon transformation from the upstream degradation of recalcitrant organic carbon with fermentative production of labile organic entities and methane to downstream methane oxidation and metal reduction near the surface. Such a metabolic architecture enables effective methane removal under ferruginous, sulfate-depleted conditions in terrestrial MVs.

Biochemistry, physiology and biotechnology of sulfate-reducing bacteria.

PubMed

Barton, Larry L; Fauque, Guy D

2009-01-01

Chemolithotrophic bacteria that use sulfate as terminal electron acceptor (sulfate-reducing bacteria) constitute a unique physiological group of microorganisms that couple anaerobic electron transport to ATP synthesis. These bacteria (220 species of 60 genera) can use a large variety of compounds as electron donors and to mediate electron flow they have a vast array of proteins with redox active metal groups. This chapter deals with the distribution in the environment and the major physiological and metabolic characteristics of sulfate-reducing bacteria (SRB). This chapter presents our current knowledge of soluble electron transfer proteins and transmembrane redox complexes that are playing an essential role in the dissimilatory sulfate reduction pathway of SRB of the genus Desulfovibrio. Environmentally important activities displayed by SRB are a consequence of the unique electron transport components or the production of high levels of H(2)S. The capability of SRB to utilize hydrocarbons in pure cultures and consortia has resulted in using these bacteria for bioremediation of BTEX (benzene, toluene, ethylbenzene and xylene) compounds in contaminated soils. Specific strains of SRB are capable of reducing 3-chlorobenzoate, chloroethenes, or nitroaromatic compounds and this has resulted in proposals to use SRB for bioremediation of environments containing trinitrotoluene and polychloroethenes. Since SRB have displayed dissimilatory reduction of U(VI) and Cr(VI), several biotechnology procedures have been proposed for using SRB in bioremediation of toxic metals. Additional non-specific metal reductase activity has resulted in using SRB for recovery of precious metals (e.g. platinum, palladium and gold) from waste streams. Since bacterially produced sulfide contributes to the souring of oil fields, corrosion of concrete, and discoloration of stonework is a serious problem, there is considerable interest in controlling the sulfidogenic activity of the SRB. The production of biosulfide by SRB has led to immobilization of toxic metals and reduction of textile dyes, although the process remains unresolved, SRB play a role in anaerobic methane oxidation which not only contributes to carbon cycle activities but also depletes an important industrial energy reserve.

Benzene oxidation coupled to sulfate reduction

USGS Publications Warehouse

Lovley, D.R.; Coates, J.D.; Woodward, J.C.; Phillips, E.J.P.

1995-01-01

Highly reduced sediments from San Diego Bay, Calif., that were incubated under strictly anaerobic conditions metabolized benzene within 55 days when they were exposed initially to I ??M benzene. The rate of benzene metabolism increased as benzene was added back to the benzene-adapted sediments. When a [14C]benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as 14CO2. Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of 14CO2 from [14C]benzene. Benzene metabolism stopped when the sediments became sulfate depleted, and benzene uptake resumed when sulfate was added again. The stoichiometry of benzene uptake and sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for benzene oxidation. Isotope trapping experiments performed with [14C]benzene revealed that there was no production of such potential extracellular intermediates of benzene oxidation as phenol, benzoate, p-hydroxybenzoate, cyclohexane, catechol, and acetate. The results demonstrate that benzene can be oxidized in the absence of O2, with sulfate serving as the electron acceptor, and suggest that some sulfate reducers are capable of completely oxidizing benzene to carbon dioxide without the production of extracellular intermediates. Although anaerobic benzene oxidation coupled to chelated Fe(III) has been documented previously, the study reported here provides the first example of a natural sediment compound that can serve as an electron acceptor for anaerobic benzene oxidation.

Understanding the response of Desulfovibrio desulfuricans ATCC 27774 to the electron acceptors nitrate and sulfate - biosynthetic costs modulate substrate selection.

PubMed

Sousa, Joana R; Silveira, Célia M; Fontes, Pedro; Roma-Rodrigues, Catarina; Fernandes, Alexandra R; Van Driessche, Gonzalez; Devreese, Bart; Moura, Isabel; Moura, José J G; Almeida, M Gabriela

2017-11-01

Sulfate-reducing bacteria (SRB) are a diverse group of anaerobic microorganisms that obtain their energy from dissimilatory sulfate reduction. Some SRB species have high respiratory versatility due to the possible use of alternative electron acceptors. A good example is Desulfovibrio desulfuricans ATCC 27774, which grows in the presence of nitrate (end product: ammonium) with higher rates and yields to those observed in sulfate containing medium (end product: sulfide). In this work, the mechanisms supporting the respiratory versatility of D. desulfuricans were unraveled through the analysis of the proteome of the bacterium under different experimental conditions. The most remarkable difference in the two-dimensional gel electrophoresis maps is the high number of spots exclusively represented in the nitrate medium. Most of the proteins with increase abundance are involved in the energy metabolism and the biosynthesis of amino acids (or proteins), especially those participating in ammonium assimilation processes. qPCR analysis performed during different stages of the bacterium's growth showed that the genes involved in nitrate and nitrite reduction (napA and nrfA, respectively) have different expressions profiles: while napA did not vary significantly, nrfA was highly expressed at a 6h time point. Nitrite levels measured along the growth curve revealed a peak at 3h. Thus, the initial consumption of nitrate and concomitant production of nitrite must induce nrfA expression. The activation of alternative mechanisms for energy production, aside several N-assimilation metabolisms and detoxification processes, solves potential survival problems in adapting to different environments and contributes to higher bacterial growth rates. Copyright © 2017 Elsevier B.V. All rights reserved.

Desulfofrigus sp. prevails in sulfate-reducing dilution cultures from sediments of the Benguela upwelling area.

PubMed

Kraft, Beate; Engelen, Bert; Goldhammer, Tobias; Lin, Yu-Shih; Cypionka, Heribert; Könneke, Martin

2013-04-01

Sediments of coastal upwelling areas are generally characterized by a high content of organic carbon that is mainly degraded via anaerobic microbial processes including sulfate reduction as a major terminal oxidation step. Despite the high importance of sulfate reduction in these sediments, the identity of sulfate-reducing bacteria (SRB) has remained almost unknown. Here, we applied a cultivation-based approach using selective enrichment conditions to study the diversity and distribution of active SRB in sediments along a transect perpendicular to the continental slope off the coast of Namibia (Meteor-cruise M76/1). To promote growth of the most abundant SRB, dilution series were prepared and amended with hydrogen, acetate, or a mixture of monomers representing typical substrates for SRB. Growth of SRB could be detected in the presence of all electron donors and from sediment down to 4 m depth. 16S rRNA gene-based DGGE analysis and sequencing revealed the predominance of SRB related to psychrophiles in particular to the genus Desulfofrigus, which made up 1 % of the total microbial community, accounting for an absolute abundance of up to 4.8 × 10(7)  cells mL(-1) . In general, the abundance of cultured SRB changed with depth and between the different sampling sites and correlated with the content of organic carbon as previously reported. Growth of chemolithotrophic SRB in relatively high dilution steps and the enrichment of methanogens as well as acetogens from deeper sediment point to a competition between hydrogen-utilizing microbial processes and their biogeochemical significance in deep sediment layers of the Benguela upwelling area. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Biological sulfate removal from construction and demolition debris leachate: effect of bioreactor configuration.

PubMed

Kijjanapanich, Pimluck; Do, Anh Tien; Annachhatre, Ajit P; Esposito, Giovanni; Yeh, Daniel H; Lens, Piet N L

2014-03-30

Due to the contamination of construction and demolition debris (CDD) by gypsum drywall, especially, its sand fraction (CDD sand, CDDS), the sulfate content in CDDS exceeds the posed limit of the maximum amount of sulfate present in building sand (1.73 g sulfate per kg of sand for the Netherlands). Therefore, the CDDS cannot be reused for construction. The CDDS has to be washed in order to remove most of the impurities and to obtain the right sulfate content, thus generating a leachate, containing high sulfate and calcium concentrations. This study aimed at developing a biological sulfate reduction system for CDDS leachate treatment and compared three different reactor configurations for the sulfate reduction step: the upflow anaerobic sludge blanket (UASB) reactor, inverse fluidized bed (IFB) reactor and gas lift anaerobic membrane bioreactor (GL-AnMBR). This investigation demonstrated that all three systems can be applied for the treatment of CDDS leachate. The highest sulfate removal efficiency of 75-85% was achieved at a hydraulic retention time (HRT) of 15.5h. A high calcium concentration up to 1,000 mg L(-1) did not give any adverse effect on the sulfate removal efficiency of the IFB and GL-AnMBR systems. Copyright © 2013 Elsevier B.V. All rights reserved.

Arsenophilic Bacterial Processes in Searles Lake: A Salt-saturated, Arsenic-rich, Alkaline Soda Lake.

NASA Astrophysics Data System (ADS)

Oremland, R. S.; Kulp, T. R.; Hoeft, S. E.; Miller, L. G.; Swizer Blum, J.; Stolz, J. F.

2005-12-01

Searles Lake, located in the Mojave Desert of California, is essentially a chemically-similar, concentrated version of Mono Lake, but having a much higher salinity (e.g., 340 vs. 90 g/L) and a greater dissolved inorganic arsenic content in its brine (e.g., 3.9 vs. 0.2 mM). The source of all this arsenic ultimately comes from hydrothermal spring inputs, thereby underscoring the importance of volcanic and fluvial processes in transporting this toxic element into these closed basin lakes. Nonetheless, the presence of microbial activities with regard to respiration of arsenate oxyanions under anaerobic conditions and the oxidation of arsenite oxyanions under aerobic conditions can be inferred from porewater profiles taken from handcores retrieved beneath Searles Lake's salt crust. Sediment slurry incubations confirmed biological arsenate respiration and arsenite oxidation, with the former processes notably enhanced by provision of the inorganic electron donor sulfide or H2. Hence, arsenic-linked chemo-autotrophy appears to be an important means of carbon fixation in this system. Subsequent efforts using 73As-arsenate as radiotracer detected dissimilatory arsenate reduction activity down the length of the core, but we were unable to detect any evidence for sulfate-reduction using 35S-sulfate. An extremely halophilic anaerobic bacterium of the order Haloanaerobiales [strain SLAS-1] was isolated from the sediments that grew via arsenate respiration using lactate or sulfide as its electron donors. These results show that, unlike sulfate-reduction, arsenic metabolism (i.e., both oxidation of arsenite and dissimilatory reduction of arsenate) is operative and even vigorous under the extreme conditions of salt-saturation and high pH. The occurrence of arsenophilic microbial processes in Searles Lake is relevant to the search for extant or extinct microbial life on Mars. It is evident from surface imagery that Mars had past episodes of volcanism, fluvial transport, and most likely brine concentration reactions (e.g., evapo- and cryo-concentration) occurring in its early Noachian/Hesperian epochs. We speculate that these processes may have created arsenic-rich, dense brines on the Martian surface or even within its underlying regolith. Whether such brines persisted long enough for prokaryotic life to evolve in them, and if so, was such life capable of adapting to and exploiting arsenic redox reactions for the purpose of generating metabolic energy remain tantalizing, but still hypothetical questions.

Biological conversion of anglesite (PbSO(4)) and lead waste from spent car batteries to galena (PbS).

PubMed

Weijma, Jan; De Hoop, Klaas; Bosma, Wobby; Dijkman, Henk

2002-01-01

Lead paste, a solid mixture containing PbSO(4), PbO(2), PbO/Pb(OH)(2) precipitate, and elemental Pb, is one of the main waste fractions from spent car batteries. Biological sulfidation represents a new process for recovery of lead from this waste. In this process the lead salts in lead paste are converted to galena (PbS) by sulfate-reducing bacteria. This paper investigates a continuous process for sulfidation of anglesite (PbSO(4)), the main constituent of lead paste, and lead paste, consisting of a laboratory-scale gas-lift bioreactor to which a slurry of anglesite or lead paste was supplied. Sulfate or elemental sulfur was added as an additional sulfur source. Hydrogen gas served as an electron donor for the biological reduction of sulfate and elemental sulfur to sulfide by sulfate- and sulfur-reducing bacteria. Anglesite was almost completely converted to galena at a loading rate of 19 kg of PbSO(4) m(-)(3) day(-)(1), producing a sludge of which the crystalline lead phases consisted of >98% PbS (galena) and 1-2% elemental Pb. With lead paste, stable sulfidation rates of up to 17 kg of lead paste m(-)(3) day(-)(1) were demonstrated, producing a sludge of which the crystalline lead phases consisted of an estimated >96% PbS, 1-2% elemental Pb, and 1-2% PbO(2).

SULFATE-REDUCING BACTERIA IN THE SEAGRASS RHIZOSPHERE

EPA Science Inventory

Seagrasses are rooted in anoxic sediments that support high levels of microbial activity including utilization of sulfate as a terminal electron acceptor which is reduced to sulfide. Sulfate reduction in seagrass bed sediments is stimulated by input of organic carbon through the ...

Algae as an electron donor promoting sulfate reduction for the bioremediation of acid rock drainage.

PubMed

Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, Jim A

2016-11-05

This study assessed bioremediation of acid rock drainage in simulated permeable reactive barriers (PRB) using algae, Chlorella sorokiniana, as the sole electron donor for sulfate-reducing bacteria. Lipid extracted algae (LEA), the residues of biodiesel production, were compared with whole cell algae (WCA) as an electron donor to promote sulfate-reducing activity. Inoculated columns containing anaerobic granular sludge were fed a synthetic medium containing H2SO4 and Cu(2+). Sulfate, sulfide, Cu(2+) and pH were monitored throughout the experiment of 123d. Cu recovered in the column packing at the end of the experiment was evaluated using sequential extraction. Both WCA and LEA promoted 80% of sulfate removal (12.7mg SO4(2-) d(-1)) enabling near complete Cu removal (>99.5%) and alkalinity generation raising the effluent pH to 6.5. No noteworthy sulfate reduction, alkalinity formation and Cu(2+) removal were observed in the endogenous control. In algae amended-columns, Cu(2+) was precipitated with biogenic H2S produced by sulfate reduction. Formation of CuS was evidenced by sequential extraction and X-ray diffraction. LEA and WCA provided similar levels of electron donor based on the COD balance. The results demonstrate an innovative passive remediation system using residual algae biomass from the biodiesel industry. Copyright © 2016 Elsevier B.V. All rights reserved.

Isotope biogeochemical assessment of natural biodegradation processes in open cast pit mining landscapes

NASA Astrophysics Data System (ADS)

Jeschke, Christina; Knöller, Kay; Koschorreck, Matthias; Ussath, Maria; Hoth, Nils

2014-05-01

In Germany, a major share of the energy production is based on the burning of lignite from open cast pit mines. The remediation and re-cultivation of the former mining areas in the Lusatian and Central German lignite mining district is an enormous technical and economical challenge. After mine closures, the surrounding landscapes are threatened by acid mine drainage (AMD), i.e. the acidification and mineralization of rising groundwater with metals and inorganic contaminants. The high content of sulfur (sulfuric acid, sulfate), nitrogen (ammonium) and iron compounds (iron-hydroxides) deteriorates the groundwater quality and decelerates sustainable development of tourism in (former) mining landscapes. Natural biodegradation or attenuation (NA) processes of inorganic contaminants are considered to be a technically low impact and an economically beneficial solution. The investigations of the stable isotope compositions of compounds involved in NA processes helps clarify the dynamics of natural degradation and provides specific informations on retention processes of sulfate and nitrogen-compounds in mine dump water, mine dump sediment, and residual pit lakes. In an active mine dump we investigated zones where the process of bacterial sulfate reduction, as one very important NA process, takes place and how NA can be enhanced by injecting reactive substrates. Stable isotopes signatures of sulfur and nitrogen components were examined and evaluated in concert with hydrogeochemical data. In addition, we delineated the sources of ammonium pollution in mine dump sediments and investigated nitrification by 15N-labeling techniques to calculate the limit of the conversion of harmful ammonium to nitrate in residual mining lakes. Ultimately, we provided an isotope biogeochemical assessment of natural attenuation of sulfate and ammonium at mine dump sites and mining lakes. Also, we estimated the risk potential for water in different compartments of the hydrological system. In laboratory experiments, we tested reactive materials that may speed up the process of bacterial sulfate reduction. In in-situ experiments, we quantified nitrification rates. Based on the results, we are able to suggest promising technical measures that enhance natural attenuation processes at mine dump site and in mining lakes. The natural water cycle in lignite mining landscapes is heavily impacted by human activities. Basically, nature is capable of cleaning itself to a certain extent after mining activities stopped. However, it is our responsibility to support biogeochemical processes to make them more efficient and more sustainable. Isotopic monitoring proved to be an excellent tool for assessing the relevance and performance of different re-cultivation measures for a positive long-term development of the water quality in large-scale aquatic systems affected by the impact of lignite mining.

Synthetic effect between iron oxide and sulfate mineral on the anaerobic transformation of organic substance.

PubMed

Chen, Tian-Hu; Wang, Jin; Zhou, Yue-Fei; Yue, Zheng-Bo; Xie, Qiao-Qin; Pan, Min

2014-01-01

Synthetic effect between sulfate minerals (gypsum) and iron oxide (hematite) on the anaerobic transformation of organic substance was investigated in the current study. The results showed that gypsum was completely decomposed while hematite was partially reduced. The mineral phase analysis results showed that FeS and CaCO3 was the major mineralization product. Methane generation process was inhibited and inorganic carbon contents in the precipitates were enhanced compared to the control without hematite and gypsum. The inorganic carbon content increased with the increasing of hematite dosages. Co-addition of sulfate minerals and iron oxide would have a potential application prospect in the carbon sequestration area and reduction of the greenhouse gas release. The results would also reveal the role of inorganic mineral in the global carbon cycle. Copyright © 2013 Elsevier Ltd. All rights reserved.

Novel processes for anaerobic sulfate production from elemental sulfur by sulfate-reducing bacteria

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1994-01-01

Sulfate reducers and related organisms which had previously been found to reduce Fe(III) with H2 or organic electron donors oxidized S0 to sulfate when Mn(IV) was provided as an electron acceptor. Organisms catalyzing this reaction in washed cell suspensions included Desulfovibrio desulfuricans, Desulfomicrobium baculatum. Desulfobacterium autotrophicum, Desulfuromonas acetoxidans, and Geobacter metallireducens. These organisms produced little or no sulfate from S0 with Fe(III) as a potential electron acceptor or in the absence of an electron acceptor. In detailed studies with Desulfovibrio desulfuricans, the stoichiometry of sulfate and Mn(II) production was consistent with the reaction S0 + 3 MnO2 + 4H+ ???SO42- + 3Mn(II) + 2H2O. None of the organisms evaluated could be grown with S0 as the sole electron donor and Mn(IV) as the electron acceptor. In contrast to the other sulfate reducers evaluated, Desulfobulbus propionicus produced sulfate from S0 in the absence of an electron acceptor and Fe(III) oxide stimulated sulfate production. Sulfide also accumulated in the absence of Mn(IV) or Fe(III). The stoichiometry of sulfate and sulfide production indicated that Desulfobulbus propionicus disproportionates S0 as follows: 4S0 + 4H2O???SO42- + 3HS- + 5 H+. Growth of Desulfobulbus propionicus with S0 as the electron donor and Fe(III) as a sulfide sink and/or electron acceptor was very slow. The S0 oxidation coupled to Mn(IV) reduction described here provides a potential explanation for the Mn(IV)-dependent sulfate production that previous studies have observed in anoxic marine sediments. Desulfobulbus propionicus is the first example of a pure culture known to disproportionate S0.

Sulfur diagenesis in marine sediments

NASA Technical Reports Server (NTRS)

Goldhaber, M.

1985-01-01

Bacterial sulfate reduction occurs in all marine sediments that contain organic matter. Aqueous sulfide (HS-, H2S), one of the initial products of bacterial sulfide reduction, is extremely reactive with iron bearing minerals: sulfur is fixed into sediments as iron sulfide (first FeS and then Fe2S2). A working definition is given of sulfur diagenesis in marine sediments. Controls and consequences of sulfate reduction rates in marine sediments are examined.

Bacterial Community Succession During in situ Uranium Bioremediation: Spatial Similarities Along Controlled Flow Paths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, Chiachi; Wu, Weimin; Gentry, Terry J.

2009-05-22

Bacterial community succession was investigated in a field-scale subsurface reactor formed by a series of wells that received weekly ethanol additions to re-circulating groundwater. Ethanol additions stimulated denitrification, metal reduction, sulfate reduction, and U(VI) reduction to sparingly soluble U(IV). Clone libraries of SSU rRNA gene sequences from groundwater samples enabled tracking of spatial and temporal changes over a 1.5 y period. Analyses showed that the communities changed in a manner consistent with geochemical variations that occurred along temporal and spatial scales. Canonical correspondence analysis revealed that the levels of nitrate, uranium, sulfide, sulfate, and ethanol strongly correlated with particular bacterialmore » populations. As sulfate and U(VI) levels declined, sequences representative of sulfate-reducers and metal-reducers were detected at high levels. Ultimately, sequences associated with sulfate-reducing populations predominated, and sulfate levels declined as U(VI) remained at low levels. When engineering controls were compared to the population variation via canonical ordination, changes could be related to dissolved oxygen control and ethanol addition. The data also indicated that the indigenous populations responded differently to stimulation for bio-reduction; however, the two bio-stimulated communities became more similar after different transitions in an idiosyncratic manner. The strong associations between particular environmental variables and certain populations provide insight into the establishment of practical and successful remediation strategies in radionuclide-contaminated environments with respect to engineering controls and microbial ecology.« less

Sulfur in serpentinized oceanic peridotites: Serpentinization processes and microbial sulfate reduction

USGS Publications Warehouse

Alt, J.C.; Shanks, Wayne C.

1998-01-01

The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of <1 Ma peridotites at Hess Deep occurred at high temperatures (200??-400??C) and low water/rock ratios. Oxidation of ferrous iron to magnetite maintained low fO2and produced a reduced, low-sulfur assemblage including NiFe alloy. Small amounts of sulfate reduction by thermophilic microbes occurred as the system cooled, producing low-??34S sulfide (1.5??? to -23.7???). In contrast, serpentinization of Iberian Margin peridotites occurred at low temperatures (???20??-200??C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-??34S sulfide (-15 to -43???) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high ??34S of total sulfur (mean ??? 8???). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in ??34S of total sulfur (mean ??? -5???). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 ?? 1012 g S yr-1 from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

Microbe-Mineral Interactions Along Biogeochemical Gradients in Bahamian Stromatolites: Key to Lithification and Preservation

NASA Astrophysics Data System (ADS)

Andres, M. S.; Sumner, D. Y.; Visscher, P. T.; Swart, P. K.; Reid, R. P.

2005-12-01

Understanding on how modern stromatolites form and lithify is critical to properly interpreting the origins of ancient stromatolites and the early evolution of life. Lithification in Bahamian stromatolites is tied to specific, 20-60-micron thick horizons characterized by laterally continuous sheets of microcrystalline carbonate (aragonite). Microbial processes associated with these horizons are 1) photosynthetic production by cyanobacteria and 2) heterotrophic respiration by bacteria as well as the production of extrapolymeric substances (EPS). The aim of this study is to better understand the coupling of microstructure and microbial processes. The competing influences of photosynthetic CO2 uptake, sulfate reduction, and degradation of Ca-binding EPS influence both carbonate saturation states and the isotopic composition of dissolved inorganic carbon (DIC). In Bahamian stromatolites, photosynthesis and sulfate reduction are associated with specific microbial mat types creating distinctive chemical gradients that can be preserved in authigenic carbonate. Aragonite that precipitated within stromatolites is > 1 per mill depleted in 13C relative to aragonite precipitated in equilibrium with local seawater. These data suggest that more aragonite precipitates when and where respiration, rather than photosynthesis, influences local DIC, which is consistent with sulfate reduction promoting carbonate precipitation and calcium release during decay of exopolymeric substances. Biogeochemical gradients vary on a temporal and spatial scale as indicated by in-situ pH measurements across a the living mat. Highest pH correlates to maximum photosynthesis signal in the early afternoon while the lowest pH to that of maximum respiration just before sunrise. Corresponding carbon isotope analysis of authigenic carbonate precipitate will determine when microscale biological activity is captured in the mineral phase and potentially preserved.

Assessing the Potential for Expression of Metabolically Diverse Genes in Subseafloor Sediments

NASA Astrophysics Data System (ADS)

Dick, J. M.; Shock, E.

2009-12-01

A combination of geochemical and biochemical processes defines the transition between sulfate reduction and methanogenesis in subseafloor sediments. One line of investigation that promises to help elucidate this transition is metagenomic characterization of the subseafloor sediment column. Analysis of metagenomic data from sediment at the Peru Margin reveals that sequences homologous to known genes in the methanogenic and sulfate reductive pathways can be identified at different depths below the seafloor [1]. However, without metatranscriptomic or metaprotoeomic data it is unclear whether the presence of these genes implies that these metabolic pathways are being utilized. In this study, we describe a theoretical method for assessing the potential for gene expression. Constructing a thermodynamic model for the relative stabilities of proteins depends on knowing the amino acid sequences of the proteins and defining model environments, which can then be compared and refined using geochemical observations. We report the results of a series of stability calculations that are consistent with a greater overall energetic potential for the expression of enzymes for sulfate reduction and methanogenesis at shallow and deep horizons, respectively. The results are also consistent with a decrease in the oxidation state of the pore fluid with depth, which is mirrored in the chemical compositions of the proteins involved in methanogenesis. At sediment near the seafloor, where genes for both sulfate reduction and methanogenesis were identified [1], fluctuations in oxidation state could be responsible for differing levels of expression of these proteins and therefore contribute to a shift to a different metabolic strategy. [1] J. F. Biddle, S. Fitz-Gibbon, S. C. Schuster, J. E. Brenchley and C. H. House. Proc. Natl. Acad. Sci. U.S.A., 105:10583, 2008. Relative stabilities of sulfite reductases ("sulf") and methylene-5,6,7,8-tetrahydromethanopterin dehydrogenases ("meth") that are homologous to sequences from 1, 16, 32 and 50 meters below seafloor. Filled points indicate a trend of changing fluid compositions that progressively favor formation of the proteins from deeper sediments.

Environmental controls on sulfur isotopic composition of sulfide minerals in seep carbonates from the South China Sea

NASA Astrophysics Data System (ADS)

Gong, S.; Li, N.; Liang, Q.; Chen, D.; Feng, D.

2017-12-01

Authigenic carbonates and pyrite associated with sulfate-driven anaerobic oxidation of methane (AOM) at methane seeps provide archives to explore the biogeochemical processes involved and seepage dynamics over time. The wide range and extremely high δ34Spy value of authigenic sulfide has been used to trace the AOM-related processes. However, the detail mechanism for this is unknown. We proposed the δ34Spy characteristics result from high sulfate reduction rate and its competition with sulfate supply rate. To test this hypothesis, we investigated Mo content, Sr/Ca and Mg/Ca ratios, pyrite content, and its sulfur isotopic compositions in methane-derived carbonates from Site F and Haima in northern South China Sea. Calcite and aragonite were distinguished through the Sr/Ca and Mg/Ca ratios. The data show that aragonites are always associated with relatively low δ34Spy values compared to calcites. The Mo content and pyrite have good linear correlations in both aragonites and calcites, and aragonites have more positive slope than calcites. This indicates that there is more Mo available from seawater during the aragonite precipitation. The data suggest that the low δ34Spy values are formed at higher supply rate of sulfate under relatively open system, and high δ34Spy values result from a deep sulfate methane transition zone where dissolve sulfate near to complete exhausted via AOM. The combination of a detailed elemental study of authigenic carbonate with sulfur isotopes of sulfide minerals in carbonates are promising tools for reconstructing the dynamics of seep intensities in modern and, potentially, geological record.

Optimization of arsenic removal water treatment system through characterization of terminal electron accepting processes.

PubMed

Upadhyaya, Giridhar; Clancy, Tara M; Brown, Jess; Hayes, Kim F; Raskin, Lutgarde

2012-11-06

Terminal electron accepting process (TEAP) zones developed when a simulated groundwater containing dissolved oxygen (DO), nitrate, arsenate, and sulfate was treated in a fixed-bed bioreactor system consisting of two reactors (reactors A and B) in series. When the reactors were operated with an empty bed contact time (EBCT) of 20 min each, DO-, nitrate-, sulfate-, and arsenate-reducing TEAP zones were located within reactor A. As a consequence, sulfate reduction and subsequent arsenic removal through arsenic sulfide precipitation and/or arsenic adsorption on or coprecipitation with iron sulfides occurred in reactor A. This resulted in the removal of arsenic-laden solids during backwashing of reactor A. To minimize this by shifting the sulfate-reducing zone to reactor B, the EBCT of reactor A was sequentially lowered from 20 min to 15, 10, and 7 min. While 50 mg/L (0.81 mM) nitrate was completely removed at all EBCTs, more than 90% of 300 μg/L (4 μM) arsenic was removed with the total EBCT as low as 27 min. Sulfate- and arsenate-reducing bacteria were identified throughout the system through clone libraries and quantitative PCR targeting the 16S rRNA, dissimilatory (bi)sulfite reductase (dsrAB), and dissimilatory arsenate reductase (arrA) genes. Results of reverse transcriptase (RT) qPCR of partial dsrAB (i.e., dsrA) and arrA transcripts corresponded with system performance. The RT qPCR results indicated colocation of sulfate- and arsenate-reducing activities, in the presence of iron(II), suggesting their importance in arsenic removal.

Electrodic voltages in the presence of dissolved sulfide: Implications for monitoring natural microbial activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slater, L.; Ntarlagiannis, D.; Yee, N.

2008-10-01

There is growing interest in the development of new monitoring strategies for obtaining spatially extensive data diagnostic of microbial processes occurring in the earth. Open-circuit potentials arising from variable redox conditions in the fluid local-to-electrode surfaces (electrodic potentials) were recorded for a pair of silver-silver chloride electrodes in a column experiment, whereby a natural wetland soil containing a known community of sulfate reducers was continuously fed with a sulfate-rich nutrient medium. Measurements were made between five electrodes equally spaced along the column and a reference electrode placed on the column inflow. The presence of a sulfate reducing microbial population, coupledmore » with observations of decreasing sulfate levels, formation of black precipitate (likely iron sulfide),elevated solid phase sulfide, and a characteristic sulfurous smell, suggest microbial-driven sulfate reduction (sulfide generation) in our column. Based on the known sensitivity of a silver electrode to dissolved sulfide concentration, we interpret the electrodic potentials approaching 700 mV recorded in this experiment as an indicator of the bisulfide (HS-) concentration gradients in the column. The measurement of the spatial and temporal variation in these electrodic potentials provides a simple and rapid method for monitoring patterns of relative HS- concentration that are indicative of the activity of sulfate-reducing bacteria. Our measurements have implications both for the autonomous monitoring of anaerobic microbial processes in the subsurface and the performance of self-potential electrodes, where it is critical to isolate, and perhaps quantify, electrochemical interfaces contributing to observed potentials.« less

Barite, BIFs and bugs: evidence for the evolution of the Earth's early hydrosphere

NASA Astrophysics Data System (ADS)

Huston, David L.; Logan, Graham A.

2004-03-01

The presence of relatively abundant bedded sulfate deposits before 3.2 Ga and after 1.8 Ga, the peak in iron formation abundance between 3.2 and 1.8 Ga, and the aqueous geochemistry of sulfur and iron together suggest that the redox state and the abundances of sulfur and iron in the hydrosphere varied widely during the Archean and Proterozoic. We propose a layered hydrosphere prior to 3.2 Ga in which sulfate produced by atmospheric photolytic reactions was enriched in an upper layer, whereas the underlying layer was reduced and sulfur-poor. Between 3.2 and 2.4 Ga, sulfate reduction removed sulfate from the upper layer, producing broadly uniform, reduced, sulfur-poor and iron-rich oceans. As a result of increasing atmospheric oxygenation around 2.4 Ga, the flux of sulfate into the hydrosphere by oxidative weathering was greatly enhanced, producing layered oceans, with sulfate-enriched, iron-poor surface waters and reduced, sulfur-poor and iron-rich bottom waters. The rate at which this process proceeded varied between basins depending on the size and local environment of the basin. By 1.8 Ga, the hydrosphere was relatively sulfate-rich and iron-poor throughout. Variations in sulfur and iron abundances suggest that the redox state of the oceans was buffered by iron before 2.4 Ga and by sulfur after 1.8 Ga.

Mechanisms of direct inhibition of the respiratory sulfate-reduction pathway by (per)chlorate and nitrate.

PubMed

Carlson, Hans K; Kuehl, Jennifer V; Hazra, Amrita B; Justice, Nicholas B; Stoeva, Magdalena K; Sczesnak, Andrew; Mullan, Mark R; Iavarone, Anthony T; Engelbrektson, Anna; Price, Morgan N; Deutschbauer, Adam M; Arkin, Adam P; Coates, John D

2015-06-01

We investigated perchlorate (ClO(4)(-)) and chlorate (ClO(3)(-)) (collectively (per)chlorate) in comparison with nitrate as potential inhibitors of sulfide (H(2)S) production by mesophilic sulfate-reducing microorganisms (SRMs). We demonstrate the specificity and potency of (per)chlorate as direct SRM inhibitors in both pure cultures and undefined sulfidogenic communities. We demonstrate that (per)chlorate and nitrate are antagonistic inhibitors and resistance is cross-inducible implying that these compounds share at least one common mechanism of resistance. Using tagged-transposon pools we identified genes responsible for sensitivity and resistance in Desulfovibrio alaskensis G20. We found that mutants in Dde_2702 (Rex), a repressor of the central sulfate-reduction pathway were resistant to both (per)chlorate and nitrate. In general, Rex derepresses its regulon in response to increasing intracellular NADH:NAD(+) ratios. In cells in which respiratory sulfate reduction is inhibited, NADH:NAD(+) ratios should increase leading to derepression of the sulfate-reduction pathway. In support of this, in (per)chlorate or nitrate-stressed wild-type G20 we observed higher NADH:NAD(+) ratios, increased transcripts and increased peptide counts for genes in the core Rex regulon. We conclude that one mode of (per)chlorate and nitrate toxicity is as direct inhibitors of the central sulfate-reduction pathway. Our results demonstrate that (per)chlorate are more potent inhibitors than nitrate in both pure cultures and communities, implying that they represent an attractive alternative for controlling sulfidogenesis in industrial ecosystems. Of these, perchlorate offers better application logistics because of its inhibitory potency, solubility, relative chemical stability, low affinity for mineral cations and high mobility in environmental systems.

Anaerobic digestion of sulfate-acidified cattle slurry: One-stage vs. two-stage.

PubMed

Moset, Veronica; Ottosen, Lars Ditlev Mørck; Xavier, Cristiane de Almeida Neves; Møller, Henrik Bjarne

2016-05-15

Two strategies to include acidified cattle manure (AcCM) in co-digestion with normal cattle manure (CM) are presented in this work. The strategies are a single thermophilic (50 °C) continuous stirred tank reactor (CSTR) anaerobic digestion and a two-step (65 °C + 50 °C) CSTR process. In both strategies, two different inclusion levels of H2SO4-acidified CM (10% and 20%) in co-digestion with normal CM were tested and compared with a control CSTR fed only CM. Important enhancement of methane (CH4) yield and solid reductions were observed in the thermophilic one-step CSTR working with 10% AcCM. However, a higher inclusion level of AcCM (20%) caused volatile fatty acid accumulation in the reactor and a more than 30% reduction in CH4 production. In terms of CH4 production, when 10% of AcCM was co-digested with 90% of CM, the two-step anaerobic co-digestion yielded less than the single step. During the first step of the two-step CSTR process, acidogenesis and a partial sulfate reduction were achieved. However, sulfide stripping between the first and the second step must be promoted in order to advance this technology. Copyright © 2016 Elsevier Ltd. All rights reserved.

Disturbed subsurface microbial communities follow equivalent trajectories despite different structural starting points: Microbial community succession and disturbance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Handley, Kim M.; Wrighton, Kelly C.; Miller, Christopher S.

2014-04-18

Microbial community structure, and niche and neutral processes can all influence response to disturbance. Here, we provide experimental evidence for niche versus neutral and founding community effects during a bioremediation-related organic carbon disturbance. Subsurface sediment, partitioned into 22 flow-through columns, was stimulated in situ by the addition of acetate as a carbon and electron donor source. This drove the system into a new transient biogeochemical state characterized by iron reduction and enriched Desulfuromonadales, Comamonadaceae and Bacteroidetes lineages. After approximately 1 month conditions favoured sulfate reduction, and were accompanied by a substantial increase in the relative abundance of Desulfobulbus, Desulfosporosinus, Desulfitobacteriummore » and Desulfotomaculum. Two subsets of four to five columns each were switched from acetate to lactate amendment during either iron (earlier) or sulfate (later) reduction. Hence, subsets had significantly different founding communities. All lactate treatments exhibited lower relative abundances of Desulfotomaculum and Bacteroidetes, enrichments of Clostridiales and Psychrosinus species, and a temporal succession from highly abundant Clostridium sensu stricto to Psychrosinus. Regardless of starting point, lactate-switch communities followed comparable structural trajectories, whereby convergence was evident 9 to 16 days after each switch, and significant after 29 to 34 days of lactate addition. Results imply that neither the founding community nor neutral processes influenced succession following perturbation.« less

Geochemical and geological factors controlling the spatial distribution of sulfate-methane transition zone in the Ría de Vigo (NW Spain)

NASA Astrophysics Data System (ADS)

Martínez-Carreño, N.; García-Gil, S.; Cartelle, V.; de Blas, E.; Ramírez-Pérez, A. M.; Insua, T. L.

2017-05-01

High-resolution seismic profiles, gravity core analysis and radiocarbon data have been used to identify the factors behind the methane production and free gas accumulation in the Ría de Vigo. Lithological and geochemical parameters (sulfate and methane concentration) from seventeen gravity cores were analyzed to characterize the sediment of the ria. The distribution of methane-charged sediments is mainly controlled by the quantity and quality of organic matter. Geochemical analyses reveal minimum methane concentrations ranging between 1 μM and 1 mM in sediments located outside the acoustic gas field, while gas-bearing sediments, show methane concentrations up to 5 mM. A shallowing of the sulfate-methane transition zone (SMTZ) is observed from the outer to the inner area of the ria. The presence of methane in the sulfate reduction zone (SRZ) likely to reflect the existence of methylotropic methanogenesis and/or migration processes of deeper methane gas in the sediments of the Ría de Vigo. The presence of an 'anomalous' high-sulfate concentration layer below the SMTZ in the inner and middle area of the ria, is attributed to the intrusion of sulfate-rich waters from adjacent areas that could be transported laterally through more porous layers.

SULFATE REDUCTION RATES IN A THALASSIA TESTUDINUM SEAGRASS BED, NORTHWEST FLORIDA USA GULF OF MEXICO COAST

EPA Science Inventory

Devereux, R., D.F. Yates and Robert L. Quarles. In press. Sulfate Reduction Rates in a Thalassia testudinum Seagrass Bed, Northwest Florida USA Gulf of Mexico Coast (Abstract). To be presented at the ASLO 2004 Summer Meeting: The Changing Landscapes of Oceans and Freshwater, 13-1...

Microbial Community Phylogenetic and Functional Succession in Chromium-Reducing Aquifer-Derived Microcosms

NASA Astrophysics Data System (ADS)

Brodie, E. L.; Beller, H. R.; Goldfarb, K. C.; Han, R.; Santee, C. A.

2009-12-01

In situ reductive immobilization, whereby highly soluble Cr(VI) species are reduced to poorly soluble Cr(III) species, is a favored approach for remediating Cr-contaminated groundwater. How microbial populations respond phylogenetically and functionally to the injection of an organic electron donor to stimulate Cr(VI) reduction is unclear, as are the relative contributions of direct enzymatic Cr(VI) reduction versus indirect (e.g. sulfide-mediated) reduction. In this study, we inoculated anaerobic microcosms with groundwater from the Cr-contaminated Hanford 100H site (WA) and supplemented them with lactate and the electron acceptors nitrate, sulfate, and amorphous ferric oxyhydroxide. The microcosms progressed successively through nitrate-reducing, sulfate-reducing, and Fe(III)-reducing conditions, and after a second nitrate amendment, nitrate-dependent Fe(II)-oxidizing conditions. Cr(VI) reduction occurred during both the denitrification and the sulfate/iron reduction phases. DNA and RNA were harvested during each major biogeochemical phase and were subjected to PhyloChip analysis, qPCR, and transcript sequencing. Bacterial community succession followed a trajectory related to the sequential use of electron acceptors. During denitrification, bacterial communities were enriched in known denitrifiers within the Beta- and Gamma-proteobacteria and became phylogenetically clustered. Fermenters became enriched following nitrate reduction, preceding both iron and sulfate reduction. Iron reduction was stoichiometrically related to the formation of hydrogen sulfide and, although iron reducers were detected during this phase, their iron-reducing activity was not confirmed. Following the depletion of lactate and sulfate, iron reduction rates decreased and acetate and propionate concentrations stabilized, indicating a marginal contribution of acetate-coupled iron reduction. Rapid Fe(II) oxidation occurred following the nitrate amendment with a concomitant reduction of nitrate to nitrite and an increased abundance of Beta-proteobacterial species related to known anaerobic Fe(II)-oxidizing bacteria. To uncover the microbial mechanisms contributing to the biogeochemical complexity encountered, even under controlled laboratory incubations, requires alternatives to standard phylogenetic analyses. Our ongoing efforts in analyzing the community transcriptomes (mRNA) should provide valuable insight into the relative rates of direct versus indirect mechanisms of Cr(VI) immobilization in contaminated aquifers.

Ambient aerosols remain highly acidic despite dramatic sulfate reductions

NASA Astrophysics Data System (ADS)

Nenes, Athanasios; Weber, Rodney; Guo, Hongyu; Russell, Armistead

2016-04-01

The pH of fine particles has many vital environmental impacts. By affecting aerosol concentrations, chemical composition and toxicity, particle pH is linked to regional air quality and climate, and adverse effects on human health. Sulfate is often the main acid component that drives pH of fine particles (i.e., PM2.5) and is neutralized to varying degrees by gas phase ammonia. Sulfate levels have decreased by approximately 70% over the Southeastern United States in the last fifteen years, but measured ammonia levels have been fairly steady implying the aerosol may becoming more neutral. Using a chemically comprehensive data set, combined with a thermodynamic analysis, we show that PM2.5 in the Southeastern U.S. is highly acidic (pH between 0 and 2), and that pH has remained relatively unchanged throughout the past decade and a half of decreasing sulfate. Even with further sulfate reductions, pH buffering by gas-particle partitioning of ammonia is expected to continue until sulfate drops to near background levels, indicating that fine particle pH will remain near current levels into the future. These results are non-intuitive and reshape expectations of how sulfur emission reductions impact air quality in the Southeastern U.S. and possibly other regions across the globe.

Transient exposure to oxygen or nitrate reveals ecophysiology of fermentative and sulfate‐reducing benthic microbial populations

PubMed Central

Saad, Sainab; Bhatnagar, Srijak; Tegetmeyer, Halina E.; Geelhoed, Jeanine S.; Strous, Marc

2017-01-01

Summary For the anaerobic remineralization of organic matter in marine sediments, sulfate reduction coupled to fermentation plays a key role. Here, we enriched sulfate‐reducing/fermentative communities from intertidal sediments under defined conditions in continuous culture. We transiently exposed the cultures to oxygen or nitrate twice daily and investigated the community response. Chemical measurements, provisional genomes and transcriptomic profiles revealed trophic networks of microbial populations. Sulfate reducers coexisted with facultative nitrate reducers or aerobes enabling the community to adjust to nitrate or oxygen pulses. Exposure to oxygen and nitrate impacted the community structure, but did not suppress fermentation or sulfate reduction as community functions, highlighting their stability under dynamic conditions. The most abundant sulfate reducer in all cultures, related to Desulfotignum balticum, appeared to have coupled both acetate‐ and hydrogen oxidation to sulfate reduction. We describe a novel representative of the widespread uncultured candidate phylum Fermentibacteria (formerly candidate division Hyd24‐12). For this strictly anaerobic, obligate fermentative bacterium, we propose the name ‘USabulitectum silens’ and identify it as a partner of sulfate reducers in marine sediments. Overall, we provide insights into the function of fermentative, as well as sulfate‐reducing microbial communities and their adaptation to a dynamic environment. PMID:28836729

Liver heparan sulfate proteoglycans mediate clearance of triglyceride-rich lipoproteins independently of LDL receptor family members

PubMed Central

MacArthur, Jennifer M.; Bishop, Joseph R.; Stanford, Kristin I.; Wang, Lianchun; Bensadoun, André; Witztum, Joseph L.; Esko, Jeffrey D.

2007-01-01

We examined the role of hepatic heparan sulfate in triglyceride-rich lipoprotein metabolism by inactivating the biosynthetic gene GlcNAc N-deacetylase/N-sulfotransferase 1 (Ndst1) in hepatocytes using the Cre-loxP system, which resulted in an approximately 50% reduction in sulfation of liver heparan sulfate. Mice were viable and healthy, but they accumulated triglyceride-rich lipoprotein particles containing apoB-100, apoB-48, apoE, and apoCI-IV. Compounding the mutation with LDL receptor deficiency caused enhanced accumulation of both cholesterol- and triglyceride-rich particles compared with mice lacking only LDL receptors, suggesting that heparan sulfate participates in the clearance of cholesterol-rich lipoproteins as well. Mutant mice synthesized VLDL normally but showed reduced plasma clearance of human VLDL and a corresponding reduction in hepatic VLDL uptake. Retinyl ester excursion studies revealed that clearance of intestinally derived lipoproteins also depended on hepatocyte heparan sulfate. These findings show that under normal physiological conditions, hepatic heparan sulfate proteoglycans play a crucial role in the clearance of both intestinally derived and hepatic lipoprotein particles. PMID:17200715

Fate of microbial metabolites of hydrocarbons in a coastal plain aquifer: The role of electron acceptors

USGS Publications Warehouse

Cozzarelli, I.M.; Herman, J.S.; Baedecker, M. Jo

1995-01-01

A combined field and laboratory study was undertaken to understand the distribution and geochemical conditions that influence the prevalence of low molecular weight organic acids in groundwater of a shallow aquifer contaminated with gasoline. Aromatic hydrocarbons from gasoline were degraded by microbially mediated oxidation-reduction reactions, including reduction of nitrate, sulfate, and Fe(III). The biogeochemical reactions changed overtime in response to changes in the hydrogeochemical conditions in the aquifer. Aliphatic and aromatic organic acids were associated with hydrocarbon degradation in anoxic zones of the aquifer. Laboratory microcosms demonstrated that the biogeochemical fate of specific organic acids observed in groundwater varied with the structure of the acid and the availability of electron acceptors. Benzoic and phenylacetic acid were degraded by indigenous aquifer microorganisms when nitrate was supplied as an electron acceptor. Aromatic acids with two or more methyl substituants on the benzene ring persisted under nitrate-reducing conditions. Although iron reduction and sulfate reduction were important processes in situ and occurred in the microcosms, these reactions were not coupled to the biological oxidation of aromatic organic acids that were added to the microcosms as electron donors. ?? 1995 American Chemical Society.

Geochemistry of water in the Fort Union Formation of the northern Powder River basin, southeastern Montana

USGS Publications Warehouse

Lee, Roger W.

1980-01-01

Shallow water in the coal-bearing Fort Union Formation of southeastern Montana was investigated to provide a better understanding of the geochemistry. Springs, wells less than 200 feet deep, and wells greater then 200 feet deep were observed to have different water qualities. Overall, the ground water exists as two systems: a mosaic of shallow, chemically dynamic, and localized recharge-discharge cells superimposed on a deeper, chemically static regional system. Water chemistry is highly variable in the shallow system, whereas sodium and bicarbonate waters characterize the deeper system. Within the shallow system , springs, and wells less than 200 feet deep show predominantly sodium and sulfate enrichment processes from recharge to discharge. These processes are consistent with the observed aquifer mineralogy and aqueous chemistry. However, intermittent mixing with downward moving recharge waters or upward moving deeper waters, and bacterially catalyzed sulfate reduction, may cause apparent reversals in these processes. (USGS)

Geochemistry of water in the Fort Union formation of the northern Powder River basin, southeastern Montana

USGS Publications Warehouse

Lee, Roger W.

1981-01-01

Shallow water in the coal-bearing Paleocene Fort Union Formation of southeastern Montana was investigated to provide a better understanding of its geochemistry. Springs, wells less than 200 feet deep, and wells greater than 200 feet deep were observed to have different water qualities. Overall, the ground water exists as two systems: a mosaic of shallow, chemically dynamic, and localized recharge-discharge cells superimposed on a deeper, chemically static regional system. Water chemistry is highly variable in the shallow system; whereas, waters containing sodium and bicarbonate characterize the deeper system. Within the shallow system, springs and wells less than 200 feet deep show predominantly sodium and sulfate enrichment processes from recharge to discharge. These processes are consistent with the observed aquifer mineralogy and aqueous chemistry. However, intermittent mixing with downward moving recharge waters or upward moving deeper waters, and bacterially catalyzed sulfate reduction, may cause apparent reversals in these processes.

Using stable isotopes to trace sources and formation processes of sulfate aerosols from Beijing, China

PubMed Central

Han, Xiaokun; Guo, Qingjun; Liu, Congqiang; Fu, Pingqing; Strauss, Harald; Yang, Junxing; Hu, Jian; Wei, Lianfang; Ren, Hong; Peters, Marc; Wei, Rongfei; Tian, Liyan

2016-01-01

Particulate pollution from anthropogenic and natural sources is a severe problem in China. Sulfur and oxygen isotopes of aerosol sulfate (δ34Ssulfate and δ18Osulfate) and water-soluble ions in aerosols collected from 2012 to 2014 in Beijing are being utilized to identify their sources and assess seasonal trends. The mean δ34S value of aerosol sulfate is similar to that of coal from North China, indicating that coal combustion is a significant contributor to atmospheric sulfate. The δ34Ssulfate and δ18Osulfate values are positively correlated and display an obvious seasonality (high in winter and low in summer). Although an influence of meteorological conditions to this seasonality in isotopic composition cannot be ruled out, the isotopic evidence suggests that the observed seasonality reflects temporal variations in the two main contributions to Beijing aerosol sulfate, notably biogenic sulfur emissions in the summer and the increasing coal consumption in winter. Our results clearly reveal that a reduction in the use of fossil fuels and the application of desulfurization technology will be important for effectively reducing sulfur emissions to the Beijing atmosphere. PMID:27435991

Application of Biostimulation for Remediation of Sulfate-Contaminated Groundwater at a Mining Site

NASA Astrophysics Data System (ADS)

Miao, Z.; Carroll, K. C.; Carreon, C.; Brusseau, M. L.

2011-12-01

There is growing concern regarding sulfate contamination of groundwater. One innovative in-situ remediation option under investigation is biostimulation through addition of electron-donor amendments to enhance sulfate reduction. Two pilot-scale ethanol-injection tests were conducted at a former uranium mining site that is contaminated with sulfate and nitrate (with a lack of heavy metals), and for which there appears to be minimal natural attenuation of sulfate. The first test was a push-pull test that had a limited zone of influence, while the second test was a single-well injection test in which additional downgradient wells were monitored. For both tests, sulfate concentrations began to decline within a few weeks of injection, after nitrate concentrations were significantly reduced. Concomitantly, aqueous concentrations of manganese, iron, and hydrogen sulfide increased from background. Monitoring over many months revealed that the declines in sulfate concentration conformed to exponential decay, with first-order decay rates of approximately 0.01 /d. Analysis of sulfur stable isotope data indicated that the decrease in sulfate concentrations was microbially mediated. The results also indicated that sulfides formed during sulfate reduction may have undergone partial re-oxidation. This study illustrates the feasibility of using ethanol injection for remediation of sulfate-contaminated groundwater. However, re-oxidation of sulfides (both metal sulfide precipitates and hydrogen sulfide gas) is a potential issue of significance that would need to be addressed.

Selenium isotope fractionation during reduction by Fe(II)-Fe(III) hydroxide-sulfate (green rust)

USGS Publications Warehouse

Johnson, T.M.; Bullen, T.D.

2003-01-01

We have determined the extent of Se isotope fractionation induced by reduction of selenate by sulfate interlayered green rust (GRSO4), a Fe(II)-Fe(III) hydroxide-sulfate. This compound is known to reduce selenate to Se(0), and it is the only naturally relevant abiotic selenate reduction pathway documented to date. Se reduction reactions, when they occur in nature, greatly reduce Se mobility and bioavailability. Se stable isotope analysis shows promise as an indicator of Se reduction, and Se isotope fractionation by various Se reactions must be known in order to refine this tool. We measured the increase in the 80Se/76Se ratio of dissolved selenate as lighter isotopes were preferentially consumed during reduction by GRSO4. Six different experiments that used GRSO4 made by two methods, with varying solution compositions and pH, yielded identical isotopic fractionations. Regression of all the data yielded an instantaneous isotope fractionation of 7.36 ?? 0.24???. Selenate reduction by GRSO4 induces much greater isotopic fractionation than does bacterial selenate reduction. If selenate reduction by GRSO4 occurs in nature, it may be identifiable on the basis of its relatively large isotopic fractionation. ?? 2003 Elsevier Science Ltd.

Quantitative Relationships between Photosynthetic, Nitrogen Fixing, and Fermentative H2 Metabolism in a Photosynthetic Microbial Mat

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Albert, Daniel B.; Bebout, Brad M.; Turk, Kendra A.; DesMarais, David J.

2004-01-01

The ultimate potential of any microbial ecosystem to contribute chemically to its environment - and therefore, to impact planetary biogeochemistry or to generate recognizable biosignatures - depends not only on the individual metabolic capabilities of constituent organisms, but also on how those capabilities are expressed through interactions with neighboring organisms. This is particularly important for microbial mats, which compress an extremely broad range of metabolic potential into a small and dynamic system. H2 participates in many of these metabolic processes, including the major elemental cycling processes of photosynthesis, nitrogen fixation, sulfate reduction, and fermentation, and may therefore serve as a mediator of microbial interactions within the mat system. Collectively, the requirements of energy, electron transfer, and biomass element stoichiometry suggest quantitative relationships among the major element cycling processes, as regards H2 metabolism We determined experimentally the major contributions to 32 cycling in hypersaline microbial mats from Baja California, Mexico, and compared them to predicted relationships. Fermentation under dark, anoxic conditions is quantitatively the most important mechanism of H2 production, consistent with expectations for non-heterocystous mats such as those under study. Up to 16% of reducing equivalents fixed by photosynthesis during the day may be released by this mechanism. The direct contribution of nitrogen fixation to H2 production is small in comparison, but this process may indirectly stimulate substantial H2 generation, by requiring higher rates of fermentation. Sulfate reduction, aerobic consumption, diffusive and ebulitive loss, and possibly H2-based photoreduction of CO2 serve as the principal H2 sinks. Collectively, these processes interact to create an orders-of-magnitude daily variation in H2 concentrations and fluxes, and thereby in the oxidation-reduction potential that is imposed on microbial processes occuring within the mat matrix.

The bioenergetics mechanisms and applications of sulfate-reducing bacteria in remediation of pollutants in drainage: A review.

PubMed

Li, Xin; Lan, Shi-Ming; Zhu, Zhong-Ping; Zhang, Chang; Zeng, Guang-Ming; Liu, Yun-Guo; Cao, Wei-Cheng; Song, Biao; Yang, Hong; Wang, Sheng-Fan; Wu, Shao-Hua

2018-04-20

Sulfate-reducing bacteria (SRB), a group of anaerobic prokaryotes, can use sulfur species as a terminal electron acceptor for the oxidation of organic compounds. They not only have significant ecological functions, but also play an important role in bioremediation of contaminated sites. Although numerous studies on metabolism and applications of SRB have been conducted, they still remain incompletely understood and even controversial. Fully understanding the metabolism of SRB paves the way for allowing the microorganisms to provide more beneficial services in bioremediation. Here we review progress in bioenergetics mechanisms and application of SRB including: (1) electron acceptors and donors for SRB; (2) pathway for sulfate reduction; (3) electron transfer in sulfate reduction; (4) application of SRB for economical and concomitant treatment of heavy metal, organic contaminants and sulfates. Moreover, current knowledge gaps and further research needs are identified. Copyright © 2018 Elsevier Inc. All rights reserved.

Anaerobic dechlorination of 2,4-dichlorophenol in freshwater sediments in the presence of sulfate.

PubMed Central

Kohring, G W; Zhang, X M; Wiegel, J

1989-01-01

In the presence of added sulfate, 2,4-dichlorophenol and 4-chlorophenol were transformed stoichiometrically to 4-chlorophenol and phenol, respectively, in anaerobic freshwater lake sediments between 18 and 40 degrees C. The concomitantly occurring sulfate reduction reduced the initial sulfate concentration from 25 mM to about 6 to 8 mM and depressed methane formation. PMID:2604410

Bioreactor performance and functional gene analysis of microbial community in a limited-oxygen fed bioreactor for co-reduction of sulfate and nitrate with high organic input.

PubMed

Xu, Xi-jun; Chen, Chuan; Wang, Ai-jie; Yu, Hao; Zhou, Xu; Guo, Hong-liang; Yuan, Ye; Lee, Duu-jong; Zhou, Jizhong; Ren, Nan-qi

2014-08-15

Limited-oxygen mediated synergistic relationships between sulfate-reducing bacteria (SRB), nitrate-reducing bacteria (NRB) and sulfide-oxidizing bacteria (SOB, including nitrate-reducing, sulfide-oxidizing bacteria NR-SOB) were predicted to simultaneously remove contaminants of nitrate, sulfate and high COD, and eliminate sulfide generation. A lab-scale experiment was conducted to examine the impact of limited oxygen on these oxy-anions degradation, sulfide oxidation and associated microbial functional responses. In all scenarios tested, the reduction of both nitrate and sulfate was almost complete. When limited-oxygen was fed into bioreactors, S(0) formation was significantly improved up to ∼ 70%. GeoChip 4.0, a functional gene microarray, was used to determine the microbial gene diversity and functional potential for nitrate and sulfate reduction, and sulfide oxidation. The diversity of the microbial community in bioreactors was increased with the feeding of limited oxygen. Whereas the intensities of the functional genes involved in sulfate reduction did not show a significant difference, the abundance of the detected denitrification genes decreased in limited oxygen samples. More importantly, sulfide-oxidizing bacteria may alter their populations/genes in response to limited oxygen potentially to function more effectively in sulfide oxidation, especially to elemental sulfur. The genes fccA/fccB from nitrate-reducing, sulfide-oxidizing bacteria (NR-SOB), such as Paracoccus denitrificans, Thiobacillus denitrificans, Beggiatoa sp., Thiomicrospira sp., and Thioalkalivibrio sp., were more abundant under limited-oxygen condition. Copyright © 2014 Elsevier B.V. All rights reserved.

Origin of sulfide and phosphate deposits in Upper Proterozoic carbonate strata, Irece basin, Bahia, Brazil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyle, J.R.; Misi, A.

1991-03-01

Carbonate strata of the Una Group represent late Proterozoic platform sedimentation in the Irece basin of north-central Brazil. Stratabound sulfide- and phosphate-rich units occur within a 50-m thick tidal flat sequence of dolomitic limestone and cherty dolomite. Three types of primary phosphate concentrations are present: columnar stromatolitic, laminar stromatolitic, and intraclastic. Resedimented phosphate clasts and phosphatic units interbedded with non phosphatic dolomites suggest early diagenetic replacement of algal carbonate units. Local stratabound Zn-Pb-Ag sulfide concentrations at the Tres Irmas prospect occur within silty dolomite with shallow water sedimentary structures and local disturbed laminae, synsedimentary faults, and breccias. Sulfide minerals includemore » pyrite, sphalerite, galena, marcasite, jordanite, tetrahedrite, and covellite. Pyrite crystal aggregates commonly show bladed forms. Nodular aggregates of length-slow quartz are locally associated with sulfides. Sulfur isotope analyses indicate relatively uniform heavy {delta}{sup 34}S values. Barite shows a {delta}{sup 34}S range from +25.2 to +29.6{per thousand}, CDT. Pyrite and sphalerite representative of a variety of textural types have a {delta}{sup 34}S range of +20.2 to +22.6{per thousand}. Late Proterozoic evaporite sulfates show a wide range of {delta}{sup 34} S values from about +10 to +28{per thousand}. Thus, the {delta}{sup 34}S values for Irece barite could reflect original seawater sulfate values. However, the relatively heavy {delta}{sup 34}S values of the associated sulfides suggests that the original seawater sulfate was modified by bacterial sulfate reduction processes in shallow sea floor sediments. Textural and {delta}{sup 34}S evidence suggests that a later stage of metallic mineralization scavenged sulfur from preexisting sulfides or from direct reduction of evaporitic sulfate minerals.« less

Comparison of lactate, formate, and propionate as hydrogen donors for the reductive dehalogenation of trichloroethene in a continuous-flow column.

PubMed

Azizian, Mohammad F; Marshall, Ian P G; Behrens, Sebastian; Spormann, Alfred M; Semprini, Lewis

2010-04-01

A continuous-flow column study was conducted to analyze the reductive dehalogenation of trichloroethene (TCE) with aquifer material with high content of iron oxides. The column was bioaugmented with the Point Mugu (PM) culture, which is a mixed microbial enrichment culture capable of completely transforming TCE to ethene (ETH). We determined whether lactate, formate, or propionate fermentation resulted in more effective dehalogenation. Reductive dehalogenation, fermentation, and sulfate, Fe(III), and Mn(IV) reduction were all exhibited within the column. Different steady-states of dehalogenation were achieved based on the concentration of substrates added, with effective transformation to ETH obtained when ample electron donor equivalents were provided. Most of the metabolic reducing equivalents were channeled to sulfate, Fe(III), and Mn(IV) reduction. When similar electron reducing equivalents were added, the most effective dehalogenation was achieved with formate, with 14% of the electron equivalents going towards dehalogenation reactions, compared to 6.5% for lactate and 9.6% for propionate. Effective dehalogenation was maintained over 1000 days of column operation. Over 90% of electron equivalents added could be accounted for by the different electron accepting processes in the column, with 50% associated with soluble and precipitated Fe(II) and Mn(II). Bulk Fe(III) and Mn(IV) reduction was rather associated with lactate and propionate addition than formate addition. Sulfate reduction was a competing electron acceptor reaction with all three electron donors. DNA was extracted from solid coupon samples obtained during the course of the experiment and analyzed using 16S rRNA gene clone libraries and quantitative PCR. Lactate and propionate addition resulted in a significant increase in Geobacter, Spirochaetes, and Desulfitobacterium phylotypes relative to "Dehalococcoides" when compared to formate addition. Results from the molecular biological analyses support chemical observations that a greater percentage of the electron donor addition was channeled to Fe(III) reduction when lactate and propionate were added compared to formate, and formate was more effective than lactate in supporting dehalogenation. The results demonstrate the importance of electron donor selection and competing electron acceptor reactions when implementing reductive dehalogenation remediation technologies. Published by Elsevier B.V.

Comparison of lactate, formate, and propionate as hydrogen donors for the reductive dehalogenation of trichloroethene in a continuous-flow column

NASA Astrophysics Data System (ADS)

Azizian, Mohammad F.; Marshall, Ian P. G.; Behrens, Sebastian; Spormann, Alfred M.; Semprini, Lewis

2010-04-01

A continuous-flow column study was conducted to analyze the reductive dehalogenation of trichloroethene (TCE) with aquifer material with high content of iron oxides. The column was bioaugmented with the Point Mugu (PM) culture, which is a mixed microbial enrichment culture capable of completely transforming TCE to ethene (ETH). We determined whether lactate, formate, or propionate fermentation resulted in more effective dehalogenation. Reductive dehalogenation, fermentation, and sulfate, Fe(III), and Mn(IV) reduction were all exhibited within the column. Different steady-states of dehalogenation were achieved based on the concentration of substrates added, with effective transformation to ETH obtained when ample electron donor equivalents were provided. Most of the metabolic reducing equivalents were channeled to sulfate, Fe(III), and Mn(IV) reduction. When similar electron reducing equivalents were added, the most effective dehalogenation was achieved with formate, with 14% of the electron equivalents going towards dehalogenation reactions, compared to 6.5% for lactate and 9.6% for propionate. Effective dehalogenation was maintained over 1000 days of column operation. Over 90% of electron equivalents added could be accounted for by the different electron accepting processes in the column, with 50% associated with soluble and precipitated Fe(II) and Mn(II). Bulk Fe(III) and Mn(IV) reduction was rather associated with lactate and propionate addition than formate addition. Sulfate reduction was a competing electron acceptor reaction with all three electron donors. DNA was extracted from solid coupon samples obtained during the course of the experiment and analyzed using 16S rRNA gene clone libraries and quantitative PCR. Lactate and propionate addition resulted in a significant increase in Geobacter, Spirochaetes, and Desulfitobacterium phylotypes relative to " Dehalococcoides" when compared to formate addition. Results from the molecular biological analyses support chemical observations that a greater percentage of the electron donor addition was channeled to Fe(III) reduction when lactate and propionate were added compared to formate, and formate was more effective than lactate in supporting dehalogenation. The results demonstrate the importance of electron donor selection and competing electron acceptor reactions when implementing reductive dehalogenation remediation technologies.

Regeneration and sulfur poisoning behavior of In/H-BEA catalyst for NOx reduction by CH4

NASA Astrophysics Data System (ADS)

Pan, Hua; Jian, Yanfei; Yu, Yanke; He, Chi; Shen, Zhenxing; Liu, Hongxia

2017-04-01

Sulfur poisoning and regeneration behavior of In/H-BEA catalyst were carried out in NOx reduction by CH4. In/H-BEA catalyst exhibited a poor resistance to sulfur dioxide after addition of 200 ppm SO2 and 10 vol.% H2O into NO reduction with CH4 at 450 °C for 45 h. Sulfur poisoning of In/H-BEA was attributed to the inhibition of NOx adsorption on Brønsted acid sites, suppression of reaction intermediates generation on the active sites, and the formation of surface sulfate species. The formation of surface sulfate reduced the availability of surface active sites, blocked the pore structure and decreased the surface area of catalyst. These changes in chemical and textural properties resulted in a severe loss in the activity of sulfated In/H-BEA catalyst for NO reduction with CH4. H2 reduction is a promising technology for regeneration of In/H-BEA deactivated by SO2 for removing NOx from lean-burn and diesel exhausts. Indium sulfate could be reduced by H2 to InO+ with In2O3 and In(OH)2+ as the intermediates. The optimal parameters of H2 reduction was regeneration temperature of 400 °C and regeneration time of 60 min which completely recovered the catalytic activity of In/H-BEA.

ELECTROCHEMISTRY OF FUSED SALTS.

DTIC Science & Technology

Chronopotentiometric and electrolysis data indicate the formation of Li2O.2V2O4V2O5 during the first reduction process of V2O5 in molten LiCl-KCl...The results were obtained with a pyrographite cathode. Also discussed is the spectra of CO(2+) and Ni(2+) in molten and solid sulfate media. (Author)

σ 54-dependent regulome in Desulfovibrio vulgaris Hildenborough

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kazakov, Alexey E.; Rajeev, Lara; Chen, Amy

2015-11-10

The σ 54 subunit controls a unique class of promoters in bacteria. Such promoters, without exception, require enhancer binding proteins (EBPs) for transcription initiation. Desulfovibrio vulgaris Hildenborough, a model bacterium for sulfate reduction studies, has a high number of EBPs, more than most sequenced bacteria. Finally, the cellular processes regulated by many of these EBPs remain unknown.

Geochemical and microbial community determinants of reductive dechlorination at a site biostimulated with glycerol.

PubMed

Atashgahi, Siavash; Lu, Yue; Zheng, Ying; Saccenti, Edoardo; Suarez-Diez, Maria; Ramiro-Garcia, Javier; Eisenmann, Heinrich; Elsner, Martin; J M Stams, Alfons; Springael, Dirk; Dejonghe, Winnie; Smidt, Hauke

2017-03-01

Biostimulation is widely used to enhance reductive dechlorination of chlorinated ethenes in contaminated aquifers. However, the knowledge on corresponding biogeochemical responses is limited. In this study, glycerol was injected in an aquifer contaminated with cis-dichloroethene (cDCE), and geochemical and microbial shifts were followed for 265 days. Consistent with anoxic conditions and sulfate reduction after biostimulation, MiSeq 16S rRNA gene sequencing revealed temporarily increased relative abundance of Firmicutes, Bacteriodetes and sulfate reducing Deltaproteobacteria. In line with 13 C cDCE enrichment and increased Dehalococcoides mccartyi (Dcm) numbers, dechlorination was observed toward the end of the field experiment, albeit being incomplete with accumulation of vinyl chloride. This was concurrent with (i) decreased concentrations of dissolved organic carbon (DOC), reduced relative abundances of fermenting and sulfate reducing bacteria that have been suggested to promote Dcm growth by providing electron donor (H 2 ) and essential corrinoid cofactors, (ii) increased sulfate concentration and increased relative abundance of Epsilonproteobacteria and Deferribacteres as putative oxidizers of reduced sulfur compounds. Strong correlations of DOC, relative abundance of fermenters and sulfate reducers, and dechlorination imply the importance of syntrophic interactions to sustain robust dechlorination. Tracking microbial and environmental parameters that promote/preclude enhanced reductive dechlorination should aid development of sustainable bioremediation strategies. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

PubMed Central

Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

2016-01-01

Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic relationship. PMID:26872267

Isotope geochemistry of waters affected by acid mine drainage in old labour sites (SE, Spain).

NASA Astrophysics Data System (ADS)

Pérez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Garcia-Lorenzo, Maria Luz; Agudo, Ines; Hernandez-Cordoba, Manuel; Recio, Clemente

2015-04-01

The ore deposits of this zone have iron, lead and zinc as the main metal components. Iron is present in oxides, hydroxides, sulfides, sulfates, carbonates, and silicates; lead and zinc occur in sulfides (galena and sphalerite, respectively), carbonates, sulfates, and lead or zinc-bearing (manganese, iron) oxides. Mining started with the Romans and activity peaked in the second half of the 19th century and throughout the 20th century until the 1980's. From 1940 to 1957, mineral concentration was made by froth flotation and, prior to this, by gravimetric techniques. The mining wastes, or tailings, with a very fine particle size were deposited inland (tailings dams) and, since 1957, huge releases were made in directly the sea coast. The objective of this work was to evaluate processes affecting waters from abandoned mine sites by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. Several common chemical and physical processes, such as evaporation, water-rock interaction and mixing could alter water isotopic composition. Evaporation, which causes an enrichment in δD and δ18O in the residual water, is an important process in semiarid areas. The results obtained indicate that, for sites near the coast, waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by A. ferrooxidans, while at depth, sulfate reduction occurred.

Comparative proteomic analysis of Desulfotomaculum reducens MI-1: Insights into the metabolic versatility of a gram-positive sulfate- and metal-reducing bacterium

DOE PAGES

Otwell, Anne E.; Callister, Stephen J.; Zink, Erika M.; ...

2016-02-19

In this study, the proteomes of the metabolically versatile and poorly characterized Gram-positive bacterium Desulfotomaculum reducens MI-1 were compared across four cultivation conditions including sulfate reduction, soluble Fe(III) reduction, insoluble Fe(III) reduction, and pyruvate fermentation. Collectively across conditions, we observed at high confidence ~38% of genome-encoded proteins. Here, we focus on proteins that display significant differential abundance on conditions tested. To the best of our knowledge, this is the first full-proteome study focused on a Gram-positive organism cultivated either on sulfate or metal-reducing conditions. Several proteins with uncharacterized function encoded within heterodisulfide reductase ( hdr)-containing loci were upregulated on eithermore » sulfate (Dred_0633-4, Dred_0689-90, and Dred_1325-30) or Fe(III)-citrate-reducing conditions (Dred_0432-3 and Dred_1778-84). Two of these hdr-containing loci display homology to recently described flavin-based electron bifurcation (FBEB) pathways (Dred_1325-30 and Dred_1778-84). Additionally, we propose that a cluster of proteins, which is homologous to a described FBEB lactate dehydrogenase (LDH) complex, is performing lactate oxidation in D. reducens (Dred_0367-9). Analysis of the putative sulfate reduction machinery in D. reducens revealed that most of these proteins are constitutively expressed across cultivation conditions tested. In addition, peptides from the single multiheme c-type cytochrome (MHC) in the genome were exclusively observed on the insoluble Fe(III) condition, suggesting that this MHC may play a role in reduction of insoluble metals.« less

Comparative proteomic analysis of Desulfotomaculum reducens MI-1: Insights into the metabolic versatility of a gram-positive sulfate- and metal-reducing bacterium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Otwell, Anne E.; Callister, Stephen J.; Zink, Erika M.

In this study, the proteomes of the metabolically versatile and poorly characterized Gram-positive bacterium Desulfotomaculum reducens MI-1 were compared across four cultivation conditions including sulfate reduction, soluble Fe(III) reduction, insoluble Fe(III) reduction, and pyruvate fermentation. Collectively across conditions, we observed at high confidence ~38% of genome-encoded proteins. Here, we focus on proteins that display significant differential abundance on conditions tested. To the best of our knowledge, this is the first full-proteome study focused on a Gram-positive organism cultivated either on sulfate or metal-reducing conditions. Several proteins with uncharacterized function encoded within heterodisulfide reductase ( hdr)-containing loci were upregulated on eithermore » sulfate (Dred_0633-4, Dred_0689-90, and Dred_1325-30) or Fe(III)-citrate-reducing conditions (Dred_0432-3 and Dred_1778-84). Two of these hdr-containing loci display homology to recently described flavin-based electron bifurcation (FBEB) pathways (Dred_1325-30 and Dred_1778-84). Additionally, we propose that a cluster of proteins, which is homologous to a described FBEB lactate dehydrogenase (LDH) complex, is performing lactate oxidation in D. reducens (Dred_0367-9). Analysis of the putative sulfate reduction machinery in D. reducens revealed that most of these proteins are constitutively expressed across cultivation conditions tested. In addition, peptides from the single multiheme c-type cytochrome (MHC) in the genome were exclusively observed on the insoluble Fe(III) condition, suggesting that this MHC may play a role in reduction of insoluble metals.« less

Early diagenesis in the sediments of the Congo deep-sea fan dominated by massive terrigenous deposits: Part III - Sulfate- and methane- based microbial processes

NASA Astrophysics Data System (ADS)

Pastor, L.; Toffin, L.; Decker, C.; Olu, K.; Cathalot, C.; Lesongeur, F.; Caprais, J.-C.; Bessette, S.; Brandily, C.; Taillefert, M.; Rabouille, C.

2017-08-01

Geochemical profiles (SO42-, H2S, CH4, δ13CH4) and phylogenetic diversity of Archaea and Bacteria from two oceanographic cruises dedicated to the lobes sediments of the Congo deep-sea fan are presented in this paper. In this area, organic-rich turbidites reach 5000 m and allow the establishment of patchy cold-seep-like habitats including microbial mats, reduced sediments, and vesicomyid bivalves assemblages. These bivalves live in endosymbiosis with sulfur-oxidizing bacteria and use sulfides to perform chemosynthesis. In these habitats, unlike classical abyssal sediments, anoxic processes are dominant. Total oxygen uptake fluxes and methane fluxes measured with benthic chambers are in the same range as those of active cold-seep environments, and oxygen is mainly used for reoxidation of reduced compounds, especially in bacterial mats and reduced sediments. High concentrations of methane and sulfate co-exist in the upper 20 cm of sediments, and evidence indicates that sulfate-reducing microorganisms and methanogens co-occur in the shallow layers of these sediments. Simultaneously, anaerobic oxidation of methane (AOM) with sulfate as the electron acceptor is evidenced by the presence of ANMEs (ANaerobic MEthanotroph). Dissolved sulfide produced through the reduction of sulfate is reoxidized through several pathways depending on the habitat. These pathways include vesicomyid bivalves uptake (adults or juveniles in the bacterial mats habitats), reoxidation by oxygen or iron phases within the reduced sediment, or reoxidation by microbial mats. Sulfide uptake rates by vesicomyids measured in sulfide-rich sea water (90±18 mmol S m-2 d-1) were similar to sulfide production rates obtained by modelling the sulfate profile with different bioirrigation constants, highlighting the major control of vesicomyids on sulfur cycle in their habitats.

Bacterial community succession during in situ uranium bioremediation: spatial similarities along controlled flow paths.

PubMed

Hwang, Chiachi; Wu, Weimin; Gentry, Terry J; Carley, Jack; Corbin, Gail A; Carroll, Sue L; Watson, David B; Jardine, Phil M; Zhou, Jizhong; Criddle, Craig S; Fields, Matthew W

2009-01-01

Bacterial community succession was investigated in a field-scale subsurface reactor formed by a series of wells that received weekly ethanol additions to re-circulating groundwater. Ethanol additions stimulated denitrification, metal reduction, sulfate reduction and U(VI) reduction to sparingly soluble U(IV). Clone libraries of SSU rRNA gene sequences from groundwater samples enabled tracking of spatial and temporal changes over a 1.5-year period. Analyses showed that the communities changed in a manner consistent with geochemical variations that occurred along temporal and spatial scales. Canonical correspondence analysis revealed that the levels of nitrate, uranium, sulfide, sulfate and ethanol were strongly correlated with particular bacterial populations. As sulfate and U(VI) levels declined, sequences representative of sulfate reducers and metal reducers were detected at high levels. Ultimately, sequences associated with sulfate-reducing populations predominated, and sulfate levels declined as U(VI) remained at low levels. When engineering controls were compared with the population variation through canonical ordination, changes could be related to dissolved oxygen control and ethanol addition. The data also indicated that the indigenous populations responded differently to stimulation for bioreduction; however, the two biostimulated communities became more similar after different transitions in an idiosyncratic manner. The strong associations between particular environmental variables and certain populations provide insight into the establishment of practical and successful remediation strategies in radionuclide-contaminated environments with respect to engineering controls and microbial ecology.

Formation and reduction of furan in a soy sauce model system.

PubMed

Kim, Min Yeop; Her, Jae-Young; Kim, Mina K; Lee, Kwang-Geun

2015-12-15

The formation and reduction of furan using a soy sauce model system were investigated in the present study. The concentration of furan fermented up to 30 days increased by 211% after sterilization compared to without sterilization. Regarding fermentation temperature, furan level after 30 days' fermentation was the highest at 30°C (86.21 ng/mL). The furan levels in the soy sauce fermentation at 20°C and 40°C were reduced by 45% and 88%, respectively compared to 30°C fermentation. Five metal ions (iron sulfate, zinc sulfate, manganese sulfate, magnesium sulfate, and calcium sulfate), sodium sulfite, ascorbic acid, dibutyl hydroxyl toluene (BHT), and butylated hydroxyanisole (BHA) were added in a soy sauce model system. The addition of metal ions such as magnesium sulfate and calcium sulfate reduced the furan concentration significantly by 36-90% and 27-91%, respectively in comparison to furan level in the control sample (p<0.05). Iron sulfate and ascorbic acid increased the furan level at 30 days' fermentation in the soy sauce model system by 278% and 87%, respectively. In the case of the BHT and BHA, furan formation generally was reduced in the soy sauce model system by 84%, 56%, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species

NASA Astrophysics Data System (ADS)

Watts, Richard J.; Yu, Miao; Teel, Amy L.

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical + sulfate radical probe, and hexachloroethane as a reductant + nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole > > TCE > PCE > > nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion.

A case study of the intrinsic bioremediation of petroleum hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barker, G.W.; Raterman, K.T.; Fisher, J.B.

1995-12-31

Condensate liquids have been found to contaminate soil and groundwater at two gas production sites in the Denver Basin operated by Amoco Production Co. These sites have been closely monitored since July 1993 to determine whether intrinsic aerobic or anaerobic bioremediation of hydrocarbons occurs at a sufficient rate and to an adequate endpoint to support a no-intervention decision. Groundwater monitoring and analysis of soil cores suggest that intrinsic bioremediation is occurring at these sites by multiple pathways including aerobic oxidation, Fe{sup 3+} reduction, and sulfate reduction. In laboratory experiments the addition of gas condensate hydrocarbons to saturated soil from themore » gas production site stimulated sulfate reduction under anaerobic and oxygen-limiting conditions, and nitrate and Fe{sup 3+} reduction under oxygen-limiting conditions, compared to biotic controls that lacked hydrocarbon and sterile controls. The sulfate reduction corresponded to a reduction in the amount of toluene relative to other hydrocarbons. These results confirmed that subsurface soils at the gas production site have the potential for intrinsic bioremediation of hydrocarbons.« less

Potential sulfate reduction in deeply buried coalbeds 2 km below the seafloor off the Shimokita Peninsula (Japan)

NASA Astrophysics Data System (ADS)

Glombitza, C.; Inagaki, F.; Lever, M. A.; Jørgensen, B. B.

2013-12-01

Integrated Ocean Drilling Program (IODP) Expedition 337 aboard the drilling vessel Chikyu in summer 2012 was the first IODP expedition to drill into a deeply buried hydrocarbon system by riser drilling and, in the process, extended the depth record of scientific ocean drilling to 2466 meters below seafloor (mbsf). A main scientific goal of Expedition 337 was to explore microbial communities associated with deeply buried coalbeds 2 km below the seafloor at Site C0020 off the Shimokita Peninsula of Japan, northwestern coast of the Pacific Ocean. Four lithological units were defined according to sedimentological observations (Inagaki et al. 2012). Temperature measurements during wireline logging revealed in-situ temperatures in the range habitable for life, with ~40-45°C in 2km-deep coalbeds and 60°C at the bottom of the hole. To determine potential sulfate reduction rates (pSRRs) throughout the lower half of the borehole (1200-2466 mbsf; Units II - IV), we prepared slurries from fresh core material in artificial seawater medium containing 1 mM of sulfate and incubated these onboard with 35S-labeled sulfate at approximate in-situ temperatures (i.e., 25, 35, and 45°C). A duplicate set of incubations was started from each sample, one with only N2 in the headspace, and one with N2 + CH4 in the headspace. We incubated samples with 3.7 MBq 35S for a period of 10 days to achieve a detection limit of ca. 10 fmol sulfate cm-3 d-1. pSRRs were close to the detection limit in Unit II and increased by two orders of magnitude up to 2 pmol cm-3 d-1 in the coal-bearing strata (Unit III), decreasing again below in Unit IV. Maximum rates in Unit III reached values similar to those determined during the Chikyu shakedown cruise at 350 mbsf at the same site in 2006. In contrast to the pSRRs determined previously, however, addition of methane did not stimulate pSRRs, suggesting that potential sulfate reduction was supported by electron donors other than methane. The increase of pSRR in the coal-bearing unit is in accordance with other indicators of increased microbial activity in this depth interval, such as high C1/C2 ratios with low 13C/12C isotope ratios of methane observed by real-time mud gas logging during riser drilling. Inagaki, F., K.-U. Hinrichs, Y. Kubo, and the Expedition 337 Scientists (2012), Deep coalbed biosphere off Shimokita: microbial processes and hydrocarbon system associated with deeply buried coalbed in the ocean, IODP Prel. Rept., 337, doi: 10.2204/iodp.pr.337.2012

Unraveling multiple phases of sulfur cycling during the alteration of ancient ultramafic oceanic lithosphere

NASA Astrophysics Data System (ADS)

Schwarzenbach, Esther M.; Gill, Benjamin C.; Johnston, David T.

2018-02-01

Ultramafic-hosted hydrothermal systems - characterized by ongoing serpentinization reactions - exert an important influence on the global sulfur cycle. Extensive water-rock interaction causes elemental exchange between seawater and the oceanic lithosphere, effectively removing sulfate from seawater through both abiogenic and biogenic processes. Here, we use bulk rock multiple sulfur isotope signatures (32S, 33S, 34S) and in situ sulfide analyses together with petrographic observations to track the sulfur cycling processes and the hydrothermal evolution of ancient peridotite-hosted hydrothermal systems. We investigate serpentinized peridotites from the Northern Apennine ophiolite in Italy and the Santa Elena ophiolite in Costa Rica and compare those with the Iberian Margin (Ocean Drilling Program (ODP) Leg 149 and 173) and the 15°20‧N Fracture Zone along the Mid-Atlantic Ridge (ODP Leg 209). In situ measurements of sulfides in the Northern Apennine serpentinites preserve a large range in δ34Ssulfide of -33.8 to +13.3‰ with significant heterogeneities within single sulfide grains and depending on mineralogy. Detailed mineralogical investigation and comparison with bulk rock Δ33Ssulfide and in situ δ34Ssulfide data implies a thermal evolution of the system from high temperatures (∼350 °C) that allowed thermochemical sulfate reduction and input of hydrothermal sulfide to lower temperatures (<120 °C) that permitted microbial activity. The change in temperature regime is locally preserved in individual samples and correlates with the progressive uplift and exposure of mantle rock associated with detachment faulting along a mid-ocean ridge spreading center. The Santa Elena peridotites preserve distinct signatures for fluid circulation at high temperatures with both closed system thermochemical sulfate reduction and input of mafic-derived sulfur. In addition, the peridotites provide strong evidence that low Ca2+ concentrations in peridotite-hosted systems can limit sulfate removal during anhydrite precipitation at temperatures above 150 °C. This may play a central role for the availability of sulfate to microbial communities within these systems. Overall, the combined application of in situ and bulk rock multiple sulfur isotope measurements with petrographic observations allows us to resolve the different episodes of sulfur cycling during alteration of the oceanic lithosphere and the temporal changes between abiogenic and biogenic processes that control the sulfur cycling in these systems.

Monitoring TCE Degradation by In-situ Bioremediation in TCE-Contaminated site

NASA Astrophysics Data System (ADS)

Han, K.; Hong, U.; Ahn, G.; Jiang, H.; Yoo, H.; Park, S.; Kim, N.; Ahn, H.; Kwon, S.; Kim, Y.

2012-12-01

Trichloroethylene (TCE) is a long-term common groundwater pollutant because the compound with high density is slowly released into groundwater. Physical and chemical remediation processes have been used to clean-up the contaminant, but novel remediation technology is required to overcome a low efficiency of the traditional treatment process. Many researchers focused on biological process using an anaerobic TCE degrading culture, but it still needs to evaluate whether the process can be applied into field scale under aerobic condition. Therefore, in this work we investigated two different tests (i.e., biostimulation and bioaugmentation) of biological remediation through the Well-to-Well test (injection well to extraction well) in TCE-contaminated site. Also solutions (Electron donor & acceptor, tracer) were injected into the aquifer using a liquid coupled with nitrogen gas sparging. In biostimulation, we use 3 phases to monitoring biological remediation. Phase 1: we inject formate solution to get electron donor hydrogen (hydrogen can be generated from fermentation of formate). We also inject bromide as tracer. Phase 2: we made injection solution by formate, bromide and sulfate. The reason why we inject sulfate is that as a kind of electron accepter, sulfate reduction process is helpful to create anaerobic condition. Phase 3: we inject mixed solution made by formate, sulfate, fumarate, and bromide. The degradation of fumarate has the same mechanism and condition with TCE degradation, so we added fumarate to make sure that if the anaerobic TCE degradation by indigenous microorganisms started up (Because low TCE concentration by gas sparging). In the bioaugmentation test, we inject the Evanite culture (containing dehalococcoides spp) and TCE degradation to c-DCE, VC, ETH was monitored. We are evaluating the transport of the Evanite culture in the field by measuring TCE and VC reductases.

Reduction of Cr(VI) to Cr(III) in Artificially-Contaminated Soil using Chemical Reagents

NASA Astrophysics Data System (ADS)

Kostarelos, Konstantinos; Rao, Ennio; Reale, Daniela

2010-05-01

The presence of hexavalent chromium (CrVI) in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. A remediation approach that has been studied in the literature is that of reducing the hexavalent chromium to its trivalent form using a chemical reagent, namely ferrous sulfate heptahydrate (FeSO4.7H20). In this study, we compared performance of ferrous sulfate heptahydrate to sodium thiosulfate (Na2S2O3), a less costly reductant. The means of measuring the performance of the reductants is the US EPA's Toxicity Characteristic Leaching Procedure (TCLP), which states that the total chromium release from the soil must be less than 5 ppm. Because this treatment approach is pH sensitive and thus, susceptible to acid rain effects, it was studied with the intention that it be coupled with a stabilization/fixation approach so as to provide a second level of treatment; i.e., it is not intended to be the stand-alone treatment approach. In this study, the reductants were initially used to treat a contaminated, artificial soil and allowed to cure for varying time periods to determine the minimum curing time. Contaminated artificial soil were then prepared using the same percentage of white sand, kaolinite clay and potassium chromate and varying amount of water as a function of the humidity of the specimens in order to illucidate the effect of moisture on the reductant performance. Finally, the reductant (either ferrous sulfate heptahydrate or sodium thiosulfate) was added in varying doses to determine the best ratio Cr/reagent dose. Chromium release from the soil was evaluated with a modified Toxicity Characteristic Leaching Procedure (TCLP) test after allowing the samples to cure. Results indicated that chromium(VI) released from the specimens was less than 5 ppm for the samples treated with either ferrous sulfate heptahydrate (99.9% of reduction) and sodium thiosulfate (98.7% of reduction) with ratio Cr/reagent equal to 18.7 in both cases. In addition, samples treated with ferrous sulfate also exhibited a binding effect. In summary, reduction to a lower valence state can be an effective treatment option when coupled with a stabilization/solidification treatment, so that any chromium subsequently leached from the treated soil into groundwater is the less toxic and less mobile trivalent form of chromium. An alternative to ferrous sulfate heptahydrate, the less-expensive sodium thiosulfate, performed well as a reductant and is suggested for further study.

Dynamics of microbial community composition and function during in-situ bioremediation of a uranium-contaminated aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nostrand, J.D. Van; Wu, L.; Wu, W.M.

2010-08-15

A pilot-scale system was established to examine the feasibility of in situ U(VI) immobilization at a highly contaminated aquifer (U.S. DOE Integrated Field Research Challenge site, Oak Ridge, TN). Ethanol was injected intermittently as an electron donor to stimulate microbial U(VI) reduction, and U(VI) concentrations fell to below the Environmental Protection Agency drinking water standard (0.03 mg liter{sup -1}). Microbial communities from three monitoring wells were examined during active U(VI) reduction and maintenance phases with GeoChip, a high-density, comprehensive functional gene array. The overall microbial community structure exhibited a considerable shift over the remediation phases examined. GeoChip-based analysis revealed thatmore » Fe(III)-reducing bacterial (FeRB), nitrate-reducing bacterial (NRB), and sulfate-reducing bacterial (SRB) functional populations reached their highest levels during the active U(VI) reduction phase (days 137 to 370), in which denitrification and Fe(III) and sulfate reduction occurred sequentially. A gradual decrease in these functional populations occurred when reduction reactions stabilized, suggesting that these functional populations could play an important role in both active U(VI) reduction and maintenance of the stability of reduced U(IV). These results suggest that addition of electron donors stimulated the microbial community to create biogeochemical conditions favorable to U(VI) reduction and prevent the reduced U(IV) from reoxidation and that functional FeRB, SRB, and NRB populations within this system played key roles in this process.« less

Dynamics of Microbial Community Composition and Function during In Situ Bioremediation of a Uranium-Contaminated Aquifer▿‡

PubMed Central

Van Nostrand, Joy D.; Wu, Liyou; Wu, Wei-Min; Huang, Zhijian; Gentry, Terry J.; Deng, Ye; Carley, Jack; Carroll, Sue; He, Zhili; Gu, Baohua; Luo, Jian; Criddle, Craig S.; Watson, David B.; Jardine, Philip M.; Marsh, Terence L.; Tiedje, James M.; Hazen, Terry C.; Zhou, Jizhong

2011-01-01

A pilot-scale system was established to examine the feasibility of in situ U(VI) immobilization at a highly contaminated aquifer (U.S. DOE Integrated Field Research Challenge site, Oak Ridge, TN). Ethanol was injected intermittently as an electron donor to stimulate microbial U(VI) reduction, and U(VI) concentrations fell to below the Environmental Protection Agency drinking water standard (0.03 mg liter−1). Microbial communities from three monitoring wells were examined during active U(VI) reduction and maintenance phases with GeoChip, a high-density, comprehensive functional gene array. The overall microbial community structure exhibited a considerable shift over the remediation phases examined. GeoChip-based analysis revealed that Fe(III)-reducing bacterial (FeRB), nitrate-reducing bacterial (NRB), and sulfate-reducing bacterial (SRB) functional populations reached their highest levels during the active U(VI) reduction phase (days 137 to 370), in which denitrification and Fe(III) and sulfate reduction occurred sequentially. A gradual decrease in these functional populations occurred when reduction reactions stabilized, suggesting that these functional populations could play an important role in both active U(VI) reduction and maintenance of the stability of reduced U(IV). These results suggest that addition of electron donors stimulated the microbial community to create biogeochemical conditions favorable to U(VI) reduction and prevent the reduced U(IV) from reoxidation and that functional FeRB, SRB, and NRB populations within this system played key roles in this process. PMID:21498771

Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

PubMed

Killingsworth, Bryan A; Bao, Huiming; Kohl, Issaku E

2018-05-17

Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .

A rapid and simple method for estimating sulfate reduction activity and quantifying inorganic sulfides

USGS Publications Warehouse

Ulrich, G.A.; Krumholz, L.R.; Suflita, J.M.

1997-01-01

A simplified passive extraction procedure for quantifying reduced inorganic sulfur compounds from sediments and water is presented. This method may also be used for the estimation of sulfate reduction rates. Efficient extraction of FeS, FeS(inf2), and S(sup2-) was obtained with this procedure; however, the efficiency for S(sup0) depended on the form that was tested. Passive extraction can be used with samples containing up to 20 mg of reduced sulfur. We demonstrated the utility of this technique in a determination of both sulfate reduction rates and reduced inorganic sulfur pools in marine and freshwater sediments. A side-by-side comparison of the passive extraction method with the established single-step distillation technique yielded comparable results with a fraction of the effort.

In situ Bioreduction of Uranium (VI) in Groundwater and Sediments with Edible Oil as the Electron Donor

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Mehlhorn, T.; Zhang, G.; Earles, J.; Lowe, K.; Phillips, J.; Boyanov, M.; Kemner, K. M.; Schadt, C. W.; Brooks, S. C.; Criddle, C.; Jardine, P.

2009-12-01

In situ bioremediation of a uranium-contaminated aquifer was conducted at the US DOE Environmental Remediation Sciences Program (ERSP) Integrated Field Research Challenge (IFRC) site, in Oak Ridge, TN. Edible oil was tested as a slow-release electron donor for microbially mediated U (VI) reduction. Uranium contaminated sediments from the site were used in laboratory microcosm tests to study the feasibility of using this electron donor under anaerobic, ambient temperature conditions. Parallel microcosms were established using ethanol as electron donor for comparison. The tests also examined the impact of sulfate concentrations on U (VI) reduction. The oil was degraded by indigenous microorganisms with acetate as a major product but at a much slower rate than ethanol. The rapid removal of U (VI) from the aqueous phase occurred concurrently with acetate production and sulfate reduction. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 vs. 5 mM), likely due to U(VI) desorption from the solid phase, but more U(VI) was reduced with higher initial sulfate level. Finally, the bioreaction in microcosms progressed to methanogenesis. Subsequently, a field test with the edible oil was conducted in a highly permeable gravelly layer (hydraulic conductivity 0.076 cm/sec). Groundwater at the site contained 5-6 μM U; 1.0-1.2 mM sulfate; 3-4 mM Ca; pH 6.8. Diluted emulsified oil (20% solution) was injected into three injection wells within 2 hrs. Geochemical analysis of site groundwater demonstrated the sequential reduction of nitrate, Mn, Fe(III) and sulfate. Transient accumulation of acetate was observed as an intermediate in the oil degradation. Reduction and removal of uranium from groundwater was observed in all wells connected to the injection wells after 2-4 weeks. Uranium concentrations in groundwater were reduced to below 0.126 μM (EPA drinking water standard), at some well locations. Rebound of U in groundwater was observed together with the rebound of sulfate concentrations as the oil was consumed. Uranium (VI) reduction to U (IV) in the microcosm and in situ field tests was confirmed by X-ray near-edge absorption spectroscopy analysis. Bacterial populations in microcosms and field samples were analyzed using 16S rRNA gene libraries and Geochip analysis.

INFLUENCE OF THE SEAGRASS THALASSIA TESTUDINUM ON THE COMMUNITY COMPOSITION AND ACTIVITY OF SULFATE-REDUCING BACTERIA IN AN ESSENTIAL COAST MARINE HABITAT

EPA Science Inventory

Biogeochemical cycling of nutrients and sulfate reduction rates (SRR) were studied in relation to the community composition of sulfate-reducing bacteria SRB) in a Thalassia testudinum bed and in adjacent unvegetated areas. Sampling took place in Santa Rosa Sound, Pensacola, Flori...

High rates of sulfate reduction in a low-sulfate hot spring microbial mat are driven by a low level of diversity of sulfate-respiring microorganisms.

PubMed

Dillon, Jesse G; Fishbain, Susan; Miller, Scott R; Bebout, Brad M; Habicht, Kirsten S; Webb, Samuel M; Stahl, David A

2007-08-01

The importance of sulfate respiration in the microbial mat found in the low-sulfate thermal outflow of Mushroom Spring in Yellowstone National Park was evaluated using a combination of molecular, microelectrode, and radiotracer studies. Despite very low sulfate concentrations, this mat community was shown to sustain a highly active sulfur cycle. The highest rates of sulfate respiration were measured close to the surface of the mat late in the day when photosynthetic oxygen production ceased and were associated with a Thermodesulfovibrio-like population. Reduced activity at greater depths was correlated with novel populations of sulfate-reducing microorganisms, unrelated to characterized species, and most likely due to both sulfate and carbon limitation.

High Rates of Sulfate Reduction in a Low-Sulfate Hot Spring Microbial Mat Are Driven by a Low Level of Diversity of Sulfate-Respiring Microorganisms▿

PubMed Central

Dillon, Jesse G.; Fishbain, Susan; Miller, Scott R.; Bebout, Brad M.; Habicht, Kirsten S.; Webb, Samuel M.; Stahl, David A.

2007-01-01

The importance of sulfate respiration in the microbial mat found in the low-sulfate thermal outflow of Mushroom Spring in Yellowstone National Park was evaluated using a combination of molecular, microelectrode, and radiotracer studies. Despite very low sulfate concentrations, this mat community was shown to sustain a highly active sulfur cycle. The highest rates of sulfate respiration were measured close to the surface of the mat late in the day when photosynthetic oxygen production ceased and were associated with a Thermodesulfovibrio-like population. Reduced activity at greater depths was correlated with novel populations of sulfate-reducing microorganisms, unrelated to characterized species, and most likely due to both sulfate and carbon limitation. PMID:17575000

Sulfur isotope and porewater geochemistry of Florida escarpment seep sediments

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Paull, C.K.; Coston, J.A.

1993-01-01

Distributions of porewater constituents, SO4=, NH4+, Cl-, ???CO2, and H2S, solid phase iron, and sulfur concentrations, and the sulfur isotopic composition of dissolved and solid phases were investigated in sediments from abyssal seeps at the base of the Florida escarpment. Despite the apparent similarity of seep sediment porewater chemistry to that of typical marine sediments undergoing early diagenesis, relationships between chemical distributions and isotopic measurements revealed that the distribution of pore fluid constituents was dominated by processes occurring within the platform rather than by in situ microbial processes. Ammonium and sulfate concentrations were linearly correlated with chloride concentrations, indicating that variations in porewater chemistry were controlled by the admixture of seawater and a sulfate depleted brine with a chlorinity of 27.5 ?? 1.9%. and 2.2 ?? 1.3 mM ammonium concentration. At sites dominated by seepage, dissolved sulfate isotopic composition remained near seawater values despite depletion in porewater concentrations. Porewater ???CO2 concentrations were found to be elevated relative to seawater, but not to the extent predicted from the observed sulfate depletion. Sediment solid phase sulfur was predominantly pyrite, at concentrations as high as 20% S by weight. In contrast to typical marine deposits, pyrite concentrations were not related to the quantity of sedimentary organic matter. Pyrite ??34S values ranged from -29%. to + 21%. (CDT). However, only positive ??34S values were observed at sites associated with high pyrite concentrations. Isotopically heavy pyrite was observed at sites with porewater sulfate of seawater-like isotopic composition. Isotopically light pyrite was associated with sites where porewater sulfate exhibited ??34S values greater than those in seawater, indicating the activity of in situ microbial sulfate reduction. Thus, dual sulfide sources are suggested to explain the range in sediment pyrite isotopic composition: a ??34S enriched (+10 to +20%.) source adverted from within the Florida platform, and a lighter 34S depleted component generated in situ from microbial reduction of seawater sulfate. The degree of pyritization of seep sediments was as high as 0.9 and was controlled by pyrite concentrations, which varied over a wider range than did the non-pyrite solid phase iron concentrations. The highest non-sulfide solid phase iron concentrations were observed in sediments that are believed to be at the "front" of the advancing seep fluids (i.e., hemipelagic sediments newly exposed to the seep fluids), indicating that dissolution of hemipelagic background sediment may be the source of at least half of the iron to the highly pyritized seep sediments. Porewater sulfide concentrations were variable, reaching a maximum of 5.7 mM, and were not correlated with the degree of pyritization of the sediments, suggesting that iron was not particularly limiting to pyrite formation. ?? 1993.

Isotopic evidence for oxygenated Mesoarchaean shallow oceans

NASA Astrophysics Data System (ADS)

Eickmann, Benjamin; Hofmann, Axel; Wille, Martin; Bui, Thi Hao; Wing, Boswell A.; Schoenberg, Ronny

2018-02-01

Mass-independent fractionation of sulfur isotopes (MIF-S) in Archaean sediments results from photochemical processing of atmospheric sulfur species in an oxygen-depleted atmosphere. Geological preservation of MIF-S provides evidence for microbial sulfate reduction (MSR) in low-sulfate Paleoarchaean (3.8-3.2 billion years ago (Ga)) and Neoarchaean (2.8-2.5 Ga) oceans, but the significance of MSR in Mesoarchaean (3.2-2.8 Ga) oceans is less clear. Here we present multiple sulfur and iron isotope data of early diagenetic pyrites from 2.97-Gyr-old stromatolitic dolomites deposited in a tidal flat environment of the Nsuze Group, Pongola Supergroup, South Africa. We identified consistently negative Δ33S values in pyrite, which indicates photochemical reactions under anoxic atmospheric conditions, but large mass-dependent sulfur isotope fractionations of 30‰ in δ34S, identifying active MSR. Negative pyrite δ56Fe values (-1.31 to -0.88‰) record Fe oxidation in oxygen-bearing shallow oceans coupled with biogenic Fe reduction during diagenesis, consistent with the onset of local Fe cycling in oxygen oases 3.0 Ga. We therefore suggest the presence of oxygenated near-shore shallow-marine environments with ≥5 μM sulfate at this time, in spite of the clear presence of an overall reduced Mesoarchaean atmosphere.

Oxygen-Dependent Growth of the Sulfate-Reducing Bacterium Desulfovibrio oxyclinae in Coculture with Marinobacter sp. Strain MB in an Aerated Sulfate-Depleted Chemostat

PubMed Central

Sigalevich, Pavel; Cohen, Yehuda

2000-01-01

A chemostat coculture of the sulfate-reducing bacterium Desulfovibrio oxyclinae and the facultatively aerobic heterotroph Marinobacter sp. strain MB was grown for 1 week under anaerobic conditions at a dilution rate of 0.05 h−1. It was then exposed to an oxygen flux of 223 μmol min−1 by gassing the growth vessel with 5% O2. Sulfate reduction persisted under these conditions, though the amount of sulfate reduced decreased by 45% compared to the amount reduced during the initial anaerobic mode. After 1 week of growth under these conditions, sulfate was excluded from the incoming medium. The sulfate concentration in the growth vessel decreased exponentially from 4.1 mM to 2.5 μM. The coculture consumed oxygen effectively, and no residual oxygen was detected during either growth mode in which oxygen was supplied. The proportion of D. oxyclinae cells in the coculture as determined by in situ hybridization decreased from 86% under anaerobic conditions to 70% in the microaerobic sulfate-reducing mode and 34% in the microaerobic sulfate-depleted mode. As determined by the most-probable-number (MPN) method, the numbers of viable D. oxyclinae cells during the two microaerobic growth modes decreased compared to the numbers during the anaerobic growth mode. However, there was no significant difference between the MPN values for the two modes when oxygen was supplied. The patterns of consumption of electron donors and acceptors suggested that when oxygen was supplied in the absence of sulfate and thiosulfate, D. oxyclinae performed incomplete aerobic oxidation of lactate to acetate. This is the first observation of oxygen-dependent growth of a sulfate-reducing bacterium in the absence of either sulfate or thiosulfate. Cells harvested during the microaerobic sulfate-depleted stage and exposed to sulfate and thiosulfate in a respiration chamber were capable of anaerobic sulfate and thiosulfate reduction. PMID:11055958

Methylmercury oxidative degradation potentials in contaminated and pristine sediments of the Carson River, Nevada

USGS Publications Warehouse

Oremland, R.S.; Miller, L.G.; Dowdle, P.; Connell, T.; Barkay, T.

1995-01-01

Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [14C]MeHg was detected at all sites as indicated by the formation of 14CO2 and 14CH4. Oxidative demethylation was indicated by the formation of 14CO2 and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., 14CO2/14CH4 ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of 14CO2 was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and 14CO2 accounted for 98% of the product formed from [14C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of 14CO2 from [14C]MeHg, while 2-bromoethanesulfonic acid blocked production of 14CH4. These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.

Annual variability and regulation of methane and sulfate fluxes in Baltic Sea estuarine sediments

NASA Astrophysics Data System (ADS)

Sawicka, Joanna E.; Brüchert, Volker

2017-01-01

Marine methane emissions originate largely from near-shore coastal systems, but emission estimates are often not based on temporally well-resolved data or sufficient understanding of the variability of methane consumption and production processes in the underlying sediment. The objectives of our investigation were to explore the effects of seasonal temperature, changes in benthic oxygen concentration, and historical eutrophication on sediment methane concentrations and benthic fluxes at two type localities for open-water coastal versus eutrophic, estuarine sediment in the Baltic Sea. Benthic fluxes of methane and oxygen and sediment pore-water concentrations of dissolved sulfate, methane, and 35S-sulfate reduction rates were obtained over a 12-month period from April 2012 to April 2013. Benthic methane fluxes varied by factors of 5 and 12 at the offshore coastal site and the eutrophic estuarine station, respectively, ranging from 0.1 mmol m-2 d-1 in winter at an open coastal site to 2.6 mmol m-2 d-1 in late summer in the inner eutrophic estuary. Total oxygen uptake (TOU) and 35S-sulfate reduction rates (SRRs) correlated with methane fluxes showing low rates in the winter and high rates in the summer. The highest pore-water methane concentrations also varied by factors of 6 and 10 over the sampling period with the lowest values in the winter and highest values in late summer-early autumn. The highest pore-water methane concentrations were 5.7 mM a few centimeters below the sediment surface, but they never exceeded the in situ saturation concentration. Of the total sulfate reduction, 21-24 % was coupled to anaerobic methane oxidation, lowering methane concentrations below the sediment surface far below the saturation concentration. The data imply that bubble emission likely plays no or only a minor role in methane emissions in these sediments. The changes in pore-water methane concentrations over the observation period were too large to be explained by temporal changes in methane formation and methane oxidation rates due to temperature alone. Additional factors such as regional and local hydrostatic pressure changes and coastal submarine groundwater flow may also affect the vertical and lateral transport of methane.

Operational and biological analyses of branched water-adjustment and combined treatment of wastewater from a chemical industrial park.

PubMed

Xu, Ming; Cao, Jiashun; Li, Chao; Tu, Yong; Wu, Haisuo; Liu, Weijing

2018-01-01

The combined biological processes of branched water-adjustment, chemical precipitation, hydrolysis acidification, secondary sedimentation, Anoxic/Oxic and activated carbon treatment were used for chemical industrial wastewater treatment in the Taihu Lake Basin. Full-scale treatment resulted in effluent chemical oxygen demand, total nitrogen, NH 3 -N and total phosphorus of 35.1, 5.20, 3.10 and 0.15 mg/L, respectively, with a total removal efficiency of 91.1%, 67.1%, 70.5% and 89.3%, respectively. In this process, short-circuited organic carbon from brewery wastewater was beneficial for denitrification and second-sulfate reduction. The concentration of effluent fluoride was 6.22 mg/L, which also met the primary standard. Gas Chromatography-Mass Spectrometry analysis revealed that many types of refractory compounds were present in the inflow. Microbial community analysis performed in the summer by PCR-denaturing gradient gel electrophoresis and MiSeq demonstrated that certain special functional bacteria, such as denitrificans, phosphorus-accumulating bacteria, sulfate- and perhafnate-reducing bacteria, aromatic compound-degrading bacteria and organic fluoride-degrading bacteria, present in the bio-tanks were responsible for the acceptable specific biological pollutant reduction achieved.

Mercury mobilization in a flooded soil by incorporation into metallic copper and metal sulfide nanoparticles.

PubMed

Hofacker, Anke F; Voegelin, Andreas; Kaegi, Ralf; Kretzschmar, Ruben

2013-07-16

Mercury is a highly toxic priority pollutant that can be released from wetlands as a result of biogeochemical redox processes. To investigate the temperature-dependent release of colloidal and dissolved Hg induced by flooding of a contaminated riparian soil, we performed laboratory microcosm experiments at 5, 14, and 23 °C. Our results demonstrate substantial colloidal Hg mobilization concomitant with Cu prior to the main period of sulfate reduction. For Cu, we previously showed that this mobilization was due to biomineralization of metallic Cu nanoparticles associated with suspended bacteria. X-ray absorption spectroscopy at the Hg LIII-edge showed that colloidal Hg corresponded to Hg substituting for Cu in the metallic Cu nanoparticles. Over the course of microbial sulfate reduction, colloidal Hg concentrations decreased but continued to dominate total Hg in the pore water for up to 5 weeks of flooding at all temperatures. Transmission electron microscopy (TEM) suggested that Hg became associated with Cu-rich mixed metal sulfide nanoparticles. The formation of Hg-containing metallic Cu and metal sulfide nanoparticles in contaminated riparian soils may influence the availability of Hg for methylation or volatilization processes and has substantial potential to drive Hg release into adjacent water bodies.

Microbial Mercury Cycling in Sediments of the San Francisco Bay-Delta

USGS Publications Warehouse

Marvin-DiPasquale, M.; Agee, J.L.

2003-01-01

Microbial mercury (Hg) methylation and methylmercury (MeHg) degradation processes were examined using radiolabled model Hg compounds in San Francisco Bay-Delta surface sediments during three seasonal periods: late winter, spring, and fall. Strong seasonal and spatial differences were evident for both processes. MeHg production rates were positively correlated with microbial sulfate reduction rates during late winter only. MeHg production potential was also greatest during this period and decreased during spring and fall. This temporal trend was related both to an increase in gross MeHg degradation, driven by increasing temperature, and to a build-up in pore water sulfide and solid phase reduced sulfur driven by increased sulfate reduction during the warmer seasons. MeHg production decreased sharply with depth at two of three sites, both of which exhibited a corresponding increase in reduced sulfur compounds with depth. One site that was comparatively oxidized and alkaline exhibited little propensity for net MeHg production. These results support the hypothesis that net MeHg production is greatest when and where gross MeHg degradation rates are low and dissolved and solid phase reduced sulfur concentrations are low.

Microbial mercury cycling in sediments of the San Francisco Bay-Delta

USGS Publications Warehouse

Marvin-DiPasquale, Mark; Agee, Jennifer L.

2003-01-01

Microbial mercury (Hg) methylation and methylmercury (MeHg) degradation processes were examined using radiolabled model Hg compounds in San Francisco Bay-Delta surface sediments during three seasonal periods: late winter, spring, and fall. Strong seasonal and spatial differences were evident for both processes. MeHg production rates were positively correlated with microbial sulfate reduction rates during late winter only. MeHg production potential was also greatest during this period and decreased during spring and fall. This temporal trend was related both to an increase in gross MeHg degradation, driven by increasing temperature, and to a build-up in pore water sulfide and solid phase reduced sulfur driven by increased sulfate reduction during the warmer seasons. MeHg production decreased sharply with depth at two of three sites, both of which exhibited a corresponding increase in reduced sulfur compounds with depth. One site that was comparatively oxidized and alkaline exhibited little propensity for net MeHg production. These results support the hypothesis that net MeHg production is greatest when and where gross MeHg degradation rates are low and dissolved and solid phase reduced sulfur concentrations are low.

Assessing the Role of Iron Sulfides in the Long Term Sequestration of Uranium by Sulfate-Reducing Bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, Kim F.; Bi, Yuqiang; Carpenter, Julian

2013-12-31

This overarching aim of this project was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. The work reported herein was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM). Research at ASU, focused on the biogenesis aspects, examined the biogeochemical bases for iron-sulfide production by Desulfovibrio vulgaris, a Gram-negative bacterium that is one of the most-studied strains of sulfate-reducing bacteria. A series of experimental studies were performed to investigate comprehensively important metabolic andmore » environmental factors that affect the rates of sulfate reduction and iron-sulfide precipitation, the mineralogical characteristics of the iron sulfides, and how uranium is reduced or co-reduced by D. vulagaris. FeS production studies revealed that controlling the pH affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH produced larger-sized mackinawite (Fe 1+xS). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and stimulated mackinawite transformation to greigite (Fe 3S 4) when the free sulfide concentration was 29.3 mM. On the other hand, using solid Fe(III) (hydr)oxides as the iron source led to less productivity of FeS due to their slow and incomplete dissolution and scavenging of sulfide. Furthermore, sufficient free Fe 2+, particularly during Fe(III) (hydr)oxide reductions, led to the additional formation of vivianite [Fe 3(PO 4) 2•8(H 2O)]. The U(VI) reduction studies revealed that D. vulgaris reduced U(VI) fastest when accumulating sulfide from concomitant sulfate reduction, since direct enzymatic and sulfide-based reductions of U(VI) occurred in parallel. The UO 2 produced in presence of ferrous iron was poorly crystalline. At UM, laboratory-scale reactor studies were performed to assess the potential for the predominant abiotic reductants formed under sulfate reducing conditions (SRCs) to: (1) reduce U(VI) in contaminated groundwater sediments), and (2) inhibit the re-oxidation of U(IV) species, and in particular, uraninite (UO 2(s)). Under SRCs, mackinawite and aqueous sulfide are the key reductants expected to form. To assess their potential for abiotic reduction of U(VI) species, a series of experiments were performed in which either FeS or S(-II) was added to solutions of U(VI), with the rates of conversion to U(IV) solids monitored as a function of pH, and carbonate and calcium concentration. In the presence of FeS and absence of oxygen or carbonate, U(IV) was completely reduced uraninite. S(-II) was also found to be an effective reductant of aqueous phase U(VI) species and produced uraninite, with the kinetics and extent of reduction depending on geochemical conditions. U(VI) reduction to uraninite was faster under higher S(-II) concentrations but was slowed by an increase in the dissolved Ca or carbonate concentration. Rapid reduction of U(VI) occurred at circumneutral pH but virtually no reduction occurred at pH 10.7. In general, dissolved Ca and carbonate slowed abiotic U(VI) reduction by forming stable Ca-U(VI)-carbonate soluble complexes that are resistant to reaction with aqueous sulfide. To investigate the stability of U(IV) against re-oxidation in the presence of iron sulfides by oxidants in simulated groundwater environments, and to develop a mechanistic understanding the controlling redox processes, continuously-mixed batch reactor (CMBR) and flow-through reactor (CMFR) studies were performed at UM. In these studies a series of experiments were conducted under various oxic groundwater conditions to examine the effectiveness of FeS as an oxygen scavenger to retard UO 2 dissolution. The results indicate that FeS is an effective oxygen scavenger, and can lower the rate of oxidative dissolution of UO 2 by over an order of magnitude compared to the absence of FeS, depending on pH, FeS content, and DO concentrations. Column reactor studies were performed at UM to assess the impact of mackinawite on uraninite oxidation under hydrodynamic flow conditions more representative of packed porous media at contaminated groundwater sites. In these studies, Rifle sediments were packed in the two columns which were subjected to different bioreduction steps and then run in parallel. The first column was bioreduced under SRCs (i.e., with sulfate in the influent) to generate mackinawite, mixed with uraninite, gamma-sterilized to inhibit subsequent microbiological activity, and then subjected to groundwater influent containing first nitrite and then oxygen. The second column was bioreduced (but in absence of sulfate in the influent) so that no iron sulfides would form, and then subjected to identical steps and influent as the first column. When nitrite was introduced in the influent of both columns, no significant release of U(VI) relative to the anoxic flow prior to nitrite addition occurred. However, when oxygen was introduced, the column which had undergone sulfate reduction (and had produced mackinawite as later verified by XAS) significantly lowered the peak U(VI) effluent concentrations, and in general, slowed U(VI) release considerably compared to the column with no FeS. Overall, these studies demonstrated that the presence of mackinawite can be a significant scavenger of oxygen and inhibit the oxidation of uraninite by oxygen, whereas nitrite had little impact on uraninite oxidation either in the presence or absence of FeS.« less

Generation of Acid Mine Lakes Associated with Abandoned Coal Mines in Northwest Turkey.

PubMed

Sanliyuksel Yucel, Deniz; Balci, Nurgul; Baba, Alper

2016-05-01

A total of five acid mine lakes (AMLs) located in northwest Turkey were investigated using combined isotope, molecular, and geochemical techniques to identify geochemical processes controlling and promoting acid formation. All of the investigated lakes showed typical characteristics of an AML with low pH (2.59-3.79) and high electrical conductivity values (1040-6430 μS/cm), in addition to high sulfate (594-5370 mg/l) and metal (aluminum [Al], iron [Fe], manganese [Mn], nickel [Ni], and zinc [Zn]) concentrations. Geochemical and isotope results showed that the acid-generation mechanism and source of sulfate in the lakes can change and depends on the age of the lakes. In the relatively older lakes (AMLs 1 through 3), biogeochemical Fe cycles seem to be the dominant process controlling metal concentration and pH of the water unlike in the younger lakes (AMLs 4 and 5). Bacterial species determined in an older lake (AML 2) indicate that biological oxidation and reduction of Fe and S are the dominant processes in the lakes. Furthermore, O and S isotopes of sulfate indicate that sulfate in the older mine lakes may be a product of much more complex oxidation/dissolution reactions. However, the major source of sulfate in the younger mine lakes is in situ pyrite oxidation catalyzed by Fe(III) produced by way of oxidation of Fe(II). Consistent with this, insignificant fractionation between δ(34) [Formula: see text] and δ(34) [Formula: see text] values indicated that the oxidation of pyrite, along with dissolution and precipitation reactions of Fe(III) minerals, is the main reason for acid formation in the region. Overall, the results showed that acid generation during early stage formation of an AML associated with pyrite-rich mine waste is primarily controlled by the oxidation of pyrite with Fe cycles becoming the dominant processes regulating pH and metal cycles in the later stages of mine lake development.

Methane production in the sulfate-depleted sediments of two marine basins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuivila, K.M.; Murray, J.W.; Devol, A.H.

1990-02-01

Rates of methane production via both acetate fermentation and CO{sub 2} reduction were directly measured with radiotracer techniques in the sulfate-depleted sediments of Saanich and Princess Louisa Inlets. Comparison of measured and modeled rates suggests that these two pathways account for the majority of methane produced below the sulfate reduction zone in the sediments of both basins. Methane production via CO{sub 2} reduction was slightly more important than acetate fermentation with 57-58% of the methane in Saanich Inlet and 52-57% in Princess Louisa Inlet being produced from bicarbonate. The results from Saanich Inlet, a seasonally anoxic basin, are compared withmore » Princess Louisa Inlet, with a permanently oxic hypolimnion. Although the two basins have comparable organic-carbon rain rates, the rates of methanogenesis are much lower in Princess Louisa Inlet. This decrease in methane production can be attributed to the consumption of organic carbon via aerobic respiration occurring in the surface sediments of Princess Louisa Inlet, thereby decreasing the actual input of organic carbon to the zone of methane production. The relative importance of CO{sub 2} reduction and acetate fermentation in the production of methane was the same in both basins, suggesting that prior aerobic degradation of the organic matter has little influence on the pathways of methane production. The results from this study in the two marine systems (high sulfate) are also compared to published studies in freshwater environments (low sulfate) where acetate fermentation is the predominant pathway of methane production.« less

A HTAP Multi-Model Assessment of the Influence of Regional Anthropogenic Emission Reductions on Aerosol Direct Radiative Forcing and the Role of Intercontinental Transport

NASA Technical Reports Server (NTRS)

Yu, Hongbin; Chin, Mian; West, J. Jason; Atherton, Cynthia S.; Bellouin, Nicolas; Bergmann, Dan; Bey, Isabelle; Bian, Huisheng; Diehl, Thomas; Forberth, Gerd;

Efficacy of ε-polylysine, lauric arginate, or acidic calcium sulfate applied sequentially for Salmonella reduction on membrane filters and chicken carcasses.

PubMed

Benli, Hakan; Sanchez-Plata, Marcos X; Keeton, Jimmy T

2011-05-01

Salmonella contamination continues to be one of the major concerns for the microbiological safety of raw poultry products. Application of more than one decontamination agent as a multihurdle intervention to carcasses in a processing line might produce greater reductions than one treatment alone due to different modes of action of individual antimicrobials. In this study, all possible two-way combinations and individual applications of ε-polylysine (EPL), lauric arginate (LAE), and acidic calcium sulfate (ACS) solutions were evaluated for their effects against Salmonella enterica serovars, including Enteritidis and Typhimurium, using a sterile membrane filter model system. The combinations that provided higher Salmonella reductions were further evaluated on inoculated chicken carcasses in various concentrations applied in a sequential manner. Sequential spray applications of 300 mg of EPL per liter followed by 30% ACS and of 200 mg of LAE per liter followed by 30% ACS produced the highest Salmonella reductions on inoculated chicken carcasses, by 2.1 and 2.2 log CFU/ml, respectively. Our results indicated that these sequential spray applications of decontamination agents are effective for decreasing Salmonella contamination on poultry carcasses, but further studies are needed to determine the effectiveness of these combinations over a storage period.

Geochemistry of Peruvian near-surface sediments

NASA Astrophysics Data System (ADS)

Böning, Philipp; Brumsack, Hans-Jürgen; Böttcher, Michael E.; Schnetger, Bernhard; Kriete, Cornelia; Kallmeyer, Jens; Borchers, Sven Lars

2004-11-01

Sixteen short sediment cores were recovered from the upper edge (UEO), within (WO) and below (BO) the oxygen minimum zone (OMZ) off Peru during cruise 147 of R/V Sonne. Solids were analyzed for major/trace elements, total organic carbon, total inorganic carbon, total sulfur, the stable sulfur isotope composition (δ 34S) of pyrite, and sulfate reduction rates (SRR). Pore waters were analyzed for dissolved sulfate/sulfide and δ 34S of sulfate. In all cores highest SRR were observed in the top 5 cm where pore water sulfate concentrations varied little due to resupply of sulfate by sulfide oxidation and/or diffusion of sulfate from bottom water. δ 34S of dissolved sulfate showed only minor downcore increases. Strong 32S enrichments in sedimentary pyrite (to -48‰ vs. V-CDT) are due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction. Manganese and Co are significantly depleted in Peruvian upwelling sediments most likely due to mobilization from particles settling through the OMZ, whereas release of both elements from reducing sediments only seems to occur in near-coastal sites. Cadmium, Mo and Re are exceptionally enriched in WO sediments (<600 m water depth). High Re and moderate Cd and Mo enrichments are seen in BO sediments (>600 m water depth). Re/Mo ratios indicate anoxic and suboxic conditions for WO and BO sediments, respectively. Cadmium and Mo downcore profiles suggest considerable contribution to UEO/WO sediments by a biodetrital phase, whereas Re presumably accumulates via diffusion across the sediment-water interface to precipitation depth. Uranium is distinctly enriched in WO sediments (due to sulfidic conditions) and in some BO sediments (due to phosphorites). Silver transfer to suboxic BO sediments is likely governed by diatomaceous matter input, whereas in anoxic WO sediments Ag is presumably trapped due to sulfide precipitation. Cadmium, Cu, Zn, Ni, Cr, Ag, and T1 predominantly accumulate via biogenic pre-concentration in plankton remains. Rhenium, Sb, As, V, U and Mo are enriched in accordance with seawater TE availability. Lead and Bi enrichment in UEO surface sediments is likely contributed by anthropogenic activity (mining). Accumulation rates of TOC, Cd, Mo, U, and V from Peruvian and Namibian sediments exceed those from the Oman Margin and Gulf of California due to enhanced preservation off Peru and Namibia.

Distribution of iron- and sulfate-reducing bacteria across a coastal acid sulfate soil (CASS) environment: implications for passive bioremediation by tidal inundation.

PubMed

Ling, Yu-Chen; Bush, Richard; Grice, Kliti; Tulipani, Svenja; Berwick, Lyndon; Moreau, John W

2015-01-01

Coastal acid sulfate soils (CASS) constitute a serious and global environmental problem. Oxidation of iron sulfide minerals exposed to air generates sulfuric acid with consequently negative impacts on coastal and estuarine ecosystems. Tidal inundation represents one current treatment strategy for CASS, with the aim of neutralizing acidity by triggering microbial iron- and sulfate-reduction and inducing the precipitation of iron-sulfides. Although well-known functional guilds of bacteria drive these processes, their distributions within CASS environments, as well as their relationships to tidal cycling and the availability of nutrients and electron acceptors, are poorly understood. These factors will determine the long-term efficacy of "passive" CASS remediation strategies. Here we studied microbial community structure and functional guild distribution in sediment cores obtained from 10 depths ranging from 0 to 20 cm in three sites located in the supra-, inter- and sub-tidal segments, respectively, of a CASS-affected salt marsh (East Trinity, Cairns, Australia). Whole community 16S rRNA gene diversity within each site was assessed by 454 pyrotag sequencing and bioinformatic analyses in the context of local hydrological, geochemical, and lithological factors. The results illustrate spatial overlap, or close association, of iron-, and sulfate-reducing bacteria (SRB) in an environment rich in organic matter and controlled by parameters such as acidity, redox potential, degree of water saturation, and mineralization. The observed spatial distribution implies the need for empirical understanding of the timing, relative to tidal cycling, of various terminal electron-accepting processes that control acid generation and biogeochemical iron and sulfur cycling.

Recycled Archean sulfur in the mantle wedge of the Mariana Forearc and microbial sulfate reduction within an extremely alkaline serpentine seamount

NASA Astrophysics Data System (ADS)

Aoyama, Shinnosuke; Nishizawa, Manabu; Miyazaki, Junichi; Shibuya, Takazo; Ueno, Yuichiro; Takai, Ken

2018-06-01

The identification of microbial activity under extreme conditions is important to define potential boundaries of the habitable and uninhabitable zones of terrestrial and extraterrestrial living forms. The subseafloor regimes of serpentinite seamounts in the Mariana Forearc are among the most extreme environments for life on earth owing to the widespread presence of highly alkaline fluids with pH values greater than 12. The potential activity of sulfate-reducing microorganisms has been suggested within the South Chamorro serpentinite seamounts on the basis of depletion of sulfate and enrichment of dissolved sulfide in pore water. However, the vertical distribution of sulfate-reducing microorganisms and the origin of sulfate are still uncertain. To address these issues, we analyzed quadruple sulfur isotopes of sulfide minerals and pore water sulfate in the upper 56 m of sedimentary sequences at the summit of the S. Chamorro Seamount and those of dissolved sulfate in upwelling fluids collected as deep as 202 mbsf (meters below the seafloor) in a cased hole near the summit of the same seamount. The depth profiles of the concentrations and the δ34S and Δ33S‧ values of sulfide minerals and pore water sulfate indicate microbial sulfate reduction as deep as 30 mbsf. Further, apparent isotopic fractionations (34ε) and exponents of mass dependent relationships (33λ) during sulfate reduction are estimated to be 62 ± 14‰ and 0.512 ± 0.002, respectively. The upwelling fluids show both the chlorine depletion relative to seawater and the negative δ15N values of ammonia (-4‰). Although these signatures point to dehydration of the subducting oceanic plate, the negative Δ33S‧ values of sulfate (-0.16‰ to -0.26‰ with analytical errors of ±0.01‰) are unlikely to originate from surrounding modern crusts. Instead, sulfate in the upwelling fluid likely possess non-mass-dependent (NMD) sulfur. Because NMD sulfur was produced primarily in the Archean atmosphere, our results suggest that the presence of recycled Archean crust that could be incorporated into the upper mantle through subduction of Archean oceanic crusts or from the NMD-bearing OIB seamounts located in the southern margin of the Pacific Plate.

pH, dissolved oxygen, and adsorption effects on metal removal in anaerobic bioreactors.

PubMed

Willow, Mark A; Cohen, Ronald R H

2003-01-01

Anaerobic bioreactors were used to test the effect of the pH of influent on the removal efficiency of heavy metals from acid-rock drainage. Two studies used a near-neutral-pH, metal-laden influent to examine the heavy metal removal efficiency and hydraulic residence time requirements of the reactors. Another study used the more typical low-pH mine drainage influent. Experiments also were done to (i) test the effects of oxygen content of feed water on metal removal and (ii) the adsorptive capacity of the reactor organic substrate. Analysis of the results indicates that bacterial sulfate reduction may be a zero-order kinetic reaction relative to sulfate concentrations used in the experiments, and may be the factor that controls the metal mass removal efficiency in the anaerobic treatment systems. The sorptive capacities of the organic substrate used in the experiments had not been exhausted during the experiments as indicated by the loading rates of removal of metals exceeding the mass production rates of sulfide. Microbial sulfate reduction was less in the reactors receiving low-pH influent during experiments with short residence times. Sulfate-reducing bacteria may have been inhibited by high flows of low-pH water. Dissolved oxygen content of the feed waters had little effect on sulfate reduction and metal removal capacity.

Sulfur, a Key Water Quality Issue in the Everglades

NASA Astrophysics Data System (ADS)

Orem, W. H.; Lerch, H. E.; Bates, A. L.; Corum, M.; Beck, M.; Kleckner, S.

2002-05-01

Sulfur is an important water quality issue in the Everglades because of its role in microbial sulfate reduction and the methylation of mercury. Methylmercury (MeHg), a neurotoxin that is bioaccumulated, has been found in high concentrations in freshwater fish from the Everglades, and poses a potential threat to fish-eating wildlife and to human health through fish consumption. Sulfur appears to play a key role in regulating both the magnitude and distribution of MeHg in the Everglades. Freshwater wetlands typically have low sulfur concentrations, but marshes in portions of the northern Everglades have average surface water sulfate concentrations of 60 mg/l, compared to 1 mg/l or less at background sites. Marsh areas with excess sulfate are concentrated near sites of canal discharge and along canal levees. The canal water that is discharged into the marshes appears to be the major source of excess sulfate entering the Everglades. This canal water drains the Everglades Agricultural Area (EAA) and has sulfate concentrations averaging over 70 mg/l and periodically approaching 200 mg/l. We used sulfate concentration data and the sulfur (d34S) isotopic composition of sulfate in marsh surface water, canal water, rainwater, and groundwater to trace the source of the excess sulfate entering the Everglades. Results show that canal water from the EAA is the major source of excess sulfate entering the Everglades. Furthermore, canal water with the highest sulfate concentrations had d34S values of +16 per mil, similar to the d34S signature of agricultural sulfur used as a soil amendment in the EAA. Rainwater has too little sulfate to account for the high sulfate concentrations observed in the canals and in large portions of the Everglades. Groundwater beneath the present day Everglades generally has either too low a sulfate concentration or a d34S signature that is inconsistent with that of surface water in the Everglades. The excess sulfate entering the Everglades from canal discharge stimulates sulfate reduction and sulfide buildup in the sediments. This lowers redox potentials in sulfur-contaminated areas to values more reducing than natural, which may affect macrophyte growth in the Everglades by limiting oxygen penetration to roots. Excess sulfur has two differential effects with respect to MeHg production: stimulation through increased sulfate reduction, and inhibition through buildup of excess sulfide in sediment porewater. The balance between these two effects influences the magnitude and distribution of MeHg production in the Everglades. Results from this study and research of others suggest that the MeHg problem in the Everglades results largely from two factors: (1) increased fallout of mercury on the ecoxyxtem, and (2) sulfur contamination of the ecosystem from agricultural runoff.

Electron acceptor-based regulation of microbial greenhouse gas production from thawing permafrost

NASA Astrophysics Data System (ADS)

Bak, Ebbe; Jones, Eleanor; Yde, Jacob; Hodson, Andy; Mallon, Gunnar; Fisnter, Kai

2017-04-01

Permafrost contains about 35% of the global soil organic carbon (0-3 m depth). As a consequence of global warming, the active layer thickness is steadily increasing and its organic carbon is becoming available for degradation, causing a concomitant release of CO2 and CH4. The climate forcing feedbacks of permafrost thaw are determined by the rate of organic carbon degradation and to which degree it is released as CO2 or CH4. Methane is produced under anoxic conditions, but the factors that regulate its production are poorly constrained. In this study, we investigate how CH4 production is influenced by the presence of competing anaerobic processes with focus on the role of iron and sulfate reduction. We have collected permafrost cores to 2.2 meters depth from three different lowland sites in Adventdalen on Svalbard. From these cores, we have prepared anoxic batch incubation for each 25 cm depth interval and followed the production of CO2 and CH4 as well as the iron and sulfate reduction. This approach allows us to monitor the rate of the CO2 and CH4 production as well as to investigate the correlation between CH4 production and competing anaerobic respiration processes in the active layer as well in the permafrost. These investigations are accompanied by characterization of the carbon, iron and sulfate content in the soil and will be followed by characterization of the microbial community structure. The aim of this study is to get a better understanding of how the availability of sulfate and iron and the microbial community structure regulate the production of CO2 and CH4 in thawing permafrost, and to elucidate how the rate of the organic carbon degradation changes with depth in permafrost-affected soils. This study improves our understanding of climate feedback mechanisms operating during permafrost thaw.

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species.

PubMed

Watts, Richard J; Yu, Miao; Teel, Amy L

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical+sulfate radical probe, and hexachloroethane as a reductant+nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole>TCE>PCE >nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion. Published by Elsevier B.V.

The Importance of Sulfate Adenylyl Transferase in S and O Fractionation by Sulfate Reducing Bacteria

NASA Astrophysics Data System (ADS)

Smith, D. A.; Johnston, D. T.; Bradley, A. S.

2016-12-01

Microbial sulfate reduction (MSR) is critical to the oxidation of organic matter in modern and ancient oceans, and plays an important role in regulating the redox state of the Earth's surface. The sulfur and oxygen isotopic composition of seawater sulfate and of sulfate minerals reflect the biogeochemical processes that cycle sulfur, of which MSR is among the most important. MSR is a multi-enzymatic reaction network that partitions the isotopes of sulfur and oxygen as a consequence of both the flux of sulfate through this biochemical network and the fractionation imposed by each individual enzyme. MSR affects the δ18O of residual, extracellular sulfate mainly by the equilibration of the MSR intermediate sulfite with extracellular water (Antler et al., 2013 GCA, Wankel et al., 2013 Geobiol). A series of oxidative and exchange reactions catalyzed by APS reductase (APSr), sulfate adenylyl transferase (Sat), and sulfate transporters promote the conversion of water-equilibrated intracellular sulfite to extracellular sulfate. The flux of sulfoxy anions via these proteins will be, at least in part, dependent on the activity of these enzymes. To test this, we examined sulfur and oxygen isotope fractionation in genetically engineered mutants of the sulfate reducing bacterium Desulfovibrio vulgaris Hildenborough (DvH). In these mutants, the activity of Sat has been artificially increased by perturbing the (i) transcriptional repressor Rex and (ii) its binding site upstream of the gene encoding Sat (Christensen et al., 2015 J. Bacteriol). It was predicted that this would minimize the back reaction of Sat, enhance the intracellular pool of APS, and minimize the equilibration between sulfite and adenosine monophosphate (AMP). Both mutants, along with the wild type DvH were grown in batch culture made with water enriched in 18O. Samples were collected throughout batch growth, and we report the evolution of the S and O isotopic composition of sulfate, and of the S isotopic composition of sulfide. The results from this experiment will inform our understanding of the metabolic controls on the isotopic composition of seawater sulfate.

Symptom and structure modification in osteoarthritis with pharmaceutical-grade chondroitin sulfate: what's the evidence?

PubMed

Hochberg, M; Chevalier, X; Henrotin, Y; Hunter, D J; Uebelhart, D

2013-03-01

Osteoarthritis is a chronic disease characterized by irreversible damage to joint structures, including loss of articular cartilage, osteophyte formation, alterations in the subchondral bone and synovial inflammation. It has been shown that chondroitin sulfate interferes with the progression of structural changes in joint tissues and is used in the management of patients with osteoarthritis. This review summarizes data from relevant reports describing the mechanisms of action of chondroitin sulfate that may explain the beneficial effects of the drug and examines the evidence for clinical efficacy of oral chondroitin sulfate in osteoarthritis. Data included in the review were derived from a literature search in PubMed. Literature searches were performed in PubMed using the search terms 'chondroitin sulfate', 'pharmaceutical-grade', 'osteoarthritis', 'randomized clinical trials', 'humans'. The MEDLINE database was searched from January 1996 through August 2012 for all randomized controlled trials, meta-analyses, systematic reviews, and review articles of chondroitin sulfate in osteoarthritis. Chondroitin sulfate exerts in vitro a beneficial effect on the metabolism of different cell lines: chondrocytes, synoviocytes and cells from subchondral bone, all involved in osteoarthritis. It increases type II collagen and proteoglycan synthesis in human articular chondrocytes and is able to reduce the production of some pro-inflammatory factors and proteases, to reduce the cellular death process, and improve the anabolic/catabolic balance of the extracellular cartilage matrix (ECM). Clinical trials have reported a beneficial effect of chondroitin sulfate on pain and function. The structure-modifying effects of chondroitin sulfate have been reported and analyzed in recent meta-analyses. The results in knee osteoarthritis demonstrate a small but significant reduction in the rate of decline in joint space width. Because chondroitin sulfate quality of several nutraceuticals has been found to be poor, it is recommended that pharmaceutical-grade chondroitin sulfate is used rather than food supplements in the treatment of OA. Chondroitin sulfate is recommended by several guidelines from international societies in the management of knee and hip OA. Furthermore, its safety profile is favorable when compared with many other therapies used in OA. Chondroitin sulfate is an effective and safe treatment option for patients with osteoarthritis.

Characterisation of medical-waste sterilisation-plant wastewater and a preliminary study of coagulation-flocculation treatment options.

PubMed

Ozkan, O; Mihçiokur, H; Azgin, S T; Ozdemir, O

2010-01-01

Wastewater from a medical-waste sterilisation plant (MWSP) contains unique pollutants and requires on-site treatment to prevent contamination of the municipal sewage system and receiving water bodies. Therefore, to meet the prescribed discharge standards and comply with the legal regulations, pre-treatment must be applied to MWSP wastewater. In this study, the capabilities of coagulation-flocculation processes were investigated for MWSP wastewater treatment. Processes using ferric chloride, ferrous sulfate and aluminium sulfate as coagulants were characterised. During the coagulation experiments, seven different coagulant dosages and four different pH values were evaluated to determine the optimum coagulant dosage and pH value. The highest removal efficiency of chemical oxygen demand (COD) was obtained using 300 mg/L of ferric chloride at pH 10. A COD removal of about 60% as well as considerable reductions in the amounts of suspended solids, nitrogen and phosphorus were realised.

Sulfate-reducing bacteria and their activities in cyanobacterial mats of Solar Lake (Sinai, Egypt)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teske, A.; Ramsing, N.B.; Habicht, K.

1998-08-01

The sulfate-reducing bacteria within the surface layer of the hypersaline cyanobacterial mat of Solar Lake (Sinai, Egypt) were investigated with combined microbiological, molecular, and biogeochemical approaches. The diurnally oxic surface layer contained between 10{sup 6} and 10{sup 7} cultivable sulfate-reducing bacteria ml{sup {minus}1} day{sup {minus}1}, both in the same range as and sometimes higher than those in anaerobic deeper mat layers. In the oxic surface layer and in the mat layers below, filamentous sulfate-reducing Desulfonema bacteria were found in variable densities of 10{sup 4} and 10{sup 6} cells ml{sup {minus}1}. A Desulfonema-related, diurnally migrating bacterium was detected with PCR andmore » denaturing gradient gel electrophoresis within and below the oxic surface layer. Facultative aerobic respiration, filamentous morphology, motility, diurnal migration, and aggregate formation were the most conspicuous adaptations of Solar Lake sulfate-reducing bacteria to the mat matrix and to diurnal oxygen stress. A comparison of sulfate reduction rates within the mat and previously published photosynthesis rates showed that CO{sub 2} from sulfate reduction in the upper 5 mm accounted for 7 to 8% of the total photosynthetic CO{sub 2} demand of the mat.« less

Transport processes in intertidal sand flats

NASA Astrophysics Data System (ADS)

Wu, Christy

2010-05-01

Methane rich sulfate depleted seeps are observed along the low water line of the intertidal sand flat Janssand in the Wadden Sea. It is unclear where in the flat the methane is formed, and how it is transported to the edge of the sand flat where the sulfidic water seeps out. Methane and sulfate distributions in pore water were determined along transects from low water line toward the central area of the sand flat. The resulting profiles showed a zone of methane-rich and sulfate-depleted pore water below 2 m sediment depth. Methane production and sulfate reduction are monitored over time for surface sediments collected from the upper flat and seeping area. Both activities were at 22 C twice as high as at 15 C. The rates in sediments from the central area were higher than in sediments from the methane seeps. Methanogenesis occurred in the presence of sulfate, and was not significantly accelerated when sulfate was depleted. The observations show a rapid anaerobic degradation of organic matter in the Janssand. The methane rich pore water is obviously transported with a unidirectional flow from the central area of the intertidal sand flat toward the low water line. This pore water flow is driven by the pressure head caused by elevation of the pore water relative to the sea surface at low tide (Billerbeck et al. 2006a). The high methane concentration at the low water line accumulates due to a continuous outflow of pore water at the seepage site that prevents penetration of electron acceptors such as oxygen and sulfate to reoxidize the reduced products of anaerobic degradation (de Beer et al. 2006). It is, however, not clear why no methane accumulates or sulfate is depleted in the upper 2 m of the flats.

Mercury methylation and sulfate reduction rates in mangrove sediments, Rio de Janeiro, Brazil: The role of different microorganism consortia.

PubMed

Correia, Raquel Rose Silva; Guimarães, Jean Remy Davée

2017-01-01

Recent studies have shown Hg methylation in mangrove sediments, however, little is known about the different microorganism consortia involved. We investigated the participation of prokaryotes in general, iron-reducing bacteria-IRB, sulfate-reducing bacteria-SRB, methanogens and fungi in Hg methylation and sulfate reduction rates (SRR) in mangrove sediments using iron amendments for IRB and specific inhibitors for the other microorganisms. Sediment samples were collected from two mangrove zones, tidal flat and mangrove forest (named root sediments). Samples were incubated with 203 Hg or 35 SO 4 2- and Me 203 Hg/ 35 Sulfur were measured by liquid scintillation. Methylmercury (MeHg) formation was significantly reduced when SRB (87.7%), prokaryotes (76%) and methanogens (36.5%) were inhibited in root sediments, but only SRB (51.6%) and prokaryotes (57.3%) in tidal flat. However, in the tidal flat, inhibition of methanogens doubled Hg methylation (104.5%). All inhibitors (except fungicide) significantly reduced SRR in both zones. In iron amended tidal flat samples, Hg methylation increased 56.5% at 100 μg g -1 and decreased at 500 and 1000 μg g -1 (57.8 and 82%). In the roots region, however, MeHg formation gradually decreased in response to Fe amendments from 100 μg g -1 (37.7%) to 1000 μg g -1 (93%). SRR decreased in all iron amendments. This first simultaneous evaluation of Hg methylation and sulfate-reduction and of the effect of iron and inhibitors on both processes suggest that SRB are important Hg methylators in mangrove sediments. However, it also suggests that SRB activity could not explain all MeHg formation. This implies the direct or indirect participation of other microorganisms such as IRB and methanogens and a complex relationship among these groups. Copyright © 2016. Published by Elsevier Ltd.

Modeling anoxic aggregates in the ocean - implications for nitrogen, sulfur and trace metal cycling

NASA Astrophysics Data System (ADS)

Bianchi, D.; Weber, T. S.; Deutsch, C.

2016-02-01

Anoxic conditions are uncommon in the open ocean, and mostly confined to the cores of oxygen minimum zones (OMZs). When oxygen runs out, a suite of alternative electron acceptors are used, leading to denitrification and, rarely in open waters, sulfate reduction. Anoxic conditions have been shown to develop inside millimeter-scale organic particles and aggregates, establishing microscale gradients that could sustain diverse microbial communities along a sequence of redox niches. We develop a model of the biogeochemistry of anoxic aggregates that includes aerobic and anaerobic reactions in a diffusion-limited environment, and present analytical and numerical solutions for the conditions that allow denitrification and sulfate reduction inside aggregates. The model is applied to realistic size spectra of particles sinking through the water column, and used to estimate the potential for particle-bound denitrification and sulfate reduction in the global ocean. We show that anoxia inside aggregates may be common throughout low oxygen waters, extending the niche of denitrifying metabolisms beyond fully anoxic zones. In the OMZ cores, aggregates can sustain pockets of sulfate reduction in otherwise non-sulfidic waters, depending on ambient nitrate concentrations, particle respiration rates, and other factors. We further discuss the implications for nitrogen, sulfur and trace metal cycling in the ocean.

Metagenomic Insights Into the Microbial Community and Nutrient Cycling in the Western Subarctic Pacific Ocean.

PubMed

Li, Yingdong; Jing, Hongmei; Xia, Xiaomin; Cheung, Shunyan; Suzuki, Koji; Liu, Hongbin

2018-01-01

The composition and metabolic functions of prokaryotic communities in the western subarctic Pacific (WSP), where strong mixing of waters from the Sea of Okhotsk and the East Kamchatka Current result in transfer to the Oyashio Current, were investigated using a shotgun metagenome sequencing approach. Functional metabolic genes related to nutrient cycling of nitrogen, sulfur, carbohydrates, iron and amino acids were differently distributed between the surface and deep waters of the WSP. Genes related to nitrogen metabolism were mainly found in deep waters, where Thaumarchaeaota, Sphingomonadales , and Pseudomonadales were closely associated and performing important roles in ammonia oxidation, assimilatory nitrate reduction, and dissimilatory nitrate reduction processes, respectively. In addition, orders affiliated to Spingobacteria and Alphaproteobacteria were crucial for sulfate reduction and abundant at 3000 m, whereas orders affiliated to Gammaproteobacteria , which harbored the most sulfate reduction genes, were abundant at 1000 m. Additionally, when compared with the East Kamchatka Current, the prokaryotes in the Oyashio Current were likely to consume more energy for synthesizing cellular components. Also, genes encoding iron transport and siderophore biosynthesis proteins were in low abundance, indicating that the iron was not a limiting factor in the Oyashio current. In contrast, in the East Kamchatka Current, prokaryotes were more likely to directly utilize the amino acids and absorb iron from the environment. Overall, our data indicated that the transformation from the East Kamchatka Current to the Oyashio Current reshapes not only the composition of microbial community, but also the function of the metabolic processes. These results extended our knowledge of the microbial composition and potential metabolism in the WSP.

Metagenomic Insights Into the Microbial Community and Nutrient Cycling in the Western Subarctic Pacific Ocean

PubMed Central

Li, Yingdong; Jing, Hongmei; Xia, Xiaomin; Cheung, Shunyan; Suzuki, Koji; Liu, Hongbin

2018-01-01

The composition and metabolic functions of prokaryotic communities in the western subarctic Pacific (WSP), where strong mixing of waters from the Sea of Okhotsk and the East Kamchatka Current result in transfer to the Oyashio Current, were investigated using a shotgun metagenome sequencing approach. Functional metabolic genes related to nutrient cycling of nitrogen, sulfur, carbohydrates, iron and amino acids were differently distributed between the surface and deep waters of the WSP. Genes related to nitrogen metabolism were mainly found in deep waters, where Thaumarchaeaota, Sphingomonadales, and Pseudomonadales were closely associated and performing important roles in ammonia oxidation, assimilatory nitrate reduction, and dissimilatory nitrate reduction processes, respectively. In addition, orders affiliated to Spingobacteria and Alphaproteobacteria were crucial for sulfate reduction and abundant at 3000 m, whereas orders affiliated to Gammaproteobacteria, which harbored the most sulfate reduction genes, were abundant at 1000 m. Additionally, when compared with the East Kamchatka Current, the prokaryotes in the Oyashio Current were likely to consume more energy for synthesizing cellular components. Also, genes encoding iron transport and siderophore biosynthesis proteins were in low abundance, indicating that the iron was not a limiting factor in the Oyashio current. In contrast, in the East Kamchatka Current, prokaryotes were more likely to directly utilize the amino acids and absorb iron from the environment. Overall, our data indicated that the transformation from the East Kamchatka Current to the Oyashio Current reshapes not only the composition of microbial community, but also the function of the metabolic processes. These results extended our knowledge of the microbial composition and potential metabolism in the WSP. PMID:29670596

Redox conditions and the efficiency of chlorinated ethene biodegradation: Field studies

USGS Publications Warehouse

Chapelle, F.H.; Bradley, P.M.

2000-01-01

The effect of redox conditions on the efficiency of chlorinated ethene biodegradation was investigated at two field sites. One site (NAS Cecil Field, FL) is characterized by predominantly Fe(III)-reducing conditions in the contaminant source area, grading to predominantly sulfate- reducing conditions downgradient. This sequence of redox conditions led to relatively inefficient biodegradation of chlorinated ethenes, with high concentrations of trichloroethene extending more than 400 meters downgradient of the source area. In contrast, a second site (NBS Kings Bay, GA) characterized by predominantly sulfate-reducing conditions in the source area followed by Fe(III)-reducing conditions downgradient. In this system perchloroethene (PCE) and TCE were rapidly biodegraded and extended less than 100 meters downgradient. Rates of ground- water transport are similar at the two sites (???0.2 m/d) indicating that the succession of redox processes, rather than other hydrologic factors, is the principal control on biodegradation. In particular, redox conditions that favor the initial reduction of highly chlorinated ethenes (methanogenic or sulfate-reducing conditions) followed by more oxidizing conditions (Fe(III)- reducing or oxic conditions) favors efficient biodegradation. Thus, documenting the succession of redox processes is an important step in understanding the efficiency of chlorinated ethene biodegradation in ground-water systems.

Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

USGS Publications Warehouse

Kelemen, S.R.; Walters, C.C.; Kwiatek, P.J.; Afeworki, M.; Sansone, M.; Freund, H.; Pottorf, R.J.; Machel, H.G.; Zhang, T.; Ellis, G.S.; Tang, Y.; Peters, K.E.

2008-01-01

Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to distinguish whether solid bitumen, either in situ or removed and concentrated from the rock matrix, was formed via the TCA or TRS process. ?? 2008 Elsevier Ltd.

Seasonal variation of early diagenesis and greenhouse gas production in coastal sediments of Cadiz Bay: Influence of anthropogenic activities

NASA Astrophysics Data System (ADS)

Burgos, Macarena; Ortega, Teodora; Bohórquez, Julio; Corzo, Alfonso; Rabouille, Christophe; Forja, Jesús M.

2018-01-01

Greenhouse gas production in coastal sediments is closely associated with the early diagenesis processes of organic matter and nutrients. Discharges from anthropogenic activities, particularly agriculture, fish farming and waste-water treatment plants supply large amounts of organic matter and inorganic nutrients that affect mineralization processes. Three coastal systems of Cadiz Bay (SW Spain) (Guadalete River, Rio San Pedro Creek and Sancti Petri Channel) were chosen to determine the seasonal variation of organic matter mineralization. Two sampling stations were selected in each system; one in the outer part, close to the bay, and another more inland, close to a discharge point of effluent related to anthropogenic activities. Seasonal variation revealed that metabolic reactions were driven by the annual change of temperature in the outer station of the systems. In contrast, these reactions depended on the amount of organic matter reaching the sediments in the outermost part of the systems, which was higher during winter. Oxygen is consumed in the first 0.5 cm indicating that suboxic and anoxic processes, such as denitrification, sulfate reduction and methanogenesis are important in these sediments. Sulfate reduction seems to account for most of the mineralization of organic matter at the marine stations, while methanogenesis is the main pathway at the sole freshwater station of this study, located inside the estuary of the Guadalete River, because of the lack of sulfate as electron acceptor. Results point to denitrification being the principal process of N2O formation. Diffusive fluxes varied between 2.6 and 160 mmol m-2 d-1 for dissolved inorganic carbon (DIC); 0.9 and 164.3 mmol m-2 d-1 for TA; 0.8 and 17.4 μmol m-2 d-1 for N2O; and 0.1 μmol and 13.1 mmol m-2 d-1 for CH4, indicating that these sediments act as a source of greenhouse gases to the water column.

Modeling microbial reaction rates in a submarine hydrothermal vent chimney wall

NASA Astrophysics Data System (ADS)

LaRowe, Douglas E.; Dale, Andrew W.; Aguilera, David R.; L'Heureux, Ivan; Amend, Jan P.; Regnier, Pierre

2014-01-01

The fluids emanating from active submarine hydrothermal vent chimneys provide a window into subseafloor processes and, through mixing with seawater, are responsible for steep thermal and compositional gradients that provide the energetic basis for diverse biological communities. Although several models have been developed to better understand the dynamic interplay of seawater, hydrothermal fluid, minerals and microorganisms inside chimney walls, none provide a fully integrated approach to quantifying the biogeochemistry of these hydrothermal systems. In an effort to remedy this, a fully coupled biogeochemical reaction-transport model of a hydrothermal vent chimney has been developed that explicitly quantifies the rates of microbial catalysis while taking into account geochemical processes such as fluid flow, solute transport and oxidation-reduction reactions associated with fluid mixing as a function of temperature. The metabolisms included in the reaction network are methanogenesis, aerobic oxidation of hydrogen, sulfide and methane and sulfate reduction by hydrogen and methane. Model results indicate that microbial catalysis is generally fastest in the hottest habitable portion of the vent chimney (77-102 °C), and methane and sulfide oxidation peak near the seawater-side of the chimney. The fastest metabolisms are aerobic oxidation of H2 and sulfide and reduction of sulfate by H2 with maximum rates of 140, 900 and 800 pmol cm-3 d-1, respectively. The maximum rate of hydrogenotrophic methanogenesis is just under 0.03 pmol cm-3 d-1, the slowest of the metabolisms considered. Due to thermodynamic inhibition, there is no anaerobic oxidation of methane by sulfate (AOM). These simulations are consistent with vent chimney metabolic activity inferred from phylogenetic data reported in the literature. The model developed here provides a quantitative approach to describing the rates of biogeochemical transformations in hydrothermal systems and can be used to constrain the role of microbial activity in the deep subsurface.

Impact of sulfate pollution on anaerobic biogeochemical cycles in a wetland sediment.

PubMed

Baldwin, Darren S; Mitchell, Alison

2012-03-15

The impact of sulfate pollution is increasingly being seen as an issue in the management of inland aquatic ecosystems. In this study we use sediment slurry experiments to explore the addition of sulfate, with or without added carbon, on the anaerobic biogeochemical cycles in a wetland sediment that previously had not been exposed to high levels of sulfate. Specifically we looked at the cycling of S (sulfate, dissolved and particulate sulfide--the latter measured as acid volatile sulfide; AVS), C (carbon dioxide, bicarbonate, methane and the short chain volatile fatty acids formate, acetate, butyrate and propionate), N (dinitrogen, ammonium, nitrate and nitrite) and redox active metals (Fe(II) and Mn(II)). Sulfate had the largest effects on the cycling of S and C. All the added S at lower loadings were converted to AVS over the course of the experiment (30 days). At the highest loading (8 mmol) less than 50% of consumed S was converted to AVS, however this is believed to be a kinetic effect. Although sulfate reduction was occurring in sediments with added sulfate, dissolved sulfide concentrations remained low throughout the study. Sulfate addition affected methanogenesis. In the absence of added carbon, addition of sulfate, even at a loading of 1 mmol, resulted in a halving of methane formation. The initial rate of formation of methane was not affected by sulfate if additional carbon was added to the sediment. However, there was evidence for anaerobic methane oxidation in those sediments with added sulfate and carbon, but not in those sediments treated only with carbon. Surprisingly, sulfate addition had little apparent impact on N dynamics; previous studies have shown that sulfide can inhibit denitrification and stimulate dissimilatory nitrate reduction to ammonia. We propose that because most of the reduced sulfur was in particulate form, levels of dissolved sulfide were too low to interfere with the N cycle. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

[Analysis of chondroitin sulfate content of Cervi Cornu Pantotrichum with different processing methods and different parts].

PubMed

Gong, Rui-Ze; Wang, Yan-Hua; Sun, Yin-Shi

2018-02-01

The differences and the variations of chondroitin sulfate content in different parts of Cervi Cornu Pantotrichum(CCP) with different processing methods were investigated. The chondroitin sulfate from velvet was extracted by dilute alkali-concentrated salt method. Next， the chondroitin sulfate was digested by chondroitinase ABC.The contents of total chondroitin sulfate and chondroitin sulfate A， B and C in the samples were determined by high performance liquid chromatography(HPLC).The content of chondroitin sulfate in wax，powder，gauze，bone slices of CCP with freeze-drying processing is 14.13，11.99，1.74，0.32 g·kg⁻¹， respectively. The content of chondroitin sulfate in wax，powder，gauze，bone slices of CCP with boiling processing is 10.71，8.97，2.21，1.40 g·kg⁻¹， respectively. The content of chondroitin sulfate in wax，powder，gauze，bone slices of CCP without blood is 12.47，9.47，2.64，0.07 g·kg⁻¹， respectively. And the content of chondroitin sulfate in wax，powder，gauze，bone slices of CCP with blood is 8.22，4.39，0.87，0.28 g·kg⁻¹ respectively. The results indicated that the chondroitin sulfate content in different processing methods was significantly different.The content of chondroitin sulfate in CCP with freeze-drying is higher than that in CCP with boiling processing.The content of chondroitin sulfate in CCP without blood is higher than that in CCP with blood. The chondroitin sulfate content in differerent paris of the velvet with the same processing methods was arranged from high to low as： wax slices， powder， gauze slices， bone slices. Copyright© by the Chinese Pharmaceutical Association.

Effect of Various Food Additives on the Levels of 4(5)-Methylimidazole in a Soy Sauce Model System.

PubMed

Lee, Sumin; Lee, Jung-Bin; Hwang, Junho; Lee, Kwang-Geun

2016-01-01

In this study, the effect of food additives such as iron sulfate, magnesium sulfate, zinc sulfate, citric acid, gallic acid, and ascorbic acid on the reduction of 4(5)-methylimidazole (4(5)-MI) was investigated using a soy sauce model system. The concentration of 4(5)-MI in the soy sauce model system with 5% (v/v) caramel colorant III was 1404.13 μg/L. The reduction rate of 4(5)-MI level with the addition of 0.1M additives followed in order: iron sulfate (81%) > zinc sulfate (61%) > citric acid (40%) > gallic acid (38%) > ascorbic acid (24%) > magnesium sulfate (13%). Correlations between 4(5)-MI levels and the physicochemical properties of soy sauce, including the amount of caramel colorant, pH value, and color differences, were determined. The highest correlations were found between 4(5)-MI levels and the amount of caramel colorant and pH values (r(2) = 0.9712, r(2) = 0.9378). The concentration of caramel colorants in 8 commercial soy sauces were estimated, and ranged from 0.01 to 1.34% (v/v). © 2015 Institute of Food Technologists®

North American International Society for Microbial Electrochemical Technologies Meeting (Abstracts)

DTIC Science & Technology

2016-04-18

systems. Unlike the well-studied case of dissolved oxygen (D.O.) effects on the facultative metabolic shift between aerobic respiration and nitrate...The Pt catalyst can effectively catalyze oxygen reduction and ensure a healthy operation of bioelectrochemical systems but its high cost limits the... effect of COEs on other species in bioelectrochemical systems. Effects of additional electron acceptors in bio-anodic processes: oxygen and sulfate

Resilience of sulfate-reducing granular sludge against temperature, pH, oxygen, nitrite, and free nitrous acid.

PubMed

Hao, Tianwei; Mackey, Hamish R; Guo, Gang; Liu, Rulong; Chen, Guanghao

2016-10-01

Sulfate-reducing granular sludge has recently been developed and characterized in detail as part of the development of the sulfate reduction, autotrophic denitrification, nitrification integrated (SANI) process. However, information regarding temperature of granules to environmental fluctuation is lacking, an aspect that is important in dealing with real wastewater. A comprehensive assessment of sulfate-reducing granular sludge performance under various environmental conditions was thus conducted in this study, including temperature, pH, oxygen, nitrite, and free nitrous acid (FNA) as possible encountering conditions in the removal of organics and/or nitrate. Specific chemical oxygen demand removal rate of the granules was determined to be reduced by 65 % when the temperature varied between 10-15 °C, reduced by 70 % when dissolved oxygen (DO) was 0.5 mg/L or greater, and at least, reduced by 75 % when nitrite was 30 mg N/L or above. Nevertheless, the sludge activity recovered by 82, 100, and 86 % from exposure to high oxygen and nitrite and low temperature levels, respectively. Combined inhibition of nitrite and FNA on the sludge is strong and complex, while FNA alone reduced cell viability from 60 to 40 % when its concentration increased to 2.3 mg N/L. The present study demonstrates that sulfate-reducing bacteria (SRB) granules possess high resilience against varying environmental conditions, showing the high application potential of sulfate-reducing granular sludge in dealing with brackish and saline industrial or domestic wastewaters.

Response to Julian et al. (2015) "comment on and reinterpretation of Gabriel et al. (2014) 'fish mercury and surface water sulfate relationships in the everglades protection area'".

PubMed

Gabriel, Mark C; Axelrad, Don; Orem, William; Osborne, Todd Z

2015-06-01

The purpose of this forum is to respond to a rebuttal submitted by Julian et al., Environ Manag 55:1-5, 2015 where they outlined their overall disagreement with the data preparation, methods, and interpretation of results presented in Gabriel et al. (Environ Manag 53:583-593, 2014). Here, we provide background information on the research premise presented in Gabriel et al. (Environ Manag 53:583-593, 2014) and provide a defense for this work using five themes. In spite of what Julian et al. perceive as limitations in the sampling methods and analytical tools used for this work, the relationships found between fish total mercury and surface water sulfate concentrations in Gabriel et al. (Environ Manag 53:583-593, 2014) are comparable to relationships between pore water methylmercury (MeHg) and pore water sulfate found in past studies indicating that sulfate is important to MeHg production and bioaccumulation in the Everglades. Julian et al. state "…there is no way to justify any ecosystem-wide sulfur strategy as a management approach to reduce mercury risk in the (Everglades) as suggested by Gabriel et al. (Environ Manag 53:583-593, 2014), Corrales et al. (Sci Tot Environ 409:2156-2162, 2011) and Orem et al. (Rev Environ Sci Technol 41 (S1):249-288, 2011)." We disagree, and having stated why sulfate input reduction to the Everglades may be the most effective means of reducing mercury in Everglades fish, it is important that research on sulfur and mercury biogeochemistry continues. If further studies support the relationship between sulfate loading reduction and MeHg reduction, sulfur mass balance studies should commence to (1) better quantify agricultural and connate seawater sulfate inputs and (2) define opportunities to reduce sulfate inputs to the Everglades ecosystem.

Kinetics of uncatalyzed thermochemical sulfate reduction by sulfur-free paraffin

USGS Publications Warehouse

Zhang, Tongwei; Ellis, Geoffrey S.; Ma, Qisheng; Amrani, Alon; Tang, Yongchun

2012-01-01

To determine kinetic parameters of sulfate reduction by hydrocarbons (HC) without the initial presence of low valence sulfur, we carried out a series of isothermal gold-tube hydrous-pyrolysis experiments at 320, 340, and 360 °C under a constant confined pressure of 24.1 MPa. The reactants used consisted of saturated HC (sulfur-free) and CaSO4 in an aqueous solution buffered to three different pH conditions without the addition of elemental sulfur (S8) or H2S as initiators. H2S produced in the course of reaction was proportional to the extent of the reduction of CaSO4 that was initially the only sulfur-containing reactant. Our results show that the in situ pH of the aqueous solution (herein, in situ pH refers to the calculated pH value of the aqueous solution at certain experimental conditions) can significantly affect the rate of the thermochemical sulfate reduction (TSR) reaction. A substantial increase in the TSR reaction rate was observed with a decrease in the in situ pH. Our experimental results show that uncatalyzed TSR is a first-order reaction. The temperature dependence of experimentally measured H2S yields from sulfate reduction was fit with the Arrhenius equation. The determined activation energy for HC (sulfur-free) reacting with View the MathML sourceHSO4− in our experiments is 246.6 kJ/mol at pH values ranging from 3.0 to 3.5, which is slightly higher than the theoretical value of 227.0 kJ/mol using ab initio quantum chemical calculations on a similar reaction. Although the availability of reactive sulfate significantly affects the rate of reaction, a consistent rate constant was determined by accounting for the HSO4− ion concentration. Our experimental and theoretical approach to the determination of the kinetics of TSR is further validated by a reevaluation of several published experimental TSR datasets without the initial presence of native sulfur or H2S. When the effect of reactive sulfate concentration is appropriately accounted for, the published experimental TSR data yield kinetic parameters that are consistent with our values. Assuming MgSO4 contact-ion-pair ([MgSO4]CIP) as the reactive form of sulfate in petroleum reservoir formation waters, a simple extrapolation of our experimentally derived HSO4− reduction kinetics as a proxy for [MgSO4]CIP to geologically reasonable conditions predicts onset temperatures (130–140 °C) that are comparable to those observed in nature.

Start-up of simultaneous removal of ammonium and sulfate from an anaerobic ammonium oxidation (anammox) process in an anaerobic up-flow bioreactor.

PubMed

Yang, Zhiquan; Zhou, Shaoqi; Sun, Yanbo

2009-09-30

A laboratory testing of simultaneous removal of ammonium and sulfate (SRAS) was studied from an anammox process in an anaerobic bioreactor filled with granular activated carbon. Two different phases of experiment were investigated to start up the SRAS process, and final batch tests were performed to analyze the SRAS process. The experiment included an anammox process and an SRAS process. During the anammox process, the highest removal efficiency of ammonium and nitrite was up to 97 and 98%, respectively. After 160 days in the stationary phase of anammox process, the ratio of ammonium to nitrite consumption was approximately 1:1.15, which is much higher than 1:1.32 in the traditional anammox process. The extra electron acceptor, such as sulfate, was thought to react with ammonium by bacteria. Synthetic wastewater containing ammonium chlorine and sodium sulfate was used as the feed for the bioreactor in the second phase of experiment. During the SRAS process, the influent concentrations of ammonium and sulfate were controlled to be 50-60 and 210-240 mg L(-1) respectively. After start-up and acclimatization of this process for 60 days, the average effluent concentrations of ammonium and sulfate were 30 and 160 mg L(-1), respectively. The simultaneous ammonium and sulfate removal was detected in the reactor. In order to further validate the biochemical interaction between ammonium and sulfate, batch tests was carried out. Abiotic tests were carried out to demonstrate that the pure chemical action between ammonium and sulfate without microorganism was not possible. Biotic assays with different ammonium and sulfate concentrations were further investigated that high concentrations of ammonium and sulfate could promote simultaneous removal of ammonium and sulfate. And elemental sulfur and nitrogen gas as the products measured in the SRAS process helped to demonstrate the occurrence of new interaction between nitrogen and sulfur. The new process of SRAS in the inorganic condition, including simultaneous removal of ammonium and sulfate, and the appearance of elemental sulfur and nitrogen gas as the terminal products, widened the cycle approach between nitrogen and sulfur.

40 CFR 415.22 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... SOURCE CATEGORY Aluminum Sulfate Production Subcategory § 415.22 Effluent limitations guidelines...—Aluminum Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.22 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... SOURCE CATEGORY Aluminum Sulfate Production Subcategory § 415.22 Effluent limitations guidelines...—Aluminum Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.22 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... SOURCE CATEGORY Aluminum Sulfate Production Subcategory § 415.22 Effluent limitations guidelines...—Aluminum Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.22 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... SOURCE CATEGORY Aluminum Sulfate Production Subcategory § 415.22 Effluent limitations guidelines...—Aluminum Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.132 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... SOURCE CATEGORY Potassium Sulfate Production Subcategory § 415.132 Effluent limitations guidelines...—Potassium Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.132 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... SOURCE CATEGORY Potassium Sulfate Production Subcategory § 415.132 Effluent limitations guidelines...—Potassium Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.132 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... SOURCE CATEGORY Potassium Sulfate Production Subcategory § 415.132 Effluent limitations guidelines...—Potassium Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.132 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... SOURCE CATEGORY Potassium Sulfate Production Subcategory § 415.132 Effluent limitations guidelines...—Potassium Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.132 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... SOURCE CATEGORY Potassium Sulfate Production Subcategory § 415.132 Effluent limitations guidelines...—Potassium Sulfate Pollutant or pollutant property BPT limitations Maximum for any 1 day Average of daily...

40 CFR 415.472 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... point source subject to this subpart and producing nickel sulfate, nickel chloride, nickel nitrate, or...): Subpart AU—Nickel Sulfate, Nickel Chloride, Nickel Nitrate, Nickel Fluoborate Pollutant or pollutant...

40 CFR 415.472 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... point source subject to this subpart and producing nickel sulfate, nickel chloride, nickel nitrate, or...): Subpart AU—Nickel Sulfate, Nickel Chloride, Nickel Nitrate, Nickel Fluoborate Pollutant or pollutant...

40 CFR 415.472 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... point source subject to this subpart and producing nickel sulfate, nickel chloride, nickel nitrate, or...): Subpart AU—Nickel Sulfate, Nickel Chloride, Nickel Nitrate, Nickel Fluoborate Pollutant or pollutant...

40 CFR 415.472 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... point source subject to this subpart and producing nickel sulfate, nickel chloride, nickel nitrate, or...): Subpart AU—Nickel Sulfate, Nickel Chloride, Nickel Nitrate, Nickel Fluoborate Pollutant or pollutant...

40 CFR 415.472 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... point source subject to this subpart and producing nickel sulfate, nickel chloride, nickel nitrate, or...): Subpart AU—Nickel Sulfate, Nickel Chloride, Nickel Nitrate, Nickel Fluoborate Pollutant or pollutant...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yung, M. M.; Cheah, S.; Kuhn, J. N.

Sulfur K-edge XANES was used to monitor sulfur species transforming from sulfides to sulfates during steam + air regeneration on a Ni/Mg/K/Al{sub 2}O{sub 3} catalyst used to condition biomass-derived syngas. The catalyst was tested for multiple reaction/regeneration cycles. Post-reaction samples showed the presence of sulfides on the H{sub 2}S-poisoned nickel catalyst. Although some gaseous sulfur species were observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst and a transformation from sulfides to sulfates was observed. The subsequent H{sub 2} reduction led to a partial reduction of sulfates back to sulfides. A proposed reaction sequence is presentedmore » and recommended regeneration strategies are discussed.« less

Inflammatory microRNA-194 and -515 attenuate the biosynthesis of chondroitin sulfate during human intervertebral disc degeneration.

PubMed

Hu, Bo; Xu, Chen; Tian, Ye; Shi, Changgui; Zhang, Ying; Deng, Lianfu; Zhou, Hongyu; Cao, Peng; Chen, Huajiang; Yuan, Wen

2017-07-25

Intervertebral disc degeneration (IDD) is characterized by dehydration and loss of extracellular matrixes in the nucleus pulposus region. Chondroitin sulfate has been found to be the water-binding molecule that played a key role in IDD. Although investigators have reported that inflammatory cytokines are involved in the reduction of chondroitin sulfate in IDD, but the underlying mechanism is unrevealed. Since chondroitin sulfate synthesis is controlled by chondroitin sulfate glycosyltransferases CHSY-1/2/3 and CSGALNACT-1/2, their functional role and regulatory mechanism in IDD is not fully studied. Here, we set out to investigate the function and regulatory roles of these factors during IDD development. We found that among these chondroitin sulfate glycosyltransferases, CHSY-1/2/3 are significantly down-regulated in severe IDD samples than mild IDD samples. In vitro experiments revealed that Interleukin-1β and Tumor Necrosis Factor-α stimulation led to significant reduction of CHSY-1/2/3 at protein level than mRNA level in NP cells, indicating a post-transcriptional regulatory mechanisms are involved. By computational prediction and analysis, we found that inflammatory cytokines stimulated microRNA-194 and -515 target CHSY-1/2/3 mRNA and significantly interrupt their translation and downstream chondroitin sulfate deposition. Inhibition of microRNA-194 and -515 however, significantly rescued CHSY-1/2/3 expressions and chondroitin sulfate deposition. These findings together demonstrated a vital role of inflammatory stimulated microRNAs in promoting intervertebral disc degeneration by interrupt chondroitin sulfate synthesis, which may provide new insights into the mechanism and therapeutic approaches in IDD.

Anaerobic Methane-Oxidizing Microbial Community in a Coastal Marine Sediment: Anaerobic Methanotrophy Dominated by ANME-3.

PubMed

Bhattarai, Susma; Cassarini, Chiara; Gonzalez-Gil, Graciela; Egger, Matthias; Slomp, Caroline P; Zhang, Yu; Esposito, Giovanni; Lens, Piet N L

2017-10-01

The microbial community inhabiting the shallow sulfate-methane transition zone in coastal sediments from marine Lake Grevelingen (The Netherlands) was characterized, and the ability of the microorganisms to carry out anaerobic oxidation of methane coupled to sulfate reduction was assessed in activity tests. In vitro activity tests of the sediment with methane and sulfate demonstrated sulfide production coupled to the simultaneous consumption of sulfate and methane at approximately equimolar ratios over a period of 150 days. The maximum sulfate reduction rate was 5 μmol sulfate per gram dry weight per day during the incubation period. Diverse archaeal and bacterial clades were retrieved from the sediment with the majority of them clustered with Euryarchaeota, Thaumarcheota, Bacteroidetes, and Proteobacteria. The 16S rRNA gene sequence analysis showed that the sediment from marine Lake Grevelingen contained anaerobic methanotrophic Archaea (ANME) and methanogens as archaeal clades with a role in the methane cycling. ANME at the studied site mainly belong to the ANME-3 clade. This study provides one of the few reports for the presence of ANME-3 in a shallow coastal sediment. Sulfate-reducing bacteria from Desulfobulbus clades were found among the sulfate reducers, however, with very low relative abundance. Desulfobulbus has previously been commonly found associated with ANME, whereas in our study, ANME-3 and Desulfobulbus were not observed simultaneously in clusters, suggesting the possibility of independent AOM by ANME-3.

Health and air quality benefits of policies to reduce coal-fired power plant emissions: a case study in North Carolina.

PubMed

Li, Ya-Ru; Gibson, Jacqueline MacDonald

2014-09-02

We analyzed sulfur dioxide (SO2) emissions and fine particulate sulfate (PM2.5 sulfate) concentrations in the southeastern United States during 2002-2012, in order to evaluate the health impacts in North Carolina (NC) of the NC Clean Smokestacks Act of 2002. This state law required progressive reductions (beyond those mandated by federal rules) in pollutant emissions from NC's coal-fired power plants. Although coal-fired power plants remain NC's leading SO2 source, a trend analysis shows significant declines in SO2 emissions (-20.3%/year) and PM2.5 sulfate concentrations (-8.7%/year) since passage of the act. Emissions reductions were significantly greater in NC than in neighboring states, and emissions and PM2.5 sulfate concentration reductions were highest in NC's piedmont region, where 9 of the state's 14 major coal-fired power plants are located. Our risk model estimates that these air quality improvements decreased the risk of premature death attributable to PM2.5 sulfate in NC by about 63%, resulting in an estimated 1700 (95% CI: 1500, 1800) deaths prevented in 2012. These findings lend support to recent studies predicting that implementing the proposed federal Cross-State Air Pollution Rule (recently upheld by the U.S. Supreme Court) could substantially decrease U.S. premature deaths attributable to coal-fired power plant emissions.

Biogenic hydroxysulfate green rust, a potential electron acceptor for SRB activity

NASA Astrophysics Data System (ADS)

Zegeye, Asfaw; Huguet, Lucie; Abdelmoula, Mustapha; Carteret, Cédric; Mullet, Martine; Jorand, Frédéric

2007-11-01

Microbiological reduction of a biogenic sulfated green rust (GR2(SO42-)), was examined using a sulfate reducing bacterium ( Desulfovibrio alaskensis). Experiments investigated whether GR2(SO42-) could serve as a sulfate source for D. alaskensis anaerobic respiration by analyzing mineral transformation. Batch experiments were conducted using lactate as the electron donor and biogenic GR2(SO42-) as the electron acceptor, at circumneutral pH in unbuffered medium. GR2(SO42-) transformation was monitored with time by X-ray diffraction (XRD), Transmission Mössbauer Spectroscopy (TMS), Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The reduction of sulfate anions and the formation of iron sulfur mineral were clearly identified by XPS analyses. TMS showed the formation of additional mineral as green rust (GR) and vivianite. XRD analyses discriminated the type of the newly formed GR as GR1. The formed GR1 was GR1(CO32-) as indicated by DRIFTS analysis. Thus, the results presented in this study indicate that D. alaskensis cells were able to use GR2(SO42-) as an electron acceptor. GR1(CO32-), vivianite and an iron sulfur compound were formed as a result of GR2(SO42-) reduction by D. alaskensis. Hence, in environments where geochemical conditions promote biogenic GR2(SO42-) formation, this mineral could stimulate the anaerobic respiration of sulfate reducing bacteria.

Effects of temperature on anaerobic decomposition of high-molecular weight organic matter under sulfate-reducing conditions

NASA Astrophysics Data System (ADS)

Matsui, Takato; Kojima, Hisaya; Fukui, Manabu

2013-03-01

Most sedimentary mineralization occurs along coasts under anaerobic conditions. In the absence of oxygen, high-molecular weight organic matter in marine sediments is gradually decomposed by hydrolysis, fermentation and sulfate reduction. Because of the different responses of the respective steps to temperature, degradation may be specifically slowed or stopped in certain step. To evaluate the effect of temperature on cellobiose degradation, culture experiments were performed at six different temperatures (3 °C, 8 °C, 13 °C, 18 °C, 23 °C, and 28 °C) under sulfate-reducing conditions. This study measured the concentrations of sulfide, dissolved organic carbon (DOC), and organic acids during that degradation. Degradation patterns were divided into three temperature groups: 3 °C, 8/13 °C, and 18/23/28 °C. The decrease in DOC proceeded in two steps, except at 3 °C. The length of the stagnant phase separating these two steps differed greatly between temperatures of 8/13 °C and 18/23/28 °C. In the first step, organic carbon was consumed by hydrolysis, fermentation and sulfate reduction. In the second step, acetate accumulated during the first step was oxidized by sulfate reduction. Bacterial communities in the cultures were analyzed by denaturing gradient gel electrophoresis (DGGE); the major differences among the three temperature groups were attributed to shifts in acetate-using sulfate reducers of the genus Desulfobacter. This suggests that temperature characteristics of dominant acetate oxidizers are important factors in determining the response of carbon flow in coastal marine sediments in relation to the changes in temperature.

A modified sulfate process to lunar oxygen

NASA Technical Reports Server (NTRS)

Sullivan, Thomas A.

1992-01-01

A modified sulfate process which produces oxygen from iron oxide-bearing minerals in lunar soil is under development. Reaction rates of ilmenite in varying strength sulfuric acid have been determined. Quantitative conversion of ilmenite to ferrous sulfate was observed over a range of temperatures and concentrations. Data has also been developed on the calcination of by-product sulfates. System engineering for overall operability and simplicity has begun, suggesting that a process separating the digestion and sulfate dissolution steps may offer an optimum process.

THE NONLINEAR RESPONSE OF NITRATE REPLACEMENT THAT MITIGATES SULFATE REDUCTIONS: THE GAS RATIO AS AN INDICATOR AND SENSITIVITY TO ERRORS IN TOTAL AMMONIA AND TOTAL NITRATE

EPA Science Inventory

The poster presents an assessment, using the CMAQ air quality model, showing the inorganic gas ratio (the ratio of free ammonia to total nitrate) can function as a screening indicator of the winter replacement of sulfate by nitrate when sulfate is reduced. It also presents an as...

Everglqades Mercury: Biogeochemistry, Modeling, and Possible Mitigation

NASA Astrophysics Data System (ADS)

Orem, W. H.

2015-12-01

In the 1980s high levels of methylmercury (MeHg) were found in fish and other biota in the Florida Everglades, prompting fish consumption advisories. As part of Everglades restoration efforts Federal and State Agencies initiated a research program to study the underlying causes of the MeHg contamination. As part of this multi-agency effort, the U.S. Geological Survey developed the ACME (Aquatic Cycling of Mercury in the Everglades) project to examine the underlying biogeochemical factors controlling MeHg production and bioaccumulation in the ecosystem. Field studies by ACME and others identified the many factors impacting MeHg production in the Everglades. Thes factors include: high mercury deposition, large wetland area with organic-rich anaerobic soil, high sulfate loading in surface runoff, circumneutral pH, and high dissolved organic matter (DOM) content. Florida Department of Environmental Protection efforts that reduced local mercury emissions by 90%, produced only a small reduction in mercury deposition on the Everglades, suggesting that most Hg deposited on the ecosystem originates from distant sources, and beyond the reach of regulators. ACME studies demonstrated that high sulfate loading to the Everglades comes from discharge of canal water originating in the Everglades Agricultural Area (EAA). The use of sulfur in agriculture and soil oxidation in the EAA have been shown to be the principal sources of the sulfate loading. Sulfate entering the ecosystem drives microbial sulfate reduction and MeHg production, but inhibition of MeHg production by sulfide (a byproduct of microbial sulfate reduction) makes the biogeochemistry complex. Laboratory microcosm and field mesocosm experiments by ACME helped define the complexity of the sulfur/MeHg biogeochemistry, and demonstrated the key role of dissolved organic matter in MeHg production. A conceptual model was developed that relates MeHg production to sulfate loading, DOM, and soil composition. This conceptual model was then used in the development of a mathematical model that relates how changes in sulfate loading affect MeHg production in the ecosystem. This model is currently being used to examine how limits on sulfate loading to the ecosystem could be used as a mitigation strategy to control MeHg production and levels of MeHg in Everglades biota.

Structural analysis and anticoagulant activities of two sulfated polysaccharides from the sea cucumber Holothuria coluber.

PubMed

Yang, Wenjiao; Cai, Ying; Yin, Ronghua; Lin, Lisha; Li, Zhongkun; Wu, Mingyi; Zhao, Jinhua

2018-05-01

Sulfated polysaccharides such as fucosylated glycosaminoglycan and fucan sulfate from echinoderm possess complex chemical structure and various biological activities. The two sulfated polysaccharides were purified from the low-value sea cucumber Holothuria coluber. Their physicochemical properties and chemical structures were analyzed and characterized by chemical and instrumental methods. Structural analysis clarified that the sea cucumber fucosylated glycosaminoglycan contains a chondroitin sulfate-like backbone and fucosyl branches with four various sulfation patterns. The fucan sulfate with molecular weight of 64.6 kDa comprises a central core of regular α(1 → 4)-linked tetrasaccharide repeating units, each of which is linked by a 4-O-sulfated fucose residue. Anticoagulant assays indicated that these sulfated polysaccharides possessed strong APTT prolonging activities and intrinsic factor Xase inhibitory activities, both of which decreased with the reduction of their molecular weights. Our results expand knowledge on the structural types of sulfated polysaccharides from sea cucumbers and further illustrate their functionality. Copyright © 2018. Published by Elsevier B.V.

Biodegradation of BTEX and Other Petroleum Hydrocarbons by Enhanced and Controlled Sulfate Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song Jin

High concentrations of sulfide in the groundwater at a field site near South Lovedale, OK, were inhibiting sulfate reducing bacteria (SRB) that are known to degrade contaminants including benzene, toluene, ethylbenzene, and m+p-xylenes (BTEX). Microcosms were established in the laboratory using groundwater and sediment collected from the field site and amended with various nutrient, substrate, and inhibitor treatments. All microcosms were initially amended with FeCl{sub 2} to induce FeS precipitation and, thereby, reduce sulfide concentrations. Complete removal of BTEX was observed within 39 days in treatments with various combinations of nutrient and substrate amendments. Results indicate that elevated concentration ofmore » sulfide is a limiting factor to BTEX biodegradation at this site, and that treating the groundwater with FeCl{sub 2} is an effective remedy to facilitate and enhance BTEX degradation by the indigenous SRB population. On another site in Moore, OK, studies were conducted to investigate barium in the groundwater. BTEX biodegradation by SRB is suspected to mobilize barium from its precipitants in groundwater. Data from microcosms demonstrated instantaneous precipitation of barium when sulfate was added; however, barium was detected redissolving for a short period and precipitating eventually, when active sulfate reduction was occurring and BTEX was degraded through the process. SEM elemental spectra of the evolved show that sulfur was not present, which may exclude BaSO{sub 4} and BaS as a possible precipitates. The XRD analysis suggests that barium probably ended in BaS complexing with other amorphous species. Results from this study suggest that SRB may be able to use the sulfate from barite (BaSO{sub 4}) as an electron acceptor, resulting in the release of free barium ions (Ba{sup 2+}), and re-precipitate it in BaS, which exposes more toxicity to human and ecological health.« less

EFFECT OF BACTERIAL SULFATE REDUCTION ON IRON-CORROSION SCALES

EPA Science Inventory

Iron-sulfur geochemistry is important in many natural and engineered environments including drinking water systems. In the anaerobic environment beneath scales of corroding iron drinking water distribution system pipes, sulfate reducing bacteria (SRB) produce sulfide from natura...

Repeated occurrences of methanogenic zones, diagenetic dolomite formation and linked silicate alteration in southern Bering Sea sediments (Bowers Ridge, IODP Exp. 323 Site U1341)

NASA Astrophysics Data System (ADS)

Wehrmann, L. M.; Ockert, C.; Mix, A. C.; Gussone, N.; Teichert, B. M. A.; Meister, P.

2016-03-01

Diagenetic precipitates, such as dolomite, and the chemistry of residual deeply buried porewater often represent the only traces of past biogeochemical activity in marine sediments. A 600 m thick sedimentary section, recently drilled at Integrated Ocean Drilling Program (IODP) Site U1341 on Bowers Ridge (southern Bering Sea), provides insight into such a 4.3 Ma old paleo-diagenetic archive. Hard-lithified calcite-dolomite layers, and laminae of disseminated carbonate, were recovered in diatom-rich sediments over a depth range of 400 m. Carbon isotope values of the diagenetic carbonates between -16.6 and -14.4‰ (VPDB) and strontium isotope ratios of dolomites close to past seawater values suggest carbonate precipitation induced by the production of dissolved inorganic carbon (DIC) during elevated rates of organic carbon mineralization, primarily via sulfate reduction, at shallow sediment depth below the paleo-seafloor. Diagenetic carbonates at 280-440 m below seafloor were likely also produced by the intermittent onset of sulfate reduction coupled to the anaerobic oxidation of methane (AOM) at sulfate-methane transition zones (SMTZ). These microbially mediated processes do not occur in the sediment at this site at present but were likely connected to the presence of a methanogenic zone at 2.58-2.51 Ma. A minimum in sulfate concentrations in modern porewaters and low sedimentary Ba/Al ratios resulting from former sulfate depletion are reminiscent of the presence of this large methanogenic zone. The minimum in sulfate concentrations is reflected in a minimum in magnesium concentrations, less radiogenic strontium and isotopically light calcium in the porewater. It is proposed that magnesium was removed from the porewater during carbonate precipitation and volcanic ash alteration which occurred in the former methanogenic zone and also released strontium with a less radiogenic isotope ratio and isotopically light calcium into the porewater. The isotopic composition of porewater calcium was also influenced by ammonium-calcium exchange on clay minerals and carbonate recrystallization. Our study elucidates the response of porewater element concentrations and isotopic profiles interlinked with the formation of diagenetic carbonates to changes in the deposition of organic carbon in sediments of deeper water sites (>2000 m water depth) over prolonged timescales. It shows that variations in biogeochemical processes in response to changes in oceanographic conditions and a dynamic subseafloor biogeochemical zonation have to also be taken into account at these deep water sites for a global assessment of organic carbon burial fluxes and remineralization.

Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor.

PubMed

Balk, Melike; Weijma, Jan; Goorissen, Heleen P; Ronteltap, Mariska; Hansen, Theo A; Stams, Alfons J M

2007-01-01

A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H2/CO2, no apparent inhibition occurred up to a concentration of 500 mg l(-1). When strain WW1 was co-cultured under the same conditions with the methanol-utilizing, non-sulfate-reducing bacteria, Thermotoga lettingae and Moorella mulderi, both originating from the same bioreactor, growth and sulfide formation were observed up to 430 mg l(-1). These results indicated that in the co-cultures, a major part of the electron flow was directed from methanol via H2/CO2 to the reduction of sulfate to sulfide. Besides methanol, acetate, and hydrogen, strain WW1 was also able to use formate, malate, fumarate, propionate, succinate, butyrate, ethanol, propanol, butanol, isobutanol, with concomitant reduction of sulfate to sulfide. In the absence of sulfate, strain WW1 grew only on pyruvate and lactate. On the basis of 16S rRNA analysis, strain WW1 was most closely related to Desulfotomaculum thermocisternum and Desulfotomaculum australicum. However, physiological properties of strain WW1 differed in some aspects from those of the two related bacteria.

Biogeochemistry of anaerobic crude oil biodegradation

NASA Astrophysics Data System (ADS)

Head, Ian; Gray, Neil; Aitken, Caroline; Sherry, Angela; Jones, Martin; Larter, Stephen

2010-05-01

Anaerobic degradation of crude oil and petroleum hydrocarbons is widely recognized as a globally significant process both in the formation of the world's vast heavy oil deposits and for the dissipation of hydrocarbon pollution in anoxic contaminated environments. Comparative analysis of crude oil biodegradation under methanogenic and sulfate-reducing conditions has revealed differences not only in the patterns of compound class removal but also in the microbial communities responsible. Under methanogenic conditions syntrophic associations dominated by bacteria from the Syntropheaceae are prevalent and these are likely key players in the initial anaerobic degradation of crude oil alkanes to intermediates such as hydrogen and acetate. Syntrophic acetate oxidation plays an important role in these systems and often results in methanogenesis dominated by CO2 reduction by members of the Methanomicrobiales. By contrast the bacterial communities from sulfate-reducing crude oil-degrading systems were more diverse and no single taxon dominated the oil-degrading sulfate-reducing systems. All five proteobacterial subdivisions were represented with Delta- and Gammaproteobacteria being detected most consistently. In sediments which were pasteurized hydrocarbon degradation continued at a relatively low rate. Nevertheless, alkylsuccinates characteristic of anaerobic hydrocarbon degradation accumulated to high concentrations. This suggested that the sediments harbour heat resistant, possibly spore-forming alkane degrading sulfate-reducers. This is particularly interesting since it has been proposed recently, that spore-forming sulfate-reducing bacteria found in cold arctic sediments may have originated from seepage of geofluids from deep subsurface hydrocarbon reservoirs.

Biogeochemistry of the coupled manganese-iron-sulfur cycles of intertidal surface sediments

NASA Astrophysics Data System (ADS)

Bosselmann, K.; Boettcher, M. E.; Billerbeck, M.; Walpersdorf, E.; Debeer, D.; Brumsack, H.-J.; Huettel, M.; Joergensen, B. B.

2003-04-01

The biogeochemistry of the coupled iron-manganese-sulfur-carbon cycles was studied in temperate intertidal surface sediments of the German Wadden Sea (North Sea). Coastal sampling sites include sand, mixed and mud flats with different organic matter and metal contents and permeability reflecting different hydrodynamic regimes. The field study focusses on the influence of temperature, organic matter load, and sediment types on the dynamics of biogeochemical reactions on different time scales (season, day-night, tidal cycles). One of the main interests was related to the cycling of metals (Mn, Fe) in relation to the activity of sulfate-reducing bacteria. Pore water profiles were investigated by sediment sectioning and high resolution gel sampling techniques. Microbial sulfate reduction rates were measured using radiolabeled sulfate with the whole core incubation technique and the spatial distribution of bacterial activity was visualised by using "2D-photoemulsion-monitoring technique". The biogeochemical sulfur cycle was additionally characterised by the stable isotope ratios (S,O) of different sulfur species (e.g., SO_4, AVS, pyrite). Element transfers (metals, nutrients) across the sediment-water interface were additionally quantified by the application of benthic flux chambers. Microbial sulfate reduction was generally highest in the suboxic zone of the surface sediments indicating its potential importance for the mobilization of iron and manganese. In organic matter poor permeable sediments tidal effects additionally influence the spatial and temporal distribution of dissolved redox-sensitive metals. In organic matter-rich silty and muddy sediments, temperature controlled the microbial sulfate reduction rates. Depth-integrated sulfate reduction rates in sandy sediments were much lower and controlled by both temperature and organic matter. Formation of anoxic sediment surfaces due to local enhanced organic matter load (so-called "black spots") may create windows of an increase flux of metals, nutrients and hydrogen sulfide. Acknowledgements: The study was supported by German Science Foundation within the DFG-research group "BioGeoChemistry of the Waddensea" and Max Planck Society.

Sulfate reduction in sulfuric material after re-flooding: Effectiveness of organic carbon addition and pH increase depends on soil properties.

PubMed

Yuan, Chaolei; Fitzpatrick, Rob; Mosley, Luke M; Marschner, Petra

2015-11-15

Sulfuric material is formed upon oxidation of sulfidic material; it is extremely acidic, and therefore, an environmental hazard. One option for increasing pH of sulfuric material may be stimulation of bacterial sulfate reduction. We investigated the effects of organic carbon addition and pH increase on sulfate reduction after re-flooding in ten sulfuric materials with four treatments: control, pH increase to 5.5 (+pH), organic carbon addition with 2% w/w finely ground wheat straw (+C), and organic carbon addition and pH increase (+C+pH). After 36 weeks, in five of the ten soils, only treatment +C+pH significantly increased the concentration of reduced inorganic sulfur (RIS) compared to the control and increased the soil pore water pH compared to treatment+pH. In four other soils, pH increase or/and organic carbon addition had no significant effect on RIS concentration compared to the control. The RIS concentration in treatment +C+pH as percentage of the control was negatively correlated with soil clay content and initial nitrate concentration. The results suggest that organic carbon addition and pH increase can stimulate sulfate reduction after re-flooding, but the effectiveness of this treatment depends on soil properties. Copyright © 2015 Elsevier B.V. All rights reserved.

Thermodynamic and Kinetic Response of Microbial Reactions to High CO2.

PubMed

Jin, Qusheng; Kirk, Matthew F

2016-01-01

Geological carbon sequestration captures CO 2 from industrial sources and stores the CO 2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO 2 concentration. This study uses biogeochemical modeling to explore the influence of CO 2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO 2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO 2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO 2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO 2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

Thermodynamic and Kinetic Response of Microbial Reactions to High CO2

PubMed Central

Jin, Qusheng; Kirk, Matthew F.

2016-01-01

Geological carbon sequestration captures CO2 from industrial sources and stores the CO2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO2 concentration. This study uses biogeochemical modeling to explore the influence of CO2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses. PMID:27909425

Anaerobic oxidation of methane: an “active” microbial process

PubMed Central

Cui, Mengmeng; Ma, Anzhou; Qi, Hongyan; Zhuang, Xuliang; Zhuang, Guoqiang

2015-01-01

The anaerobic oxidation of methane (AOM) is an important sink of methane that plays a significant role in global warming. AOM was first found to be coupled with sulfate reduction and mediated by anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). ANME, often forming consortia with SRB, are phylogenetically related to methanogenic archaea. ANME-1 is even able to produce methane. Subsequently, it has been found that AOM can also be coupled with denitrification. The known microbes responsible for this process are Candidatus Methylomirabilis oxyfera (M. oxyfera) and Candidatus Methanoperedens nitroreducens (M. nitroreducens). Candidatus Methylomirabilis oxyfera belongs to the NC10 bacteria, can catalyze nitrite reduction through an “intra-aerobic” pathway, and may catalyze AOM through an aerobic methane oxidation pathway. However, M. nitroreducens, which is affiliated with ANME-2d archaea, may be able to catalyze AOM through the reverse methanogenesis pathway. Moreover, manganese (Mn4+) and iron (Fe3+) can also be used as electron acceptors of AOM. This review summarizes the mechanisms and associated microbes of AOM. It also discusses recent progress in some unclear key issues about AOM, including ANME-1 in hypersaline environments, the effect of oxygen on M. oxyfera, and the relationship of M. nitroreducens with ANME. PMID:25530008

Geochemistry of Dissolved Organic Matter in a Spatially Highly Resolved Groundwater Petroleum Hydrocarbon Plume Cross-Section.

PubMed

Dvorski, Sabine E-M; Gonsior, Michael; Hertkorn, Norbert; Uhl, Jenny; Müller, Hubert; Griebler, Christian; Schmitt-Kopplin, Philippe

2016-06-07

At numerous groundwater sites worldwide, natural dissolved organic matter (DOM) is quantitatively complemented with petroleum hydrocarbons. To date, research has been focused almost exclusively on the contaminants, but detailed insights of the interaction of contaminant biodegradation, dominant redox processes, and interactions with natural DOM are missing. This study linked on-site high resolution spatial sampling of groundwater with high resolution molecular characterization of DOM and its relation to groundwater geochemistry across a petroleum hydrocarbon plume cross-section. Electrospray- and atmospheric pressure photoionization (ESI, APPI) ultrahigh resolution mass spectrometry (FT-ICR-MS) revealed a strong interaction between DOM and reactive sulfur species linked to microbial sulfate reduction, i.e., the key redox process involved in contaminant biodegradation. Excitation emission matrix (EEM) fluorescence spectroscopy in combination with Parallel Factor Analysis (PARAFAC) modeling attributed DOM samples to specific contamination traits. Nuclear magnetic resonance (NMR) spectroscopy evaluated the aromatic compounds and their degradation products in samples influenced by the petroleum contamination and its biodegradation. Our orthogonal high resolution analytical approach enabled a comprehensive molecular level understanding of the DOM with respect to in situ petroleum hydrocarbon biodegradation and microbial sulfate reduction. The role of natural DOM as potential cosubstrate and detoxification reactant may improve future bioremediation strategies.

Reductive atmospheric acid leaching of spent alkaline batteries in H2SO4/Na2SO3 solutions

NASA Astrophysics Data System (ADS)

Morcali, Mehmet Hakan

2015-07-01

This work studies the optimum reductive leaching process for manganese and zinc recovery from spent alkaline battery paste. The effects of reducing agents, acid concentration, pulp density, reaction temperature, and leaching time on the dissolution of manganese and zinc were investigated in detail. Manganese dissolution by reductive acidic media is an intermediate-controlled process with an activation energy of 12.28 kJ·mol-1. After being leached, manganese and zinc were selectively precipitated with sodium hydroxide. The zinc was entirely converted into zincate (Zn(OH){4/2-}) ions and thus did not co-precipitate with manganese hydroxide during this treatment (2.0 M NaOH, 90 min, 200 r/min, pH > 13). After the manganese was removed from the solution, the Zn(OH){4/2-} was precipitated as zinc sulfate in the presence of sulfuric acid. The results indicated that this process could be effective in recovering manganese and zinc from alkaline batteries.

Vertical gradients in carbon flow and methane production in a sulfate-rich oil sands tailings pond.

PubMed

Stasik, Sebastian; Wendt-Potthoff, Katrin

2016-12-01

Oil sands tailings ponds are primary storage basins for tailings produced during oil sands processing in Alberta (Canada). Due to microbial metabolism, methane production contributes to greenhouse gas emissions, but positively affects tailings densification, which is relevant for operational water re-use. Depending on the age and depth of tailings, the activity of sulfate-reducing bacteria (SRB) may control methanogenesis due to the competition for substrates. To assess the depth-related impact of sulfate reduction on CH 4 emissions, original tailings of two vicinal pond profiles were incubated in anoxic microcosms with/without molybdate as selective inhibitor of microbial sulfate reduction. Integrating methane production rates, considerable volumes of CH 4 emissions (∼5.37 million L d -1 ) may be effectively prevented by the activity of SRB in sulfidic tailings between 3.5 and 7.5 m. To infer metabolic potentials controlling methanogenic pathways, a set of relevant organic acids (acetate, formate, propionate, butyrate, lactate) was added to part of the microcosms. Generally, organic acid transformation shifted with depth, with highest rates (305-446 μmol L -1  d -1 ) measured in fresh tailings at 5.5-7.5 m. In all depths, a transient accumulation of acetate revealed its importance as key intermediate during organic matter decomposition. SRB dominated the transformation of acetate, butyrate and propionate, but were not essential for lactate and formate turnover. Acetate as methanogenic substrate was important only at 13.5 m. At 1-7.5 m, methanogenesis significantly increased in presence of organic acids, most likely due to the syntrophic oxidation of acetate to CO 2 by SRB and subsequent conversion to CH 4 . Copyright © 2016 Elsevier Ltd. All rights reserved.

CO2 exposure at pressure impacts metabolism and stress responses in the model sulfate-reducing bacterium Desulfovibrio vulgaris strain Hildenborough

PubMed Central

Wilkins, Michael J.; Hoyt, David W.; Marshall, Matthew J.; Alderson, Paul A.; Plymale, Andrew E.; Markillie, L. Meng; Tucker, Abby E.; Walter, Eric D.; Linggi, Bryan E.; Dohnalkova, Alice C.; Taylor, Ron C.

2014-01-01

Geologic carbon dioxide (CO2) sequestration drives physical and geochemical changes in deep subsurface environments that impact indigenous microbial activities. The combined effects of pressurized CO2 on a model sulfate-reducing microorganism, Desulfovibrio vulgaris, have been assessed using a suite of genomic and kinetic measurements. Novel high-pressure NMR time-series measurements using 13C-lactate were used to track D. vulgaris metabolism. We identified cessation of respiration at CO2 pressures of 10 bar, 25 bar, 50 bar, and 80 bar. Concurrent experiments using N2 as the pressurizing phase had no negative effect on microbial respiration, as inferred from reduction of sulfate to sulfide. Complementary pressurized batch incubations and fluorescence microscopy measurements supported NMR observations, and indicated that non-respiring cells were mostly viable at 50 bar CO2 for at least 4 h, and at 80 bar CO2 for 2 h. The fraction of dead cells increased rapidly after 4 h at 80 bar CO2. Transcriptomic (RNA-Seq) measurements on mRNA transcripts from CO2-incubated biomass indicated that cells up-regulated the production of certain amino acids (leucine, isoleucine) following CO2 exposure at elevated pressures, likely as part of a general stress response. Evidence for other poorly understood stress responses were also identified within RNA-Seq data, suggesting that while pressurized CO2 severely limits the growth and respiration of D. vulgaris cells, biomass retains intact cell membranes at pressures up to 80 bar CO2. Together, these data show that geologic sequestration of CO2 may have significant impacts on rates of sulfate reduction in many deep subsurface environments where this metabolism is a key respiratory process. PMID:25309528

CO2 exposure at pressure impacts metabolism and stress responses in the model sulfate-reducing bacterium Desulfovibrio vulgaris strain Hildenborough

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilkins, Michael J.; Hoyt, David W.; Marshall, Matthew J.

Geologic carbon dioxide (CO2) sequestration drives physical and geochemical changes in deep subsurface environments that impact indigenous microbial activities. The combined effects of pressurized CO2 on a model sulfate-reducing microorganism, Desulfovibrio vulgaris, have been assessed using a suite of genomic and kinetic measurements. Novel high-pressure NMR time-series measurements using 13C-lactate were used to track D. vulgaris metabolism. We identified cessation of respiration at CO2 pressures of 10 bar, 25 bar, 50 bar, and 80 bar. Concurrent experiments using N2 as the pressurizing phase had no negative effect on microbial respiration, as inferred from reduction of sulfate to sulfide. Complementary pressurizedmore » batch incubations and fluorescence microscopy measurements supported NMR observations, and indicated that non-respiring cells were mostly viable at 50 bar CO2 for at least four hours, and at 80 bar CO2 for two hours. The fraction of dead cells increased rapidly after four hours at 80 bar CO2. Transcriptomic (RNA-Seq) measurements on mRNA transcripts from CO2-incubated biomass indicated that cells up-regulated the production of certain amino acids (leucine, isoleucine) following CO2 exposure at elevated pressures, likely as part of a general stress response. Evidence for other poorly understood stress responses were also identified within RNA-Seq data, suggesting that while pressurized CO2 severely limits the growth and respiration of D. vulgaris cells, biomass retains intact cell membranes at pressures up to 80 bar CO2. Together, these data show that geologic sequestration of CO2 may have significant impacts on rates of sulfate reduction in many deep subsurface environments where this metabolism is a key respiratory process.« less

Microscale speciation of arsenic and iron in ferric-based sorbents subjected to simulated landfill conditions

PubMed Central

Root, Robert A.; Fathordoobadi, Sahar; Alday, Fernando; Ela, Wendell; Chorover, Jon

2013-01-01

During treatment for potable use, water utilities generate arsenic-bearing ferric wastes that are subsequently dispatched to landfills. The biogeochemical weathering of these residuals in mature landfills affects the potential mobilization of sorbed arsenic species via desorption from solids subjected to phase transformations driven by abundant organic matter and bacterial activity. Such processes are not simulated with the Toxicity Characteristic Leaching Procedure (TCLP) currently used to characterize hazard. To examine the effect of sulfate on As retention in landfill leachate, columns of As(V) loaded amorphous ferric hydroxide were reacted biotically at two leachate sulfate concentrations (0.064 mM and 2.1 mM). After 300 d, ferric sorbents were reductively dissolved. Arsenic released to porewaters was partially co-precipitated in mixed-valent secondary iron phases whose speciation was dependent on sulfate concentration. As and Fe XAS showed that, in the low sulfate column, 75–81% of As(V) was reduced to As(III), and 53–68% of the Fe(III) sorbent was transformed, dominantly to siderite and green rust. In the high sulfate column, Fe(III) solids were reduced principally to FeS(am), whereas As(V) was reduced to a polymeric sulfide with local atomic structure of realgar. Multi-energy micro-X-ray fluorescence (ME-μXRF) imaging at Fe and As K-edges showed that As formed surface complexes with ferrihydrite > siderite > green rust in the low sulfate column; while discrete realgar-like phases formed in the high sulfate systems. Results indicate that landfill sulfur chemistry exerts strong control over the potential mobilization of As from ferric sorbent residuals by controlling secondary As and Fe sulfide co-precipitate formation. PMID:24102155

ANAMMOX-like performances for nitrogen removal from ammonium-sulfate-rich wastewater in an anaerobic sequencing batch reactor.

PubMed

Prachakittikul, Pensiri; Wantawin, Chalermraj; Noophan, Pongsak Lek; Boonapatcharoen, Nimaradee

2016-01-01

Ammonium removal by the ANaerobic AMonium OXidation (ANAMMOX) process was observed through the Sulfate-Reducing Ammonium Oxidation (SRAO) process. The same concentration of ammonium (100 mg N L(-1)) was applied to two anaerobic sequencing batch reactors (AnSBRs) that were inoculated with the same activated sludge from the Vermicelli wastewater treatment process, while nitrite was fed in ANAMMOX and sulfate in SRAO reactors. In SRAO-AnSBR, in substrates that were fed with a ratio of NH4(+)/SO4(2-) at 1:0.4 ± 0.03, a hydraulic retention time (HRT) of 48 h and without sludge draining, the Ammonium Removal Rate (ARR) was 0.02 ± 0.01 kg N m(-3).d(-1). Adding specific ANAMMOX substrates to SRAO-AnSBR sludge in batch tests results in specific ammonium and nitrite removal rates of 0.198 and 0.139 g N g(-1) VSS.d, respectively, indicating that the ANAMMOX activity contributes to the removal of ammonium in the SRAO process using the nitrite that is produced from SRAO. Nevertheless, the inability of ANAMMOX to utilize sulfate to oxidize ammonium was also investigated in batch tests by augmenting enriched ANAMMOX culture in SRAO-AnSBR sludge and without nitrite supply. The time course of sulfate in a 24-hour cycle of SRAO-AnSBR showed an increase in sulfate after 6 h. For enriched SRAO culture, the uptake molar ratio of NH4(+)/SO4(2-) at 8 hours in a batch test was 1:0.82 lower than the value of 1:0.20 ± 0.09 as obtained in an SRAO-AnSBR effluent, while the stoichiometric ratio of 1:0.5 that includes the ANAMMOX reaction was in this range. After a longer operation of more than 2 years without sludge draining, the accumulation of sulfate and the reduction of ammonium removal were observed, probably due to the gradual increase in the sulfur denitrification rate and the competitive use of nitrite with ANAMMOX. The 16S rRNA gene PCR-DGGE (polymerase chain reaction-denaturing gradient gel electrophoresis) and PCR cloning analyses resulted in the detection of the ANAMMOX bacterium (Candidatus Brocadia sinica JPN1) Desulfacinum subterraneum belonging to the genus Desulfacinum and bacteria that are involved in sulfur metabolism (Pseudomonas aeruginosa strain SBTPe-001 and Paracoccus denitrificans strain IAM12479) in SRAO-AnSBR.

Oxidation of polycyclic aromatic hydrocarbons under sulfate-reducing conditions

USGS Publications Warehouse

Coates, J.D.; Anderson, R.T.; Lovley, D.R.

1996-01-01

[14C]naphthalene and phenanthrene were oxidized to 14CO2 without a detectable lag under strict anaerobic conditions in sediments from San Diego Bay, San Diego, Calif., that were heavily contaminated with polycyclic aromatic hydrocarbons (PAHs) but not in less contaminated sediments. Sulfate reduction was necessary for PAH oxidation. These results suggest that the self-purification capacity of PAH-contaminated sulfate-reducing environments may be greater than previously recognized.

(PRESENTED AT CMAS) THE NONLINEAR RESPONSE OF NITRATE REPLACEMENT THAT MITIGATES SULFATE REDUCTION: THE GAS RATION AS AN INDICTOR AND SENSITIVITY TO ERRORS IN TOTAL AMMONIA AND TOTAL NITRATE

EPA Science Inventory

The poster presents an assessment, using the CMAQ air quality model, showing the inorganic gas ratio (the ratio of free ammonia to total nitrate) can function as a screening indicator of the winter replacement of sulfate by nitrate when sulfate is reduced. It also presents an as...

Sulfur isotope evidence for regional recharge of saline water during continental glaciation, north-central United States

NASA Astrophysics Data System (ADS)

Siegel, D. I.

1990-11-01

Sulfate concentrations in ground water from the Cambrian-Ordovician aquifer of southeastern Wisconsin and northern Illinois increase up to hundreds of times where the aquifer is confined beneath the Maquoketa Shale. There is no sulfate source in the aquifer or overlying rocks except for minor amounts of finely disseminated pyrite. Coinciding with increasing sulfate concentrations, δ34S of the dissolved sulfate increases from less than -5‰ in the unconfined part of the aquifer to a nearly constant value of +20‰ where the aquifer is confined and where sulfate reduction is minimal. The most likely source for this isotopically heavy sulfate is ground water associated with Silurian evaporites under Lake Michigan. It is uncertain if the sulfate-rich water was emplaced in pulses or mostly during the last glaciation.

Sulfur and oxygen isotope insights into sulfur cycling in shallow-sea hydrothermal vents, Milos, Greece

PubMed Central

2014-01-01

Shallow-sea (5 m depth) hydrothermal venting off Milos Island provides an ideal opportunity to target transitions between igneous abiogenic sulfide inputs and biogenic sulfide production during microbial sulfate reduction. Seafloor vent features include large (>1 m2) white patches containing hydrothermal minerals (elemental sulfur and orange/yellow patches of arsenic-sulfides) and cells of sulfur oxidizing and reducing microorganisms. Sulfide-sensitive film deployed in the vent and non-vent sediments captured strong geochemical spatial patterns that varied from advective to diffusive sulfide transport from the subsurface. Despite clear visual evidence for the close association of vent organisms and hydrothermalism, the sulfur and oxygen isotope composition of pore fluids did not permit delineation of a biotic signal separate from an abiotic signal. Hydrogen sulfide (H2S) in the free gas had uniform δ34S values (2.5 ± 0.28‰, n = 4) that were nearly identical to pore water H2S (2.7 ± 0.36‰, n = 21). In pore water sulfate, there were no paired increases in δ34SSO4 and δ18OSO4 as expected of microbial sulfate reduction. Instead, pore water δ34SSO4 values decreased (from approximately 21‰ to 17‰) as temperature increased (up to 97.4°C) across each hydrothermal feature. We interpret the inverse relationship between temperature and δ34SSO4 as a mixing process between oxic seawater and 34S-depleted hydrothermal inputs that are oxidized during seawater entrainment. An isotope mass balance model suggests secondary sulfate from sulfide oxidation provides at least 15% of the bulk sulfate pool. Coincident with this trend in δ34SSO4, the oxygen isotope composition of sulfate tended to be 18O-enriched in low pH (<5), high temperature (>75°C) pore waters. The shift toward high δ18OSO4 is consistent with equilibrium isotope exchange under acidic and high temperature conditions. The source of H2S contained in hydrothermal fluids could not be determined with the present dataset; however, the end-member δ34S value of H2S discharged to the seafloor is consistent with equilibrium isotope exchange with subsurface anhydrite veins at a temperature of ~300°C. Any biological sulfur cycling within these hydrothermal systems is masked by abiotic chemical reactions driven by mixing between low-sulfate, H2S-rich hydrothermal fluids and oxic, sulfate-rich seawater. PMID:25183951

Sulfate and chromate increased each other's uptake and translocation in As-hyperaccumulator Pteris vittata.

PubMed

de Oliveira, Letúzia M; Gress, Julia; De, Jaysankar; Rathinasabapathi, Bala; Marchi, Giuliano; Chen, Yanshan; Ma, Lena Q

2016-03-01

We investigated the effects of chromate (CrVI) and sulfate on their uptake and translocation in As-hyperaccumulator Pteris vittata. Plants were exposed to 1) 0.1 mM CrVI and 0, 0.25, 1.25 or 2.5 mM sulfate or 2) 0.25 mM sulfate and 0, 0.5, 2.5 or 5.0 mM CrVI for 1 d in hydroponics. P. vittata accumulated 26 and 1261 mg kg(-1) Cr in the fronds and roots at CrVI0.1, and 2197 and 1589 mg kg(-1) S in the fronds and roots at S0.25. Increasing sulfate concentrations increased Cr root concentrations by 16-66% and helped CrVI reduction to CrIII whereas increasing CrVI concentrations increased frond sulfate concentrations by 3-27%. Increasing sulfate concentrations enhanced TBARS concentrations in the biomass, indicating oxidative stress caused lipid peroxidation in plant cell membranes. However, addition of 0.25-2.5 mM sulfate alleviated CrVI's toxic effects and decreased TBARS from 23.5 to 9.46-12.3 μmol g(-1) FW. Though CrVI was supplied, 78-96% of CrIII was in the biomass, indicating efficient CrVI reduction to CrIII by P. vittata. The data indicated the amazing ability of P. vittata in Cr uptake at 289 mg kg(-1) h(-1) with little translocation to the fronds. These results indicated that P. vittata had potential in Cr phytoremediation in contaminated sites but further studies are needed to evaluate this potential. The facts that CrVI and sulfate helped each other in uptake by P. vittata suggest that CrVI was not competing with sulfate uptake in P. vittata. However, the mechanisms of how sulfate and CrVI enhance each other's accumulation in P. vittata need further investigation. Published by Elsevier Ltd.

Sulfide-Induced Dissimilatory Nitrate Reduction to Ammonium Supports Anaerobic Ammonium Oxidation (Anammox) in an Open-Water Unit Process Wetland

PubMed Central

Jones, Zackary L.; Jasper, Justin T.; Sedlak, David L.

2017-01-01

ABSTRACT Open-water unit process wetlands host a benthic diatomaceous and bacterial assemblage capable of nitrate removal from treated municipal wastewater with unexpected contributions from anammox processes. In exploring mechanistic drivers of anammox, 16S rRNA gene sequencing profiles of the biomat revealed significant microbial community shifts along the flow path and with depth. Notably, there was an increasing abundance of sulfate reducers (Desulfococcus and other Deltaproteobacteria) and anammox microorganisms (Brocadiaceae) with depth. Pore water profiles demonstrated that nitrate and sulfate concentrations exhibited a commensurate decrease with biomat depth accompanied by the accumulation of ammonium. Quantitative PCR targeting the anammox hydrazine synthase gene, hzsA, revealed a 3-fold increase in abundance with biomat depth as well as a 2-fold increase in the sulfate reductase gene, dsrA. These microbial and geochemical trends were most pronounced in proximity to the influent region of the wetland where the biomat was thickest and influent nitrate concentrations were highest. While direct genetic queries for dissimilatory nitrate reduction to ammonium (DNRA) microorganisms proved unsuccessful, an increasing depth-dependent dominance of Gammaproteobacteria and diatoms that have previously been functionally linked to DNRA was observed. To further explore this potential, a series of microcosms containing field-derived biomat material confirmed the ability of the community to produce sulfide and reduce nitrate; however, significant ammonium production was observed only in the presence of hydrogen sulfide. Collectively, these results suggest that biogenic sulfide induces DNRA, which in turn can explain the requisite coproduction of ammonium and nitrite from nitrified effluent necessary to sustain the anammox community. IMPORTANCE This study aims to increase understanding of why and how anammox is occurring in an engineered wetland with limited exogenous contributions of ammonium and nitrite. In doing so, the study has implications for how geochemical parameters could potentially be leveraged to impact nutrient cycling and attenuation during the operation of treatment wetlands. The work also contributes to ongoing discussions about biogeochemical signatures surrounding anammox processes and enhances our understanding of the contributions of anammox processes in freshwater environments. PMID:28526796

Comparison of preparation methods for ceria catalyst and the effect of surface and bulk sulfates on its activity toward NH3-SCR.

PubMed

Chang, Huazhen; Ma, Lei; Yang, Shijian; Li, Junhua; Chen, Liang; Wang, Wei; Hao, Jiming

2013-11-15

A series of CeO2 catalysts prepared with sulfate (S) and nitrate (N) precursors by hydrothermal (H) and precipitation (P) methods were investigated in selective catalytic reduction of NOx by NH3 (NH3-SCR). The catalytic activity of CeO2 was significantly affected by the preparation methods and the precursor type. CeO2-SH, which was prepared by hydrothermal method with cerium (IV) sulfate as a precursor, showed excellent SCR activity and high N2 selectivity in the temperature range of 230-450 °C. Based on the results obtained by temperature-programmed reduction (H2-TPR), transmission infrared spectra (IR) and thermal gravimetric analysis (TGA), the excellent performance of CeO2-SH was correlated with the surface sulfate species formed in the hydrothermal reaction. These results indicated that sulfate species bind with Ce(4+) on the CeO2-SH catalyst, and the specific sulfate species, such as Ce(SO4)2 or CeOSO4, were formed. The adsorption of NH3 was promoted by these sulfate species, and the probability of immediate oxidation of NH3 to N2O on Ce(4+) was reduced. Accordingly, the selective oxidation of NH3 was enhanced, which contributed to the high N2 selectivity in the SCR reaction. However, the location of sulfate on the CeO2-SP catalyst was different. Plenty of sulfate species were likely deposited on CeO2-SP surface, covering the active sites for NO oxidation, which resulted in poor SCR activity in the test temperature range. Moreover, the resistance to alkali metals, such as Na and K, was improved over the CeO2-SH catalyst. Copyright © 2013 Elsevier B.V. All rights reserved.

Mechanisms of sulfate removal from subsurface calcium chloride brines: Heletz-Kokhav oilfields, Israel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavrieli, I.; Starinsky, A.; Spiro, B.

1995-09-01

The evolution of the Ca-chloride brines in the Heletz Formation, Lower Cretaceous, in the southern coastal plain of Israel was reconstructed through the study of its sulfate concentration and isotopic composition. Particular emphasis was given to the brine-oil interaction in the oilfields and to the sulfate depletion and lower SO{sub 4}/Cl ratio in brines in contact with hydrocarbons (oil brines) relative to {open_quotes}oil-free{close_quotes} from dry wells in the same oilfields. A method is presented for a calculation of the amount of sulfate removed from the original seawater in the various stages of its evolution to Ca-chloride brine. Eastward migration ofmore » the Messinian Ca-Chloride brine into the Heletz Formation was accompanied by dolomitization of the country rock. Final depletion of sulfate from the brines took place, and possibly still occurs, in the presence of crude oil in the oilfields. The two oil-producing fields, Heletz and Kokhav, occupy different areas on a Rayleigh distillation diagram. Sulfate depletion in both fields is accompanied by an increase in {delta}{sup 34}S{sub SO}{sub 4}, which reaches a maximum values of 59{per_thousand}. The above correlation is explained by bacterial sulfate reduction facilitated by the contact with the crude. Samples collected from the same boreholes at time intervals of several months show two opposing trends: sulfate concentration decrease accompanied by increase in {delta}{sup 34}S{sub SO}{sub 4}, and vice versa. While the first can be explained as in situ bacterial sulfate reduction, the latter attest to subsurface brine migration, as would be expected in oil-producing fields.« less

Process for removing sulfate anions from waste water

DOEpatents

Nilsen, David N.; Galvan, Gloria J.; Hundley, Gary L.; Wright, John B.

1997-01-01

A liquid emulsion membrane process for removing sulfate anions from waste water is disclosed. The liquid emulsion membrane process includes the steps of: (a) providing a liquid emulsion formed from an aqueous strip solution and an organic phase that contains an extractant capable of removing sulfate anions from waste water; (b) dispersing the liquid emulsion in globule form into a quantity of waste water containing sulfate anions to allow the organic phase in each globule of the emulsion to extract and absorb sulfate anions from the waste water and (c) separating the emulsion including its organic phase and absorbed sulfate anions from the waste water to provide waste water containing substantially no sulfate anions.

Genomic reconstruction of novel sediment phyla enlightens roles in sedimentary biogeochemical cycling

NASA Astrophysics Data System (ADS)

Baker, B.; Lazar, C.; Seitz, K.; Teske, A.; Hinrichs, K. U.; Dick, G.

2015-12-01

Estuaries are among the most productive habitats on the planet. Microbes in estuary sediments control the turnover of organic carbon, and the anaerobic cycling of nitrogen and sulfur. These communities are complex and primarily made up of uncultured lineages, thus little is known about how ecological and metabolic processes are partitioned in sediments. We reconstructed 82 bacterial and 24 archaeal high-quality genomes from different redox regimes (sulfate-rich, sulfate-methane transition zone, and methane-rich zones) of estuary sediments. These bacteria belong to 23 distinct groups, including uncultured candidate phyla (eg. KSB1, TA06, and KD3-62), and three newly described phyla (WOR-1, and -2, and -3). The archaea encompass 8 widespread sediment lineages including MGB-D, RC-III and IV, Z7ME43, Parvarchaeota, Lokiarchoaeta (MBG-B), SAGMEG, Bathyarchaeota (groups MCG-1, -6, -7, and -15) and previously unrecognized deeply branched phylum "Thorarchaeota". The uncultured phyla mediate essential biogeochemical processes of the estuarine environment. Z7ME43 archaea have genes for S disproportionation (S0 reduction and thiosulfate reduction and oxidation). SAGMEG appear to be strict anaerobes capable of coupling CO/H2 oxidation to either S0 or nitrite reduction and have novel RubisCO genes for carbon fixation. Thorarchaeota contain pathways for acetate production from the degradation of detrital proteins and intermediate S cycling. Furthermore, the gene content of this group revealed links in the evolutionary histories of archaea and eukaryotes. This dataset extents our knowledge of the metabolic potential of several uncultured phyla. We were able to chart the flow of carbon and nutrients through the multiple layers of bacterial processing and reveal potential ecological interactions within the communities.

Structure and function of subsurface microbial communities affecting radionuclide transport and bioimmobilization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kostka, Joel E.; Prakash, Om; Green, Stefan J.

2012-05-01

Our objectives were to: 1) isolate and characterize novel anaerobic prokaryotes from subsurface environments exposed to high levels of mixed contaminants (U(VI), nitrate, sulfate), 2) elucidate the diversity and distribution of metabolically active metal- and nitrate-reducing prokaryotes in subsurface sediments, and 3) determine the biotic and abiotic mechanisms linking electron transport processes (nitrate, Fe(III), and sulfate reduction) to radionuclide reduction and immobilization. Mechanisms of electron transport and U(VI) transformation were examined under near in situ conditions in sediment microcosms and in field investigations. Field sampling was conducted at the Oak Ridge Field Research Center (ORFRC), in Oak Ridge, Tennessee. Themore » ORFRC subsurface is exposed to mixed contamination predominated by uranium and nitrate. In short, we effectively addressed all 3 stated objectives of the project. In particular, we isolated and characterized a large number of novel anaerobes with a high bioremediation potential that can be used as model organisms, and we are now able to quantify the function of subsurface sedimentary microbial communities in situ using state-of-the-art gene expression methods (molecular proxies).« less

Effect of power plant emission reductions on a nearby wilderness area: a case study in northwestern Colorado

USGS Publications Warehouse

Mast, M. Alisa; Ely, Daniel

2013-01-01

This study evaluates the effect of emission reductions at two coal-fired power plants in northwestern Colorado on a nearby wilderness area. Control equipment was installed at both plants during 1999–2004 to reduce SO2 and NOx emissions. One challenge was separating the effects of local from regional emissions, which also declined during the study period. The long-term datasets examined confirm that emission reductions had a beneficial effect on air and water quality in the wilderness. Despite a 75 % reduction in SO2 emissions, sulfate aerosols measured in the wilderness decreased by only 20 %. Because the site is relatively close to the power plants (2 to sulfate, particularly under conditions of low relative humidity, might account for this less than one-to-one response. On the clearest days, emissions controls appeared to improve visibility by about 1 deciview, which is a small but perceptible improvement. On the haziest days, however, there was little improvement perhaps reflecting the dominance of regional haze and other components of visibility degradation particularly organic carbon and dust. Sulfate and acidity in atmospheric deposition decreased by 50 % near the southern end of the wilderness of which 60 % was attributed to power plant controls and the remainder to reductions in regional sources. Lake water sulfate responded rapidly to trends in deposition declining at 28 lakes monitored in and near the wilderness. Although no change in the acid–base status was observed, few of the lakes appear to be at risk from chronic or episodic acidification.

Polyhydroxylated sulfated steroids derived from 5α-cholestanes as antiviral agents against herpes simplex virus.

PubMed

Pujol, Carlos A; Sepúlveda, Claudia S; Richmond, Victoria; Maier, Marta S; Damonte, Elsa B

2016-07-01

Twelve polyhydroxylated sulfated steroids synthesized from a 5α-cholestane skeleton with different substitutions in C-2, C-3 and C-6 were evaluated for cytotoxicity and antiviral activity against herpes simplex virus (HSV) by a virus plaque reduction assay. Four compounds elicited a selective inhibitory effect against HSV. The disodium salt of 2β,3α-dihydroxy-6E-hydroximine-5α-cholestane-2,3-disulfate, named compound 7, was the most effective inhibitor of HSV-1, HSV-2 and pseudorabies virus (PrV) strains, including acyclovir-resistant variants, in human and monkey cell lines. Preliminary mechanistic studies demonstrated that compound 7 did not affect the initial steps of virus entry but inhibited a subsequent event in the infection process of HSV.

Role of microbial processes in linking sandstone diagenesis with organic-rich clays

USGS Publications Warehouse

McMahon, P.B.; Chapelle, F.H.; Falls, W.F.; Bradley, P.M.

1992-01-01

Shows that the processes of microbial organic-acid production (via fermentation) in clays and microbial organic-acid consumption (via sulfate reduction) in sands effectively link organic-rich clays to sandstone diagenesis in the Black Creek Formation of South Carolina. Diagenetic processes have resulted in the formation of 10 volume percent calcite cement, 0.1 volume percent authigenic pyrite, and 1.5 volume percent secondary porosity in Black Creek sands. However, the distribution of these diagenetic processes is not uniform, resulting in net destruction of porosity in some parts of the sand and net porosity enchancement in other parts. -from Authors

Anaerobic oxidation of methane associated with sulfate reduction in a natural freshwater gas source

PubMed Central

Timmers, Peer HA; Suarez-Zuluaga, Diego A; van Rossem, Minke; Diender, Martijn; Stams, Alfons JM; Plugge, Caroline M

2016-01-01

The occurrence of anaerobic oxidation of methane (AOM) and trace methane oxidation (TMO) was investigated in a freshwater natural gas source. Sediment samples were taken and analyzed for potential electron acceptors coupled to AOM. Long-term incubations with 13C-labeled CH4 (13CH4) and different electron acceptors showed that both AOM and TMO occurred. In most conditions, 13C-labeled CO2 (13CO2) simultaneously increased with methane formation, which is typical for TMO. In the presence of nitrate, neither methane formation nor methane oxidation occurred. Net AOM was measured only with sulfate as electron acceptor. Here, sulfide production occurred simultaneously with 13CO2 production and no methanogenesis occurred, excluding TMO as a possible source for 13CO2 production from 13CH4. Archaeal 16S rRNA gene analysis showed the highest presence of ANME-2a/b (ANaerobic MEthane oxidizing archaea) and AAA (AOM Associated Archaea) sequences in the incubations with methane and sulfate as compared with only methane addition. Higher abundance of ANME-2a/b in incubations with methane and sulfate as compared with only sulfate addition was shown by qPCR analysis. Bacterial 16S rRNA gene analysis showed the presence of sulfate-reducing bacteria belonging to SEEP-SRB1. This is the first report that explicitly shows that AOM is associated with sulfate reduction in an enrichment culture of ANME-2a/b and AAA methanotrophs and SEEP-SRB1 sulfate reducers from a low-saline environment. PMID:26636551

Isotope Biogeochemistry of Sulfur in a Cold-Water Carbonate Mound (IODP Site 1317)

NASA Astrophysics Data System (ADS)

Ferdelman, T. G.; Boettcher, M. E.

2007-12-01

To establish a depositional model for cold-water carbonate mounds, Challenger Mound and adjacent continental slope sites were drilled during IODP Expedition 307 in May 2005. Although a role for methane seepage and subsequent anaerobic oxidation was discounted both as a hard-round substrate for mound initiation and as a principal source of carbonate within the mound succession, interstitial water profiles of sulfate, alkalinity, Mg, and Sr indicated a tight coupling between carbonate diagenesis and mircrobial sulfate reduction. The reaction of sulfide with siliciclastic iron-bearing minerals to form pyrite was proposed to account for enhanced diagenetic carbonate precipitation (Ferdelman et al., 2006; Proc. IODP, vol. 307; doi:10.2204/iodp.proc.307.2006). To characterize these geomicrobial sulfur transformations in the carbonate mound sediments, the inorganic and stable isotope geochemical compositions of pore water sulfate and solid phase reduced sulfur compounds were performed. Acid-volatile sulfur (AVS) and pyrite del 34S compositions were usually similar and exhibited an increasing trend of from -40 per mil near surface to -20 per mil at the mound base at 132 mbsf. However, several excursions to more 34S sulfur enriched pyrite to values >0 per mil were observed in the deeper sections of the mound sequence. These excursions may be linked transitory changes in the depth of the methane-sulfate transition zone during mound build-up. The oxygen isotopic composition of residual dissolved sulfate indicates intracellular isotope exchange processes within the cells of SRBs, leading to increasing equilibration between extracellular pore water and sulfate.

Large Carbonate Associated Sulfate isotopic variability between brachiopods, micrite, and other sedimentary components in Late Ordovician strata

NASA Astrophysics Data System (ADS)

Present, Theodore M.; Paris, Guillaume; Burke, Andrea; Fischer, Woodward W.; Adkins, Jess F.

2015-12-01

Carbonate Associated Sulfate (CAS) is trace sulfate incorporated into carbonate minerals during their precipitation. Its sulfur isotopic composition is often assumed to track that of seawater sulfate and inform global carbon and oxygen budgets through Earth's history. However, many CAS sulfur isotope records based on bulk-rock samples are noisy. To determine the source of bulk-rock CAS variability, we extracted CAS from different internal sedimentary components micro-drilled from well-preserved Late Ordovician and early Silurian-age limestones from Anticosti Island, Quebec, Canada. Mixtures of these components, whose sulfur isotopic compositions vary by nearly 25‰, can explain the bulk-rock CAS range. Large isotopic variability of sedimentary micrite CAS (34S-depleted from seawater by up to 15‰) is consistent with pore fluid sulfide oxidation during early diagenesis. Specimens recrystallized during burial diagenesis have CAS 34S-enriched by up to 9‰ from Hirnantian seawater, consistent with microbial sulfate reduction in a confined aquifer. In contrast to the other variable components, brachiopods with well-preserved secondary-layer fibrous calcite-a phase independently known to be the best-preserved sedimentary component in these strata-have a more homogeneous isotopic composition. These specimens indicate that seawater sulfate remained close to about 25‰ (V-CDT) through Hirnantian (end-Ordovician) events, including glaciation, mass extinction, carbon isotope excursion, and pyrite-sulfur isotope excursion. The textural relationships between our samples and their CAS isotope ratios highlight the role of diagenetic biogeochemical processes in setting the isotopic composition of CAS.

Reduction of adsorbed As(V) on nano-TiO2 by sulfate-reducing bacteria.

PubMed

Luo, Ting; Ye, Li; Ding, Cheng; Yan, Jinlong; Jing, Chuanyong

2017-11-15

Reduction of surface-bound arsenate [As(V)] and subsequent release into the aqueous phase contribute to elevated As in groundwater. However, this natural process is not fully understood, especially in the presence of sulfate-reducing bacteria (SRB). Gaining mechanistic insights into solid-As(V)-SRB interactions motivated our molecular level study on the fate of nano-TiO 2 bound As(V) in the presence of Desulfovibrio vulgaris DP4, a strain of SRB, using incubation and in situ ATR-FTIR experiments. The incubation results clearly revealed the reduction of As(V), either adsorbed on nano-TiO 2 or dissolved, in the presence of SRB. In contrast, this As(V) reduction was not observed in abiotic control experiments where sulfide was used as the reductant. Moreover, the reduction was faster for surface-bound As(V) than for dissolved As(V), as evidenced by the appearance of As(III) at 45h and 75h, respectively. ATR-FTIR results provided direct evidence that the surface-bound As(V) was reduced to As(III) on TiO 2 surfaces in the presence of SRB. In addition, the As(V) desorption from nano-TiO 2 was promoted by SRB relative to abiotic sulfide, due to the competition between As(V) and bacterial phosphate groups for TiO 2 surface sites. This competition was corroborated by the ATR-FTIR analysis, which showed inner-sphere surface complex formation by bacterial phosphate groups on TiO 2 surfaces. The results from this study highlight the importance of indirect bacteria-mediated As(V) reduction and release in geochemical systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Sulfidogenic fluidized-bed treatment of metal-containing wastewater at low and high temperatures.

PubMed

Sahinkaya, Erkan; Ozkaya, Bestamin; Kaksonen, Anna H; Puhakka, Jaakko A

2007-04-15

The applicability of a fluidized-bed reactor (FBR)-based sulfate reducing bioprocess was investigated for the treatment of iron-containing (40-90 mg/L) acidic wastewater at low (8 degrees C) and high (65 degrees C) temperatures. The FBRs operated at low and high temperatures were inoculated with cultures of sulfate-reducing bacteria (SRB) originally enriched from arctic and hot mining environments, respectively. Ethanol was supplemented as carbon and electron source for SRB. At 8 degrees C, ethanol oxidation and sulfate reduction rates increased steadily and reached 320 and 265 mg/L.day, respectively, after 1 month of operation. After this point, the rates did not change significantly during 130 days of operation. Despite the complete ethanol oxidation and iron precipitation, the average sulfate reduction efficiency was 35 +/- 4% between days 30 and 130 due to the accumulation of acetate. At 65 degrees C, a rapid startup was observed as 99.9, 46, and 29% ethanol, sulfate, acetate removals, in respective order, were observed after 6 days. The feed pH was decreased gradually from its initial value of 6 to around 3.7 during 100 days of operation. The wastewater pH of 4.3-4.4 was neutralized by the alkalinity produced in acetate oxidation and the average effluent pH was 7.8 +/- 0.8. As in the low temperature FBR, acetate accumulated. Hence, the oxidation of acetate is the rate-limiting step in the sulfidogenic ethanol oxidation by thermophilic and psychrotrophic SRB. The sulfate reduction rate is three times and acetate oxidation rate is four times higher at 65 degrees C than at 8 degrees C. (c) 2006 Wiley Periodicals, Inc.

A Multimodel Assessment of the Influence of Regional Anthropogenic Emission Reductions on Aerosol Direct Radiative Forcing and the Role of Intercontinental Transport

NASA Technical Reports Server (NTRS)

Yu, Hongbin; Chin, Mian; West, Jason; Atherton, Cynthia S.; Bellouin, Nicolas; Bergmann, Dan; Bey, Isabelle; Bian, Huisheng; Diehl, Thomas; Forberth, Gerd;

Mineralogy and Microbial Diversity of the Microbialites in the Hypersaline Storr's Lake, the Bahamas

NASA Astrophysics Data System (ADS)

Paul, Varun G.; Wronkiewicz, David J.; Mormile, Melanie R.; Foster, Jamie S.

2016-04-01

Microbialites found in the low-light-intensity, hypersaline waters of Storr's Lake (SL), San Salvador Island, the Bahamas, were investigated with respect to their morphology, mineralogy, and microbial diversity. Previously described microbialite morphologies, as well as a newly identified "multi-cuspate" morphology, were observed at various depths. Electron microscopy analysis revealed the presence of angular, blocky, and needle-shaped crystals with mineralized cyanobacterial filaments and remains of exopolymeric substances. X-ray diffraction studies confirmed the presence of both Mg-calcite and aragonite in the plateau-mushroom and pinnacle mound microbialites, whereas only Mg-calcite was identified in the other microbialite morphotypes. A comprehensive molecular analysis using barcoded pyrosequencing of five different microbial mat communities identified at least 12 dominant bacterial phyla. Cyanobacteria were generally low in abundance and ranged from ˜0.01% in the deeper pinnacle mounds to ˜3.2% in the shallow calcareous knobs. Other photosynthetic members included green nonsulfur bacteria of the phylum Chloroflexi and purple sulfur bacteria of the class Gammaproteobacteria. All mat types contained significant amounts of sulfate-reducing and dehalogenating bacteria. The low light intensity reaching the deeper microbialites, the lack of dominant cyanobacteria, and the abundance of sulfate reducers and Chloroflexi collectively suggest that sulfate reduction and anoxygenic photosynthetic processes influence the carbonate biomineralization process in these systems.

Isolation and Characterization of Microbes Mediating Thermodynamically Favorable Coupling of Anaerobic Oxidation of Methane and Metal Reduction

NASA Astrophysics Data System (ADS)

Glass, J. B.; Reed, B. C.; Sarode, N. D.; Kretz, C. B.; Bray, M. S.; DiChristina, T. J.; Stewart, F. J.; Fowle, D. A.; Crowe, S.

2014-12-01

Methane is the third most reduced environmentally relevant electron donor for microbial metabolisms after organic carbon and hydrogen. In anoxic ecosystems, the major sink for methane is anaerobic oxidation of methane (AOM) mediated by syntrophic microbial consortia that couple AOM to reduction of an oxidized electron acceptor to yield free energy. In marine sediments, AOM is generally coupled to reduction of sulfate despite an extremely small amount of free energy yield because sulfate is the most abundant electron acceptor in seawater. While AOM coupled to Fe(III) and Mn(IV) reduction (Fe- and Mn-AOM) is 10-30x more thermodynamically favorable than sulfate-AOM, and geochemical data suggests that it occurs in diverse environments, the microorganisms mediating Fe- and Mn-AOM remain unknown. Lake Matano, Indonesia is an ideal ecosystem to enrich for Fe- and Mn-AOM microbes because its anoxic ferruginous deep waters and sediments contain abundant Fe(III), Mn(IV) and methane, and extremely low sulfate and nitrate. Our research aims to isolate and characterize the microbes mediating Fe- and Mn-AOM from three layers of Lake Matano sediments through serial enrichment cultures in minimal media lacking nitrate and sulfate. 16S rRNA amplicon sequencing of sediment inoculum revealed the presence of the Fe(III)-reducing bacterium Geobacter (5-10% total microbial community in shallow sediment and 35-60% in deeper sediment) as well as 1-2% Euryarchaeota implicated in methane cycling, including ANME-1 and 2d and Methanosarcinales. After 90 days of primary enrichment, all three sediment layers showed high levels of Fe(III) reduction (60-90 μM Fe(II) d-1) in the presence of methane compared to no methane and heat-killed controls. Treatments with added Fe(III) as goethite contained higher abundances of Geobacter than the inoculum (60-80% in all layers), suggesting that Geobacter may be mediating Fe(III) reduction in these enrichments. Quantification of AOM rates is underway, and will be used to estimate the plausibility of metal-AOM as a thermodynamically favorable methane sink in anoxic ecosystems of both the modern and ancient Earth.

Radiorespirometric assays for the detection of biogenic sulfides from sulfate-reducing bacteria.

PubMed

de Queiroz, J C; de Melo Ferreira, A C; da Costa, A C A

2013-04-01

The detection of trace concentrations of biogenic sulfides can be carried out through radiorespirometric assays. The objective of this work was to improve the methodology for detection of H2 S in trace concentrations, to correlate with sulfate-reducing bacterial activity. Serial dilutions of synthetic sea water with a pure culture of Desulfovibrio alaskensis, a mixed anaerobic microbial culture and a natural saline sample from a petroleum offshore platform indicated that dilutions were followed, accordingly, by sulfate reduction. Tests performed indicated that increasing the time of incubation of a mixed anaerobic microbial culture contributed to an increase in the sulfate reduction rates, as well as the amount of carbon source and inoculum. The technique here developed proved to be a rapid test for the detection of biogenic sulfides, particularly those associated with corrosion products, being an useful tool for monitoring and controlling oil/water storage tanks, petroleum continental platforms and several types of reservoirs. © 2013 The Society for Applied Microbiology.

Reduction of carcinogenic 4(5)-methylimidazole in a caramel model system: influence of food additives.

PubMed

Seo, Seulgi; Ka, Mi-Hyun; Lee, Kwang-Geun

2014-07-09

The effect of various food additives on the formation of carcinogenic 4(5)-methylimidazole (4-MI) in a caramel model system was investigated. The relationship between the levels of 4-MI and various pyrazines was studied. When glucose and ammonium hydroxide were heated, the amount of 4-MI was 556 ± 1.3 μg/mL, which increased to 583 ± 2.6 μg/mL by the addition of 0.1 M of sodium sulfite. When various food additives, such as 0.1 M of iron sulfate, magnesium sulfate, zinc sulfate, tryptophan, and cysteine were added, the amount of 4-MI was reduced to 110 ± 0.7, 483 ± 2.0, 460 ± 2.0, 409 ± 4.4, and 397 ± 1.7 μg/mL, respectively. The greatest reduction, 80%, occurred with the addition of iron sulfate. Among the 12 pyrazines, 2-ethyl-6-methylpyrazine with 4-MI showed the highest correlation (r = -0.8239).

Multiple stable oxygen isotopic studies of atmospheric sulfate: A new quantitative way to understand sulfate formation processes in the atmosphere

NASA Astrophysics Data System (ADS)

Lee, Charles Chi-Woo

2000-11-01

Sulfate is an important trace species in the Earth's atmosphere because of its roles in numerous atmospheric processes. In addition to its inherent light-scattering properties, sulfate can serve as cloud condensation nucleus (CCN), affecting cloud formation as well as microphysical properties of clouds. Consequently, atmospheric sulfate species influence the global radiative energy balance. Sulfate is known to increase acidity of rainwater with negative consequences in both natural and urban environments. In addition, aerosol sulfate (<=2.5 μm) is respirable and poses a threat to human health as a potential carrier of toxic pollutants through the respiratory tract. Despite intense investigative effort, uncertainty regarding the relative significance of gas and aqueous phase oxidation pathways still remains. Acquisition of such information is important because the lifetime and transport of S(IV) species and sulfate aerosols are influenced by the oxidative pathways. In addition, sulfate formation processes affect the aerosol size distribution, which ultimately influences radiative properties of atmospheric aerosols. Therefore, the budgetary information of the sulfur cycle, as well as the radiative effects of sulfate on global climate variation, can be attained from better quantitative understanding of in situ sulfate formation processes in the atmosphere. Multiple stable oxygen isotopic studies of atmospheric sulfate are presented as a new tool to better comprehend the atmospheric sulfate formation processes. Coupled with isotopic studies, 35S radioactivity measurements have been utilized to assess contribution of sulfate from high altitude air masses. Atmospheric sulfate (aerosols and rainwater) samples have been collected from diverse environments. Laboratory experiments of gas and aqueous phase S(IV) oxidation by various oxidants, as well as biomass burning experiments, have also been conducted. The main isotopic results from these studies are as follows: (1)Atmospheric (aerosol and rainwater) sulfate has a mass independent oxygen isotopic composition; (2)Aqueous phase S(IV) oxidation by atmospheric ozone and hydrogen peroxide are the source of the mass independent anomaly in atmospheric sulfate; (3)The mass independent oxygen isotopic anomaly appears to enhance with increasing altitude, suggesting a stratospheric contribution; (4)Primary sulfate from biomass burning has a mass dependent oxygen isotopic composition.

Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

USGS Publications Warehouse

Johnson, C.A.; Emsbo, P.; Poole, F.G.; Rye, R.O.

2009-01-01

Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a ??34S versus ??18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The ??34S versus ??18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

Detection and characterization of a dehalogenating microorganism by terminal restriction fragment length polymorphism fingerprinting of 16S rRNA in a sulfidogenic, 2-bromophenol-utilizing enrichment.

PubMed

Fennell, Donna E; Rhee, Sung-Keun; Ahn, Young-Beom; Häggblom, Max M; Kerkhof, Lee J

2004-02-01

Terminal restriction fragment length polymorphism analysis of reverse-transcribed 16S rRNA during periods of community flux was used as a tool to delineate the roles of the members of a 2-bromophenol-degrading, sulfate-reducing consortium. Starved, washed cultures were amended with 2-bromophenol plus sulfate, 2-bromophenol plus hydrogen, phenol plus sulfate, or phenol with no electron acceptor and were monitored for substrate use. In the presence of sulfate, 2-bromophenol and phenol were completely degraded. In the absence of sulfate, 2-bromophenol was dehalogenated and phenol accumulated. Direct terminal restriction fragment length polymorphism fingerprinting of the 16S rRNA in the various subcultures indicated that phylotype 2BP-48 (a Desulfovibrio-like sequence) was responsible for the dehalogenation of 2-bromophenol. A stable coculture was established which contained predominantly 2BP-48 and a second Desulfovibrio-like bacterium (designated BP212 based on terminal restriction fragment length polymorphism fingerprinting) that was capable of dehalogenating 2-bromophenol to phenol. Strain 2BP-48 in the coculture could couple reductive dehalogenation to growth with 2-bromophenol, 2,6-dibromophenol, or 2-iodophenol and lactate or formate as the electron donor. In addition to halophenols, strain 2BP-48 appears to use sulfate, sulfite, and thiosulfate as electron acceptors and is capable of simultaneous sulfidogenesis and reductive dehalogenation in the presence of sulfate.

Detection and Characterization of a Dehalogenating Microorganism by Terminal Restriction Fragment Length Polymorphism Fingerprinting of 16S rRNA in a Sulfidogenic, 2-Bromophenol-Utilizing Enrichment

PubMed Central

Fennell, Donna E.; Rhee, Sung-Keun; Ahn, Young-Beom; Häggblom, Max M.; Kerkhof, Lee J.

2004-01-01

Terminal restriction fragment length polymorphism analysis of reverse-transcribed 16S rRNA during periods of community flux was used as a tool to delineate the roles of the members of a 2-bromophenol-degrading, sulfate-reducing consortium. Starved, washed cultures were amended with 2-bromophenol plus sulfate, 2-bromophenol plus hydrogen, phenol plus sulfate, or phenol with no electron acceptor and were monitored for substrate use. In the presence of sulfate, 2-bromophenol and phenol were completely degraded. In the absence of sulfate, 2-bromophenol was dehalogenated and phenol accumulated. Direct terminal restriction fragment length polymorphism fingerprinting of the 16S rRNA in the various subcultures indicated that phylotype 2BP-48 (a Desulfovibrio-like sequence) was responsible for the dehalogenation of 2-bromophenol. A stable coculture was established which contained predominantly 2BP-48 and a second Desulfovibrio-like bacterium (designated BP212 based on terminal restriction fragment length polymorphism fingerprinting) that was capable of dehalogenating 2-bromophenol to phenol. Strain 2BP-48 in the coculture could couple reductive dehalogenation to growth with 2-bromophenol, 2,6-dibromophenol, or 2-iodophenol and lactate or formate as the electron donor. In addition to halophenols, strain 2BP-48 appears to use sulfate, sulfite, and thiosulfate as electron acceptors and is capable of simultaneous sulfidogenesis and reductive dehalogenation in the presence of sulfate. PMID:14766602

Determination of dominant biogeochemical processes in a contaminated aquifer-wetland system using multivariate statistical analysis

USGS Publications Warehouse

Baez-Cazull, S. E.; McGuire, J.T.; Cozzarelli, I.M.; Voytek, M.A.

2008-01-01

Determining the processes governing aqueous biogeochemistry in a wetland hydrologically linked to an underlying contaminated aquifer is challenging due to the complex exchange between the systems and their distinct responses to changes in precipitation, recharge, and biological activities. To evaluate temporal and spatial processes in the wetland-aquifer system, water samples were collected using cm-scale multichambered passive diffusion samplers (peepers) to span the wetland-aquifer interface over a period of 3 yr. Samples were analyzed for major cations and anions, methane, and a suite of organic acids resulting in a large dataset of over 8000 points, which was evaluated using multivariate statistics. Principal component analysis (PCA) was chosen with the purpose of exploring the sources of variation in the dataset to expose related variables and provide insight into the biogeochemical processes that control the water chemistry of the system. Factor scores computed from PCA were mapped by date and depth. Patterns observed suggest that (i) fermentation is the process controlling the greatest variability in the dataset and it peaks in May; (ii) iron and sulfate reduction were the dominant terminal electron-accepting processes in the system and were associated with fermentation but had more complex seasonal variability than fermentation; (iii) methanogenesis was also important and associated with bacterial utilization of minerals as a source of electron acceptors (e.g., barite BaSO4); and (iv) seasonal hydrological patterns (wet and dry periods) control the availability of electron acceptors through the reoxidation of reduced iron-sulfur species enhancing iron and sulfate reduction. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Case Study: Microbial Ecology and Forensics of Chinese Drywall-Elemental Sulfur Disproportionation as Primary Generator of Hydrogen Sulfide.

PubMed

Tomei Torres, Francisco A

2017-06-21

Drywall manufactured in China released foul odors attributed to volatile sulfur compounds. These included hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Given that calcium sulfate is the main component of drywall, one would suspect bacterial reduction of sulfate to sulfide as the primary culprit. However, when the forensics, i.e., the microbial and chemical signatures left in the drywall, are studied, the evidence suggests that, rather than dissimilatory sulfate reduction, disproportionation of elemental sulfur to hydrogen sulfide and sulfate was actually the primary cause of the malodors. Forensic evidence suggests that the transformation of elemental sulfur went through several abiological and microbial stages: (1) partial volatilization of elemental sulfur during the manufacture of plaster of Paris, (2) partial abiotic disproportionation of elemental sulfur to sulfide and thiosulfate during the manufacture of drywall, (3) microbial disproportionation of elemental sulfur to sulfide and sulfate resulting in neutralization of all alkalinity, and acidification below pH 4, (4) acidophilic microbial disproportionation of elemental sulfur to sulfide and sulfuric acid, and (5) hydrogen sulfide volatilization, coating of copper fixtures resulting in corrosion, and oxidation to sulfur dioxide.

Monofluorophosphate is a selective inhibitor of respiratory sulfate-reducing microorganisms.

PubMed

Carlson, Hans K; Stoeva, Magdalena K; Justice, Nicholas B; Sczesnak, Andrew; Mullan, Mark R; Mosqueda, Lorraine A; Kuehl, Jennifer V; Deutschbauer, Adam M; Arkin, Adam P; Coates, John D

2015-03-17

Despite the environmental and economic cost of microbial sulfidogenesis in industrial operations, few compounds are known as selective inhibitors of respiratory sulfate reducing microorganisms (SRM), and no study has systematically and quantitatively evaluated the selectivity and potency of SRM inhibitors. Using general, high-throughput assays to quantitatively evaluate inhibitor potency and selectivity in a model sulfate-reducing microbial ecosystem as well as inhibitor specificity for the sulfate reduction pathway in a model SRM, we screened a panel of inorganic oxyanions. We identified several SRM selective inhibitors including selenate, selenite, tellurate, tellurite, nitrate, nitrite, perchlorate, chlorate, monofluorophosphate, vanadate, molydate, and tungstate. Monofluorophosphate (MFP) was not known previously as a selective SRM inhibitor, but has promising characteristics including low toxicity to eukaryotic organisms, high stability at circumneutral pH, utility as an abiotic corrosion inhibitor, and low cost. MFP remains a potent inhibitor of SRM growing by fermentation, and MFP is tolerated by nitrate and perchlorate reducing microorganisms. For SRM inhibition, MFP is synergistic with nitrite and chlorite, and could enhance the efficacy of nitrate or perchlorate treatments. Finally, MFP inhibition is multifaceted. Both inhibition of the central sulfate reduction pathway and release of cytoplasmic fluoride ion are implicated in the mechanism of MFP toxicity.

Determination of Natural 14C Abundances in Dissolved Organic Carbon in Organic-Rich Marine Sediment Porewaters by Thermal Sulfate Reduction

NASA Astrophysics Data System (ADS)

Johnson, L.; Komada, T.

2010-12-01

The abundances of natural 14C in dissolved organic carbon (DOC) in the marine environment hold clues regarding the processes that influence the biogeochemical cycling of this large carbon reservoir. At present, UV irradiation is the widely accepted method for oxidizing seawater DOC for determination of their 14C abundances. This technique yields precise and accurate values with low blanks, but it requires a dedicated vacuum line, and hence can be difficult to implement. As an alternative technique that can be conducted on a standard preparatory vacuum line, we modified and tested a thermal sulfate reduction method that was previously developed to determine δ13C values of marine DOC (Fry B. et al., 1996. Analysis of marine DOC using a dry combustion method. Mar. Chem., 54: 191-201.) to determine the 14C abundances of DOC in marine sediment porewaters. In this method, the sample is dried in a 100 ml round-bottom Pyrex flask in the presence of excess oxidant (K2SO4) and acid (H3PO4), and combusted at 550 deg.C. The combustion products are cryogenically processed to collect and quantify CO2 using standard procedures. Materials we have oxidized to date range from 6-24 ml in volume, and 95-1500 μgC in size. The oxidation efficiency of this method was tested by processing known amounts of reagent-grade dextrose and sucrose (as examples of labile organic matter), tannic acid and humic acid (as examples of complex natural organic matter), and porewater DOC extracted from organic-rich nearshore sediments. The carbon yields for all of these materials averaged 99±4% (n=18). The 14C abundances of standard materials IAEA C-6 and IAEA C-5 processed by this method using >1mgC aliquots were within error of certified values. The size and the isotopic value of the blank were determined by a standard dilution technique using IAEA C-6 and IAEA C-5 that ranged in size from 150 to 1500 μgC (n=4 and 2, respectively). This yielded a blank size of 6.7±0.7 μgC, and a blank isotopic value of 0.54±0.05 fMC. The size of the blank agreed well with that determined directly by processing variable volumes of UV-irradiated deionized water (5.6±0.7 μgC, n=9). The size of the blank amounts to <~5% of the size of porewater DOC samples that are typically recovered from organic-rich sediment cores (~100-500 μgC). The fMC value of the blank suggests that there may be multiple sources of extraneous carbon that range in 14C abundance. In order to assess the fidelity of 14C abundances in natural porewater DOC oxidized by thermal sulfate reduction, we oxidized porewater DOC samples collected from the central floor of the Santa Monica Basin, California Borderland, using both this method and UV irradiation (the latter carried out at the Druffel laboratory, University of California Irvine). The fMC values obtained by the two methods agreed within error. Carbon yields from the two methods also agreed closely. These findings show that thermal sulfate reduction may be a promising method to oxidize small, concentrated marine DOC samples for 14C analysis.

Transport of steroid 3-sulfates and steroid 17-sulfates by the sodium-dependent organic anion transporter SOAT (SLC10A6).

PubMed

Grosser, Gary; Bennien, Josefine; Sánchez-Guijo, Alberto; Bakhaus, Katharina; Döring, Barbara; Hartmann, Michaela; Wudy, Stefan A; Geyer, Joachim

2018-05-01

The sodium-dependent organic anion transporter SOAT/Soat shows highly specific transport activity for sulfated steroids. SOAT substrates identified so far include dehydroepiandrosterone sulfate, 16α-hydroxydehydroepiandrosterone sulfate, estrone-3-sulfate, pregnenolone sulfate, 17β-estradiol-3-sulfate, and androstenediol sulfate. Apart from these compounds, many other sulfated steroids occur in mammals. Therefore, we aimed to expand the substrate spectrum of SOAT and analyzed the SOAT-mediated transport of eight different sulfated steroids by combining in vitro transport experiments in SOAT-transfected HEK293 cells with LC-MS/MS analytics of cell lysates. In addition, we aimed to better understand the structural requirements for SOAT substrates and so selected structural pairs varying only at specific positions: 3α/3β-sulfate, 17α/17β-sulfate, mono-sulfate/di-sulfate, and 17α-hydroxylation. We found significant and sodium-dependent SOAT-mediated transport of 17α-hydroxypregnenolone sulfate, 17β-estradiol-17-sulfate, androsterone sulfate, epiandrosterone sulfate, testosterone sulfate, epitestosterone sulfate, and 5α-dihydrotestosterone sulfate. However, 17β-estradiol-3,17-disulfate was not transported by SOAT. SOAT substrates from the group of sulfated steroids are characterized by a planar and lipophilic steroid backbone in trans-trans-trans conformation of the rings and a negatively charged mono-sulfate group at positions 3' or 17' with flexibility for α- or β- orientation. Furthermore, 5α-reduction, 16α-hydroxylation, and 17α-hydroxylation are acceptable for SOAT substrate recognition, whereas addition of a second negatively charged sulfate group seems to abolish substrate binding to SOAT, and so 17β-estradiol-3,17-disulfate is not transported by SOAT. Copyright © 2017 Elsevier Ltd. All rights reserved.

The First Genomic and Proteomic Characterization of a Deep-Sea Sulfate Reducer: Insights into the Piezophilic Lifestyle of Desulfovibrio piezophilus

PubMed Central

Pradel, Nathalie; Ji, Boyang; Gimenez, Grégory; Talla, Emmanuel; Lenoble, Patricia; Garel, Marc; Tamburini, Christian; Fourquet, Patrick; Lebrun, Régine; Bertin, Philippe; Denis, Yann; Pophillat, Matthieu; Barbe, Valérie; Ollivier, Bernard; Dolla, Alain

2013-01-01

Desulfovibrio piezophilus strain C1TLV30T is a piezophilic anaerobe that was isolated from wood falls in the Mediterranean deep-sea. D. piezophilus represents a unique model for studying the adaptation of sulfate-reducing bacteria to hydrostatic pressure. Here, we report the 3.6 Mbp genome sequence of this piezophilic bacterium. An analysis of the genome revealed the presence of seven genomic islands as well as gene clusters that are most likely linked to life at a high hydrostatic pressure. Comparative genomics and differential proteomics identified the transport of solutes and amino acids as well as amino acid metabolism as major cellular processes for the adaptation of this bacterium to hydrostatic pressure. In addition, the proteome profiles showed that the abundance of key enzymes that are involved in sulfate reduction was dependent on hydrostatic pressure. A comparative analysis of orthologs from the non-piezophilic marine bacterium D. salexigens and D. piezophilus identified aspartic acid, glutamic acid, lysine, asparagine, serine and tyrosine as the amino acids preferentially replaced by arginine, histidine, alanine and threonine in the piezophilic strain. This work reveals the adaptation strategies developed by a sulfate reducer to a deep-sea lifestyle. PMID:23383081

Sulfur in the South Florida ecosystem: Distribution, sources, biogeochemistry, impacts, and management for restoration

USGS Publications Warehouse

Orem, W.; Gilmour, C.; Axelrad, D.; Krabbenhoft, D.; Scheidt, D.; Kalla, P.; McCormick, P.; Gabriel, M.; Aiken, G.

2011-01-01

Sulfur is broadly recognized as a water quality issue of significance for the freshwater Florida Everglades. Roughly 60% of the remnant Everglades has surface water sulfate concentrations above 1 mg l-1, a restoration performance measure based on present sulfate levels in unenriched areas. Highly enriched marshes in the northern Everglades have average sulfate levels of 60 mg l-1. Sulfate loading to the Everglades is principally a result of land and water management in South Florida. The highest concentrations of sulfate (average 60-70 mg l-1) in the ecosystem are in canal water in the Everglades Agricultural Area (EAA). Potential sulfur sourcesin the watershed are many, but geochemical data and a preliminary sulfur mass balance for the EAA are consistent with sulfur presently used in agricultural, and sulfur released by oxidation of organic EAA soils (including legacy agricultural applications and natural sulfur) as the primary sources of sulfate enrichment in the EAA canals. Sulfate loading to the Everglades increases microbial sulfate reduction in soils, leading to more reducing conditions, greater cycling of nutrients in soils, production of toxic sulfide, and enhanced methylmercury (MeHg) production and bioaccumulation. Wetlands are zones of naturally high MeHg production, but the combination of high atmospheric mercury deposition rates in South Florida and elevated sulfate loading leads to increased MeHg production and MeHg risk to Everglades wildlife and human consumers. Sulfate from the EAA drainage canals penetrates deep into the Everglades Water Conservation Areas, and may extend into Everglades National Park. Present plans to restore sheet flow and to deliver more water to the Everglades may increase overall sulfur loads to the ecosystem, and move sulfate-enriched water further south. However, water management practices that minimize soil drying and rewetting cycles can mitigate sulfate release during soil oxidation. A comprehensive Everglades restoration strategy should include reduction of sulfur loads as a goal because of the many detrimental impacts of sulfate on the ecosystem. Monitoring data show that the ecosystem response to changes in sulfate levels is rapid, and strategies for reducing sulfate loading may be effective in the near term. A multifaceted approach employing best management practices for sulfur in agriculture, agricultural practices that minimize soil oxidation, and changes to stormwater treatment areas that increase sulfate retention could help achieve reduced sulfate loads to the Everglades, with resulting benefits. Copyright ?? 2011 Taylor & Francis Group, LLC.

Sulfate-reducing bacteria in rice field soil and on rice roots.

PubMed

Wind, T; Stubner, S; Conrad, R

1999-05-01

Rice plants that were grown in flooded rice soil microcosms were examined for their ability to exhibit sulfate reducing activity. Washed excised rice roots showed sulfate reduction potential when incubated in anaerobic medium indicating the presence of sulfate-reducing bacteria. Rice plants, that were incubated in a double-chamber (phylloshpere and rhizosphere separated), showed potential sulfate reduction rates in the anoxic rhizosphere compartment. These rates decreased when oxygen was allowed to penetrate through the aerenchyma system of the plants into the anoxic root compartment, indicating that sulfate reducers on the roots were partially inhibited by oxygen or that sulfate was regenerated by oxidation of reduced S-compounds. The potential activity of sulfate reducers on rice roots was consistent with MPN enumerations showing that H2-utilizing sulfate-reducing bacteria were present in high numbers on the rhizoplane (4.1 x 10(7) g-1 root fresh weight) and in the adjacent rhizosperic soil (2.5 x 10(7) g-1 soil dry weight). Acetate-oxidizing sulfate reducers, on the other hand, showed highest numbers in the unplanted bulk soil (1.9 x 10(6) g-1 soil dry weight). Two sulfate reducing bacteria were isolated from the highest dilutions of the MPN series and were characterized physiologically and phylogenetically. Strain F1-7b which was isolated from the rhizoplane with H2 as electron donor was related to subgroup II of the family Desulfovibrionaceae. Strain EZ-2C2, isolated from the rhizoplane on acetate, grouped together with Desulforhabdus sp. and Syntrophobacter wolinii. Other strains of sulfate-reducing bacteria originated from bulk soil of rice soil microcosms and were isolated using different electron donors. From these isolates, strains R-AcA1, R-IbutA1, R-PimA1 and R-AcetonA170 were Gram-positive bacteria which were affiliated with the genus Desulfotomaculum. The other isolates were members of subgroup II of the Desulfovibrionaceae (R-SucA1 and R-LacA1), were related to Desulforhabdus sp. (strain BKA11), Desulfobulbus (R-PropA1), or culstered between Desulfobotulus sapovorans and Desulfosarcina variabilis (R-ButA1 and R-CaprA1).

MOLECULAR PHYLOGENETIC AND BIOGEOCHEMICAL STUDIES OF SULFATE-REDUCING BACTERIA IN THE RHIZOSPHERE OF SPARTINA ALTERNIFLORA

EPA Science Inventory

The population composition and biogeochemistry of sulfate-reducing bacteria (SRB) in the rhizosphere of the marsh grass Spartina alterniflora was investigated over two growing seasons using molecular probing, enumerations of culturable SRB, and measurements of SO42- reduction rat...

CELLULAR DIFFERENTIATION AND THE AGING PROCESS IN CARTILAGINOUS TISSUES

PubMed Central

Shulman, Herbert J.; Meyer, Karl

1968-01-01

Primary cell cultures of differentiated chondrocytes were shown to produce chondroitin-4-sulfate as the predominant mucopolysaccharide, with suggestive evidence for the synthesis of keratan sulfate and possibly chondroitin-6-sulfate. Chicken embryonic cartilage was shown to be composed mainly of chondroitin-4-sulfate, with a small amount of chondroitin-6-sulfate, but essentially no keratan sulfate. These findings were compared to the data of others, and a hypothesis explaining the aging process in cartilage in terms of cellular differentiation was presented. PMID:5688079

Microbial Sulfate Reduction Enhances Arsenic Mobility Downstream of Zerovalent-Iron-Based Permeable Reactive Barrier.

PubMed

Kumar, Naresh; Couture, Raoul-Marie; Millot, Romain; Battaglia-Brunet, Fabienne; Rose, Jérôme

2016-07-19

We assessed the potential of zerovalent-iron- (Fe(0)) based permeable reactive barrier (PRB) systems for arsenic (As) remediation in the presence or absence of microbial sulfate reduction. We conducted long-term (200 day) flow-through column experiments to investigate the mechanisms of As transformation and mobility in aquifer sediment (in particular, the PRB downstream linkage). Changes in As speciation in the aqueous phase were monitored continuously. Speciation in the solid phase was determined at the end of the experiment using X-ray absorption near-edge structure (XANES) spectroscopy analysis. We identified thio-As species in solution and AsS in solid phase, which suggests that the As(V) was reduced to As(III) and precipitated as AsS under sulfate-reducing conditions and remained as As(V) under abiotic conditions, even with low redox potential and high Fe(II) content (4.5 mM). Our results suggest that the microbial sulfate reduction plays a key role in the mobilization of As from Fe-rich aquifer sediment under anoxic conditions. Furthermore, they illustrate that the upstream-downstream linkage of PRB affects the speciation and mobility of As in downstream aquifer sediment, where up to 47% of total As initially present in the sediment was leached out in the form of mobile thio-As species.

Microbial Energetics Beneath the Taylor Glacier, Antarctica

NASA Astrophysics Data System (ADS)

Mikucki, J. A.; Turchyn, A. V.; Farquhar, J.; Priscu, J. C.; Schrag, D. P.; Pearson, A.

2007-12-01

Subglacial microbiology is controlled by glacier hydrology, bedrock lithology, and the preglacial ecosystem. These factors can all affect metabolic function by influencing electron acceptor and donor availability in the subglacial setting leaving biogeochemical signatures that can be used to determine ecosystem processes. Blood Falls, an iron-rich, episodic subglacial outflow from the Taylor Glacier in the McMurdo Dry Valleys Antarctica provides an example of how microbial community structure and function can provide insight into subglacial hydrology. This subglacial outflow contains cryoconcentrated, Pliocene-age seawater salts that pooled in the upper Taylor Valley and was subsequently covered by the advance of the Taylor Glacier. Biogeochemical measurements, culture-based techniques, and genomic analysis were used to characterize microbes and chemistry associated with the subglacial outflow. The isotopic composition of important geochemical substrates (i.e., δ34Ssulfate, Δ33Ssulfate, δ18Osulfate, δ18Owater, Δ14SDIC) were also measured to provide more detail on subglacial microbial energetics. Typically, subglacial systems, when driven to anoxia by the hydrolysis of organic matter, will follow a continuum of redox chemistries utilizing electron acceptors with decreasing reduction potential (e.g., Fe (III), sulfate, CO2). Our data provide no evidence for sulfate reduction below the Taylor Glacier despite high dissolved organic carbon (450 μM C) and measurable metabolic activity. We contend that, in the case of the Taylor Glacier, the in situ bioenergetic reduction potential has been 'short-circuited' at Fe(III)-reduction and excludes sulfate reduction and methanogenesis. Given the length of time that this marine system has been isolated from phototrophic production (~2 Mya) the ability to degrade and consume increasingly recalcitrant organic carbon is likely an important component to the observed redox chemistry. Our work indicates that glacier hydrology imparts strong feedbacks on the availability of oxygen as an electron acceptor and may be a robust regulator of the in situ metabolism. This biogeochemical regulation in turn affects the chemical nature of subglacial efflux. Blood Falls demonstrates that measurements of geochemistry and microbial diversity can support models of subglacial hydrology.

Source Of Hydrogen Sulfide To Sulfidic Spring And Watershed Ecosystems In Northern Sierra De Chiapas, Mexico Based On Sulfur And Carbon Isotopes

NASA Astrophysics Data System (ADS)

Rosales Lagarde, L.; Boston, P. J.; Campbell, A.

2013-12-01

At least four watersheds in northern Sierra de Chiapas, Mexico are fed by conspicuous karst sulfide-rich springs. The toxic hydrogen sulfide (H2S) in these springs nurtures rich ecosystems including especially adapted microorganisms, invertebrates and fish. Sulfur and carbon isotopic analysis of various chemical species in the spring water are integrated within their hydrogeologic context to evaluate the hydrogen sulfide source. Constraining the H2S origin can also increase the understanding of this compound effect in the quality of the nearby hydrocarbon reservoirs, and the extent to which its oxidation to sulfuric acid increases carbonate dissolution and steel corrosion in surface structures. The SO42-/H2S ratio in the spring water varies from 70,000 to 2 meq/L thus sulfate is the dominant species in the groundwater system. This sulfate is mainly produced from anhydrite dissolution based on its isotopic signature. The Δ SO42--H2S range of 16 spring water samples (30-50 ‰) is similar to the values determined by Goldhaber & Kaplan (1975) and Canfield (2001) for low rates of bacterial sulfate reduction suggesting that this is the most important mechanism producing H2S. Although the carbon isotopes do not constrain the nature of the organic matter participating in this reaction, this material likely comes from depth, perhaps as hydrocarbons, due to the apparent stability of the system. The organic matter availability and reactivity probably control the progress of sulfate reduction. The subsurface environments identified in the area also have different sulfur isotopic values. The heavier residual sulfate isotopic value in the Northern brackish springs (δ34S SO42- ≥ 18 ‰) compared to the Southern springs (δ34S SO42- ~18 ‰) suggests sulfate reduction is particularly enhanced in the former, probably by contribution of organic matter associated with oil produced water. In comparison, the composition of the Southern aquifer is mainly influenced by halite dissolution. Fresh water from the Local environment percolates into the Northern and the Southern environments. Mixing between these three aquifers may enhance bacterial sulfate reduction, thus increasing the H2S concentration in the sulfidic springs. The integration of the geochemical attributes and the aquatic communities at each watershed will produce a more comprehensive view of these spring ecosystems and their temporal and spatial evolution.

Evidence for Proteomic and Metabolic Adaptations Associated with Alterations of Seed Yield and Quality in Sulfur-limited Brassica napus L*

PubMed Central

D'Hooghe, Philippe; Dubousset, Lucie; Gallardo, Karine; Kopriva, Stanislav; Avice, Jean-Christophe; Trouverie, Jacques

2014-01-01

In Brassica napus, seed yield and quality are related to sulfate availability, but the seed metabolic changes in response to sulfate limitation remain largely unknown. To address this question, proteomics and biochemical studies were carried out on mature seeds obtained from plants grown under low sulfate applied at the bolting (LS32), early flowering (LS53), or start of pod filling (LS70) stage. The protein quality of all low-sulfate seeds was reduced and associated with a reduction of S-rich seed storage protein accumulation (as Cruciferin Cru4) and an increase of S-poor seed storage protein (as Cruciferin BnC1). This compensation allowed the protein content to be maintained in LS70 and LS53 seeds but was not sufficient to maintain the protein content in LS32 seeds. The lipid content and quality of LS53 and LS32 seeds were also affected, and these effects were primarily associated with a reduction of C18-derivative accumulation. Proteomics changes related to lipid storage, carbohydrate metabolism, and energy (reduction of caleosins, phosphoglycerate kinase, malate synthase, ATP-synthase β-subunit, and thiazole biosynthetic enzyme THI1 and accumulation of β-glucosidase and citrate synthase) provide insights into processes that may contribute to decreased oil content and altered lipid composition (in favor of long-chain fatty acids in LS53 and LS32 seeds). These data indicate that metabolic changes associated with S limitation responses affect seed storage protein composition and lipid quality. Proteins involved in plant stress response, such as dehydroascorbate reductase and Cu/Zn-superoxide dismutase, were also accumulated in LS53 and LS32 seeds, and this might be a consequence of reduced glutathione content under low S availability. LS32 treatment also resulted in (i) reduced germination vigor, as evidenced by lower germination indexes, (ii) reduced seed germination capacity, related to a lower seed viability, and (iii) a strong decrease of glyoxysomal malate synthase, which is essential for the use of fatty acids during seedling establishment. PMID:24554741

Experimental investigation on thermochemical sulfate reduction in the presence of 1-pentanethiol at 200 and 250 °C: Implications for in situ TSR processes occurring in some MVT deposits

USGS Publications Warehouse

Yuan, Shunda; Ellis, Geoffrey S.; Chou, I-Ming; Burruss, Robert

2017-01-01

Organic sulfur compounds are ubiquitous in natural oil and gas fields and moderate-low temperature sulfide ore deposits. Previous studies have shown that organic sulfur compounds are important in enhancing the rates of thermochemical sulfate reduction (TSR) reactions, but the details of these reaction mechanisms remain unclear. In order to assess the extent of sulfate reduction in the presence of labile sulfur species at temperature conditions near to those where TSR occurs in nature, we conducted a series of experiments using the fused silica capillary capsule (FCSS) method. The tested systems containing labile sulfur species are MgSO4 + 1-pentanethiol (C5H11SH) + 1-octene (C8H16), MgSO4 + 1-octene (C8H16), MgSO4 + 1-pentanethiol (C5H11SH), 1-pentanethiol (C5H11SH)+H2O, and MgSO4 + 1-pentanethiol (C5H11SH) + ZnBr2 systems. Our results show that: (1) intermediate oxidized carbon species (ethanol and acetic acid) are formed during TSR simulation experiments when 1-pentanethiol is present; (2) in the presence of ZnBr2, 1-pentanethiol can be oxidized by sulfate to CO2 at 200 °C, which is within the temperature range observed in natural TSR; and (3) the precipitation of sulfide minerals may significantly promote the rate of TSR, indicating that the rates of in situ TSR reactions in ore deposits could be much faster than previously thought. This may be important for understanding the possibility of in situ TSR as a mechanism for the precipitation of metal sulfides in some ore deposits. These findings provide important experimental evidence for understanding the role of organic sulfur compounds in TSR reactions and the pathway of TSR reactions initiated by organic sulfur compounds under natural conditions.

Mercury methylation in Sphagnum moss mats and its association with sulfate-reducing bacteria in an acidic Adirondack forest lake wetland.

PubMed

Yu, Ri-Qing; Adatto, Isaac; Montesdeoca, Mario R; Driscoll, Charles T; Hines, Mark E; Barkay, Tamar

2010-12-01

Processes leading to the bioaccumulation of methylmercury (MeHg) in northern wetlands are largely unknown. We have studied various ecological niches within a remote, acidic forested lake ecosystem in the southwestern Adirondacks, NY, to discover that mats comprised of Sphagnum moss were a hot spot for mercury (Hg) and MeHg accumulation (190.5 and 18.6 ng g⁻¹ dw, respectively). Furthermore, significantly higher potential methylation rates were measured in Sphagnum mats as compared with other sites within Sunday Lake's ecosystem. Although MPN estimates showed a low biomass of sulfate-reducing bacteria (SRB), 2.8 × 10⁴ cells mL⁻¹ in mat samples, evidence consisting of (1) a twofold stimulation of potential methylation by the addition of sulfate, (2) a significant decrease in Hg methylation in the presence of the sulfate reduction inhibitor molybdate, and (3) presence of dsrAB-like genes in mat DNA extracts, suggested that SRB were involved in Hg methylation. Sequencing of dsrB genes indicated that novel SRB, incomplete oxidizers including Desulfobulbus spp. and Desulfovibrio spp., and syntrophs dominated the sulfate-reducing guild in the Sphagnum moss mat. Sphagnum, a bryophyte dominating boreal peatlands, and its associated microbial communities appear to play an important role in the production and accumulation of MeHg in high-latitude ecosystems. © 2010 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrash, Daniel A.; Lalonde, Stefan V.; González-Arismendi, Gabriela

The formation of dolomite in modern peritidal environments is linked to the degradation of buried microbial mats, with complexation of Ca and Mg by extracellular polymeric substances (EPSs) and alkalinity generation through organic carbon respiration facilitating the nucleation of dolomite precursors. In the past two decades, microbial sulfate reduction, methanogenesis, and methanotrophy have all been considered as potential drivers of the nucleation process, but it remains unclear why dolomite formation could not also occur in suboxic sediments where abundant alkalinity is produced by processes linked to Mn(IV) and/or Fe(III) reduction coupled with the diffusion and reoxidation of reduced sulfur species.more » Here we report the interstitial occurrence of spheroidal aggregates of nanometer-scale Ca-rich dolomite rhombohedra within suboxic sediments associated with remnant microbial mats that developed in the peritidal zone of the Archipelago Los Roques, Venezuela. Multiple analytical tools, including EPMA, ICP-MS, synchrotron-based XRF and XRD, and spatially resolved XANES microanalyses, show that the dolomite-cemented interval exhibits depleted bulk iron concentrations, but is interstitially enriched in Mn and elemental sulfur (S⁰). Manganese occurs in several oxidation states, indicating that the dolomite-cemented interval was the locus of complex biological redox transformations characterized by coupled Mn and S cycling. The tight correspondence between sedimentary Mn and MgCO₃ concentrations further hints at a direct role for Mn during dolomitization. While additional studies are required to confirm its relevance in natural settings, we propose a model by which coupled Mn–S redox cycling may promote alkalinity generation and thus dolomite formation in manner similar to, or even more efficiently, than bacterial sulfate reduction alone.« less

High-Quality Draft Genome Sequence of Desulfovibrio carbinoliphilus FW-101-2B, an Organic Acid-Oxidizing Sulfate-Reducing Bacterium Isolated from Uranium(VI)-Contaminated Groundwater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramsay, Bradley D.; Hwang, Chiachi; Woo, Hannah L.

2015-03-12

Desulfovibrio carbinoliphilus subsp. oakridgensis FW-101-2B is an anaerobic, organic acid/alcohol-oxidizing, sulfate-reducing δ-proteobacterium. FW-101-2B was isolated from contaminated groundwater at The Field Research Center at Oak Ridge National Lab after in situ stimulation for heavy metal-reducing conditions. The genome will help elucidate the metabolic potential of sulfate-reducing bacteria during uranium reduction.

Exploring Microbial Processes with Thermal-Hydrological Models of the Eastern Flank of the Juan de Fuca Ridge

NASA Astrophysics Data System (ADS)

Weathers, T. S.; Fisher, A. T.; Winslow, D. M.; Stauffer, P. H.; Gable, C. W.

2017-12-01

The flanks of mid-ocean ridges experience coupled flows of fluid, heat, and solutes that are critical for a wide range of global processes, including the cycling of carbon and nutrients, which supports a vast crustal biosphere. Only a few ridge-flank sites have been studied in detail; hydrogeologic conditions and processes in the volcanic crust are best understood on the eastern flank of the Juan de Fuca Ridge. This area has been extensively explored with decades of drilling, submersible, observatory, and survey expeditions and experiments, including the first hole-to-hole tracer injection experiment in the ocean crust. This study describes the development of reactive transport simulations for this ridge-flank setting using three-dimensional coupled (thermal-hydrological) models of crustal-scale circulation, beginning with the exploration of tracer transport. The prevailing flow direction is roughly south to north as a result of outcrop-to-outcrop flow, with a bulk flow rate in the range of meters/year. However, tracer was detected 500 m south ("upstream") from the injection borehole during the first year following injection. This may be explained by local mixing and/or formation fluid discharge from the southern borehole during and after injection. The constraints and parameters required to fit the observed tracer behavior can be used as a basis for modeling reactive transport processes such as nutrient delivery or microbial community evolution as a function of fluid flow. For example, the sulfate concentration in fluid samples from Baby Bare outcrop ( 8 km south of the tracer transport experiment) was 17.8 mmol/kg, whereas at Mama Bare outcrop ( 8 km to north of the tracer transport experiment) the sulfate concentration was 16.3 mmol/mg. By integrating laboratory-derived sulfate reduction rates from microbial samples originating from Juan de Fuca borehole observatories into reactive transport models, we can explore the range of microbial activity that supports the observed concentration gradients of sulfate and other solutes in the volcanic ocean crust.

Use of dissolved H2 concentrations to determine distribution of microbially catalyzed redox reactions in anoxic groundwater

USGS Publications Warehouse

Lovley, D.R.; Chapelle, F.H.; Woodward, J.C.

1994-01-01

The potential for using concentrations of dissolved H2 to determine the distribution of redox processes in anoxic groundwaters was evaluated. In pristine aquifers in which standard geochemical measurements indicated that Fe-(III) reduction, sulfate reduction, or methanogenesis was the terminal electron accepting process (TEAP), the H2 concentrations were similar to the H2 concentrations that have previously been reported for aquatic sediments with the same TEAPs. In two aquifers contaminated with petroleum products, it was impossible with standard geochemical analyses to determine which TEAPs predominated in specific locations. However, the TEAPs predicted from measurements of dissolved H2 were the same as those determined directly through measurements of microbial processes in incubated aquifer material. These results suggest that H2 concentrations may be a useful tool for analyzing the redox chemistry of nonequilibrium groundwaters.