Microbial Sulfate Reduction Potential in Coal-Bearing Sediments Down to ~2.5 km below the Seafloor off Shimokita Peninsula, Japan.

PubMed

Glombitza, Clemens; Adhikari, Rishi R; Riedinger, Natascha; Gilhooly, William P; Hinrichs, Kai-Uwe; Inagaki, Fumio

2016-01-01

Sulfate reduction is the predominant anaerobic microbial process of organic matter mineralization in marine sediments, with recent studies revealing that sulfate reduction not only occurs in sulfate-rich sediments, but even extends to deeper, methanogenic sediments at very low background concentrations of sulfate. Using samples retrieved off the Shimokita Peninsula, Japan, during the Integrated Ocean Drilling Program (IODP) Expedition 337, we measured potential sulfate reduction rates by slurry incubations with 35 S-labeled sulfate in deep methanogenic sediments between 1276.75 and 2456.75 meters below the seafloor. Potential sulfate reduction rates were generally extremely low (mostly below 0.1 pmol cm -3 d -1 ) but showed elevated values (up to 1.8 pmol cm -3 d -1 ) in a coal-bearing interval (Unit III). A measured increase in hydrogenase activity in the coal-bearing horizons coincided with this local increase in potential sulfate reduction rates. This paired enzymatic response suggests that hydrogen is a potentially important electron donor for sulfate reduction in the deep coalbed biosphere. By contrast, no stimulation of sulfate reduction rates was observed in treatments where methane was added as an electron donor. In the deep coalbeds, small amounts of sulfate might be provided by a cryptic sulfur cycle. The isotopically very heavy pyrites (δ 34 S = +43‰) found in this horizon is consistent with its formation via microbial sulfate reduction that has been continuously utilizing a small, increasingly 34 S-enriched sulfate reservoir over geologic time scales. Although our results do not represent in-situ activity, and the sulfate reducers might only have persisted in a dormant, spore-like state, our findings show that organisms capable of sulfate reduction have survived in deep methanogenic sediments over more than 20 Ma. This highlights the ability of sulfate-reducers to persist over geological timespans even in sulfate-depleted environments. Our study moreover represents the deepest evidence of a potential for sulfate reduction in marine sediments to date.

Lab-scale study on the application of In-Adit-Sulfate-Reducing System for AMD control.

PubMed

Ji, S W; Kim, S J

2008-12-30

In a study of the 29 operating passive systems for acid mine drainage (AMD) treatment, 19 systems showed various performance problems. Some systems showed very low efficiency even without visible leakage or overflow. Though systems show fairly good efficiency in metal removal (mainly iron) and pH control, sulfate removal rates were very low which indicates the possibility of very poor sulfate reductions by Sulfate Reducing Bacteria (SRB). As an alternative method, In-Adit-Sulfate-Reducing System (IASRS), the method of placing the SAPS inside the adit, to have temperature constant at about 15 degrees C, was suggested. Lab-scale model experiments of IASRS were carried out. The models 1 and 2 were run at 15 degrees C and 25 degrees C, respectively. The model 1 contained about a half of COD in the beginning of the operation than that of model 2. Metal removal ratios were higher than 90% in both systems. Both systems showed the sulfate removal ratios of 23% and 27%, respectively, which were still considerably low, even though higher than those of presently operating systems. However, since the synthetic AMD used was very low in pH (2.8) and very high in sulfate concentration, if some suggested modifications were applied to the standard design, it is presumed that the sulfate removal ratio would have increased.

Evaluation of using aluminum sulfate and water-soluble Moringa oleifera seed lectin to reduce turbidity and toxicity of polluted stream water.

PubMed

Freitas, José Henrique Edmilson Souza; de Santana, Keissy Vanderley; do Nascimento, Ana Cláudia Claudina; de Paiva, Sérgio Carvalho; de Moura, Maiara Celine; Coelho, Luana Cassandra Breitenbach Barroso; de Oliveira, Maria Betânia Melo; Paiva, Patrícia Maria Guedes; do Nascimento, Aline Elesbão; Napoleão, Thiago Henrique

2016-11-01

Aluminum salts are used as coagulants in water treatment; however, the exposure to residual aluminum has been associated with human brain lesions. The water-soluble Moringa oleifera lectin (WSMoL), which is extracted with distilled water and isolated by chitin chromatography, has coagulant activity and is able to reduce the concentration of metal ions in aqueous solutions. This study evaluated the potential of using aluminum sulfate and WSMoL to reduce the turbidity and toxicity of water from the Cavouco stream located in Recife, Pernambuco, Brazil. The water sample used (called P1) was collected from the stream source, which was found to be strongly polluted based on physicochemical and water quality analyses, as well as ecotoxicity assays with Artemia salina and seeds of Eruca sativa and Lactuca sativa. The assays combining WSMoL and aluminum sulfate were more efficient than those that used these agents separately. Furthermore, the greatest reduction in turbidity (96.8%) was obtained with the treatment using aluminum sulfate followed by WSMoL, compared to when they were applied simultaneously (91.3%). In addition, aluminum sulfate followed by WSMoL treatment resulted in residual aluminum concentration (0.3 mg/L) that was much lower than that recorded after the treatment using only the salt (35.5 mg/L). The ecotoxicity of P1 was also strongly reduced after the treatments. In summary, the combined use of aluminum sulfate and WSMoL was efficient in promoting a strong reduction of turbidity and ecotoxicity of a polluted water sample, without resulting in a high residual aluminum concentration at the conclusion of the treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Efficacy of Biostimulation for Uranium Sequestration: Coupled Effects Sediment/Groundwater Geochemistry and Microbiology

NASA Astrophysics Data System (ADS)

Xu, J.; Veeramani, H.; Qafoku, N. P.; Singh, G.; Pruden, A.; Kukkadapu, R. K.; Hochella, M. F., Jr.

2015-12-01

A systematic flow-through column study was conducted using sediments and groundwater from the subsurface at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, to better understand the efficacy of uranium removal from the groundwater with and without biostimulation in the form of acetate amendments. The interactive effects of acetate amendment, groundwater/sediment geochemistry, and intrinsic bacterial community composition were evaluated using four types of sediments, collected from different uranium-contaminated (D08, LQ107, CD) or non-contaminated (RABS) aquifers. Subtle variations in the sediments' geochemistry in terms of mineral compositions, particle sizes, redox conditions, and metal(loid) co-contaminants had a marked effect on the uranium removal efficiency, following a descending trend of D08 (~ 90 to 95%) >> RABS (~ 20 to 25) ≥ LQ107 (~ 15 to 20%) > CD (~ -10 to 0%). Overall, biostimulation of the sediments with acetate drove deeper anoxic conditions and observable shifts in bacterial population structures. The abundance of dissimilatory sulfate-reduction genes (i.e., drsA), markers of sulfate-reducing bacteria, were highest in the sediments that performed best in terms of uranium removal. By comparison, no obvious associations were found between the uranium removal efficiency and the abundance of typical iron-reducing microorganisms, e.g., Geobacter spp. In the sediments where bacterial biomass was relatively low and sulfate-reduction was not detected (i.e., CD), abiotic adsorption onto fine mineral surfaces such as phyllosilates likely played a dominant role in the attenuation of aqueous uranium. In these scenarios, however, acetate amendment induced significant remobilization of the sequestered uranium and other heavy metals (e.g., strontium), leading to zero or negative uranium removal efficiencies (i.e., CD). The results of this study suggest that reductive immobilization of uranium can be effectively achieved under predominantly sulfate-reducing conditions in sediment microenvironments when bioavailable iron (III) (oxyhydr)oxides are mostly depleted, and provide insight into the integrated roles of sediment geochemistry, mineralogy, and bacterial population dynamics.

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

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.

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.

Photocatalytic reduction of nitrate using titanium dioxide for regeneration of ion exchange brine

PubMed Central

Yang, Ting; Doudrick, Kyle; Westerhoff, Paul

2016-01-01

Nitrate is often removed from groundwater by ion exchange (IX) before its use as drinking water. Accumulation of nitrate in IX brine reduces the efficiency of IX regeneration and the useful life of the regeneration brine. For the first time, we present a strategy to photocatalytically reduce nitrate in IX brine, thereby extending the use of the brine. Titanium dioxide (Evonik P90), acting as photocatalyst, reduced nitrate effectively in both synthetic brines and sulfate-removed IX brine when formic acid (FA) was used as the hole scavenger (i.e., electron donor) and the initial FA to nitrate molar ratio (IFNR) was 5.6. Increasing the NaCl level in the synthetic brine slowed the nitrate reduction rate without affecting byproduct selectivity of ammonium and gaseous N species (e.g., N2, N2O). In a non-modified IX brine, nitrate removal was greatly inhibited owing to the presence of sulfate, which competed with nitrate for active surface sites on P90 and induced aggregation of P90 nanoparticles. After removing sulfate through barium sulfate precipitation, nitrate was effectively reduced; approximately 3.6 × 1024 photons were required to reduce each mole of nitrate to 83% N Gases and 17% NH4+. To make optimum use of FA and control the residual FA level in treated brine, the IFNR was varied. High IFNRs (e.g., 4, 5.6) were found to be more efficient for nitrate reduction but left higher residual FA in brine. IX column tests were performed to investigate the impact of residual FA for brine reuse. The residual FA in the brine did not significantly affect the nitrate removal capacity of IX resins, and formate contamination of treated water could be eliminated by rinsing with one bed volume of fresh brine. PMID:23276425

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.

Iron and manganese in anaerobic respiration: environmental significance, physiology, and regulation

NASA Technical Reports Server (NTRS)

Nealson, K. H.; Saffarini, D.

1994-01-01

Dissimilatory iron and/or manganese reduction is known to occur in several organisms, including anaerobic sulfur-reducing organisms such as Geobacter metallireducens or Desulfuromonas acetoxidans, and facultative aerobes such as Shewanella putrefaciens. These bacteria couple both carbon oxidation and growth to the reduction of these metals, and inhibitor and competition experiments suggest that Mn(IV) and Fe(III) are efficient electron acceptors similar to nitrate in redox abilities and capable of out-competing electron acceptors of lower potential, such as sulfate (sulfate reduction) or CO2 (methanogenesis). Field studies of iron and/or manganese reduction suggest that organisms with such metabolic abilities play important roles in coupling the oxidation of organic carbon to metal reduction under anaerobic conditions. Because both iron and manganese oxides are solids or colloids, they tend to settle downward in aquatic environments, providing a physical mechanism for the movement of oxidizing potential into anoxic zones. The resulting biogeochemical metal cycles have a strong impact on many other elements including carbon, sulfur, phosphorous, and trace metals.

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.

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.

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.

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.

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.

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.

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

Modeling hydrologic controls on sulfur processes in sulfate-impacted wetland and stream sediments

NASA Astrophysics Data System (ADS)

Ng, G.-H. C.; Yourd, A. R.; Johnson, N. W.; Myrbo, A. E.

2017-09-01

Recent studies show sulfur redox processes in terrestrial settings are more important than previously considered, but much remains uncertain about how these processes respond to dynamic hydrologic conditions in natural field settings. We used field observations from a sulfate-impacted wetland and stream in the mining region of Minnesota (USA) to calibrate a reactive transport model and evaluate sulfur and coupled geochemical processes under contrasting hydrogeochemical scenarios. Simulations of different hydrological conditions showed that flux and chemistry differences between surface water and deeper groundwater strongly control hyporheic zone geochemical profiles. However, model results for the stream channel versus wetlands indicate sediment organic carbon content to be the more important driver of sulfate reduction rates. A complex nonlinear relationship between sulfate reduction rates and geochemical conditions is apparent from the model's higher sensitivity to sulfate concentrations in settings with higher organic content. Across all scenarios, simulated e- balance results unexpectedly showed that sulfate reduction dominates iron reduction, which is contrary to the traditional thermodynamic ladder but corroborates recent experimental findings by Hansel et al. (2015) that "cryptic" sulfur cycling could drive sulfate reduction in preference over iron reduction. Following the thermodynamic ladder, our models shows that high surface water sulfate slows methanogenesis in shallow sediments, but field observations suggest that sulfate reduction may not entirely suppress methane. Overall, our results show that sulfate reduction may serve as a major component making up and influencing terrestrial redox processes, with dynamic hyporheic fluxes controlling sulfate concentrations and reaction rates, especially in high organic content settings.

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

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.

Changes in iron, sulfur, and arsenic speciation associated with bacterial sulfate reduction in ferrihydrite-rich systems.

PubMed

Saalfield, Samantha L; Bostick, Benjamin C

2009-12-01

Biologically mediated redox processes have been shown to affect the mobility of iron oxide-bound arsenic in reducing aquifers. This work investigates how dissimilatory sulfate reduction and secondary iron reduction affect sulfur, iron, and arsenic speciation. Incubation experiments were conducted with As(III/V)-bearing ferrihydrite in carbonate-buffered artificial groundwater enriched with lactate (10 mM) and sulfate (0.08-10 mM) and inoculated with Desulfovibrio vulgaris (ATCC 7757, formerly D. desulfuricans), which reduces sulfate but not iron or arsenic. Sulfidization of ferrihydrite led to formation of magnetite, elemental sulfur, and trace iron sulfides. Observed reaction rates imply that the majority of sulfide is recycled to sulfate, promoting microbial sulfate reduction in low-sulfate systems. Despite dramatic changes in Fe and S speciation, and minimal formation of Fe or As sulfides, most As remained in the solid phase. Arsenic was not solubilized in As(V)-loaded incubations, which experienced slow As reduction by sulfide, whereas As(III)-loaded incubations showed limited and transient As release associated with iron remineralization. This suggests that As(III) production is critical to As release under reducing conditions, with sulfate reduction alone unlikely to release As. These data also suggest that bacterial reduction of As(V) is necessary for As sequestration in sulfides, even where sulfate reduction is active.

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.

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.

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.

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.

Effects of imposed salinity gradients on dissimilatory arsenate reduction, sulfate reduction, and other microbial processes in sediments from two California soda lakes

USGS Publications Warehouse

Kulp, T.R.; Han, S.; Saltikov, C.W.; Lanoil, B.D.; Zargar, K.; Oremland, R.S.

2007-01-01

Salinity effects on microbial community structure and on potential rates of arsenate reduction, arsenite oxidation, sulfate reduction, denitrification, and methanogenesis were examined in sediment slurries from two California soda lakes. We conducted experiments with Mono Lake and Searles Lake sediments over a wide range of salt concentrations (25 to 346 g liter-1). With the exception of sulfate reduction, rates of all processes demonstrated an inverse relationship to total salinity. However, each of these processes persisted at low but detectable rates at salt saturation. Denaturing gradient gel electrophoresis analysis of partial 16S rRNA genes amplified from As(V) reduction slurries revealed that distinct microbial populations grew at low (25 to 50 g liter-1), intermediate (100 to 200 g liter-1), and high (>300 g liter-1) salinity. At intermediate and high salinities, a close relative of a cultivated As-respiring halophile was present. These results suggest that organisms adapted to more dilute conditions can remain viable at high salinity and rapidly repopulate the lake during periods of rising lake level. In contrast to As reduction, sulfate reduction in Mono Lake slurries was undetectable at salt saturation. Furthermore, sulfate reduction was excluded from Searles Lake sediments at any salinity despite the presence of abundant sulfate. Sulfate reduction occurred in Searles Lake sediment slurries only following inoculation with Mono Lake sediment, indicating the absence of sulfate-reducing flora. Experiments with borate-amended Mono Lake slurries suggest that the notably high (0.46 molal) concentration of borate in the Searles Lake brine was responsible for the exclusion of sulfate reducers from that ecosystem. Copyright ?? 2007, American Society for Microbiology. All Rights Reserved.

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.

Impact of particulate air pollution on quality-adjusted life expectancy in Canada.

PubMed

Coyle, Douglas; Stieb, Dave; Burnett, Richard T; DeCivita, Paul; Krewski, Daniel; Chen, Yue; Thun, Michael J

Air pollution and premature death are important public health concerns. Analyses have repeatedly demonstrated that airborne particles are associated with increased mortality and estimates have been used to forecast the impact on life expectancy. In this analysis, we draw upon data from the American Cancer Society (ACS) cohort and literature on utility-based measures of quality of life in relation to health status to more fully quantify the effects of air pollution on mortality in terms of quality-adjusted life expectancy. The analysis was conducted within a decision analytic model using Monte Carlo simulation techniques. Outcomes were estimated based on projections of the Canadian population. A one-unit reduction in sulfate air pollution would yield a mean annual increase in Quality-Adjusted Life Years (QALYs) of 20,960, with gains being greater for individuals with lower educational status and for males compared to females. This suggests that the impact of reductions in sulfate air pollution on quality-adjusted life expectancy is substantial. Interpretation of the results is unclear. However, the potential gains in QALYs from reduced air pollutants can be contrasted to the costs of policies to bring about such reductions. Based on a tentative threshold for the value of health benefits, analysis suggests that an investment in Canada of over 1 billion dollars per annum would be an efficient use of resources if it could be demonstrated that this would reduce sulfate concentrations in ambient air by 1 microg/m(3). Further analysis can assess the efficiency of targeting such initiatives to communities that are most likely to benefit.

Occurence of sulfate- and iron-reducing bacteria in stratal waters of the Romashkinskoe oil field

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

Nazina, T.N.; Ivanova, A.E.; Goulbeva, O.V.

1995-03-01

The occurrence of microorganisms and the rates of terminal biogenic processes-sulfate reduction and methane synthesis-were studied in stratial waters in bed 302 of the Bashkir Carboniferous deposit at the Romashkinskoe oil field. It was shown that bed 302 was a dynamic, highly reduced ecosystem containing sulfates and hydrogen sulfide in considerable concentrations, in which active biogenic processes occurred. Sulfate reduction was a dominating anaerobic process by which the transformation of organic matter occurred. The sulfate-reducing microflora was diverse and characterized by a wide range of metabolic potentials. Enrichment cultures capable of oxidizing many organic substances, such as benzoate, acetate, ethanol,more » or lactate, at the expense of reduction of sulfates and ferric ion were isolated from 302. It was suggested that the sulfate-reducing microflora might be responsible not only for sulfate reduction in the stratum but also for mobilization of some insoluble iron oxides in the oil-bearing rock. These findings indicate that bacteria carrying out dissimilatory reduction of sulfate and iron can contribute to the geochemistry of organic and mineral compounds in subsurface ecosystems. 24 refs., 2 figs., 6 tabs.« less

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.

[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.

Photocatalytic reduction of nitrate using titanium dioxide for regeneration of ion exchange brine.

PubMed

Yang, Ting; Doudrick, Kyle; Westerhoff, Paul

2013-03-01

Nitrate is often removed from groundwater by ion exchange (IX) before its use as drinking water. Accumulation of nitrate in IX brine reduces the efficiency of IX regeneration and the useful life of the regeneration brine. For the first time, we present a strategy to photocatalytically reduce nitrate in IX brine, thereby extending the use of the brine. Titanium dioxide (Evonik P90), acting as photocatalyst, reduced nitrate effectively in both synthetic brines and sulfate-removed IX brine when formic acid (FA) was used as the hole scavenger (i.e., electron donor) and the initial FA to nitrate molar ratio (IFNR) was 5.6. Increasing the NaCl level in the synthetic brine slowed the nitrate reduction rate without affecting by-product selectivity of ammonium and gaseous N species (e.g., N(2), N(2)O). In a non-modified IX brine, nitrate removal was greatly inhibited owing to the presence of sulfate, which competed with nitrate for active surface sites on P90 and induced aggregation of P90 nanoparticles. After removing sulfate through barium sulfate precipitation, nitrate was effectively reduced; approximately 3.6 × 10(24) photons were required to reduce each mole of nitrate to 83% N Gases and 17% NH(4)(+). To make optimum use of FA and control the residual FA level in treated brine, the IFNR was varied. High IFNRs (e.g., 4, 5.6) were found to be more efficient for nitrate reduction but left higher residual FA in brine. IX column tests were performed to investigate the impact of residual FA for brine reuse. The residual FA in the brine did not significantly affect the nitrate removal capacity of IX resins, and formate contamination of treated water could be eliminated by rinsing with one bed volume of fresh brine. Copyright © 2012 Elsevier Ltd. All rights reserved.

[Regulation of sulfates, hydrogen sulfide and heavy metals in technogenic reservoirs by sulfate-reducing bacteria].

PubMed

Hudz', S P; Peretiatko, T B; Moroz, O M; Hnatush, S O; Klym, I R

2011-01-01

Sulfate-reducing bacteria Desulfovibrio desulfuricans Ya-11 in the presence of sulfates and organic compounds in the medium reduce sulfates to hydrogen sulfide (dissimilatory sulfate reduction). Heavy metals in concentration over 2 mM inhibit this process. Pb2+, Zn2+, Ni2+, Co2+, Fe2+ and Cd2+ ions in concentration 1-1.5 mM display insignificant inhibiting effect on sulfate reduction process, and metals precipitate in the form of sulfides. At concentrations of heavy metals 2-3 mM one can observe a decrease of sulfates reduction intensity, and a percent of metals binding does not exceed 72%. Obtained results give reason to confirm, that sulfate-reducing bacteria play an important role in regulation of the level of sulfates, hydrogen sulfide and heavy metals in reservoirs and they may be used for purification of water environment from these compounds.

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

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

PubMed

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-11-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments

PubMed Central

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-01-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration—a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder. PMID:25871933

Combined 34S, 33S and 18O isotope fractionations record different intracellular steps of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Antler, Gilad; Turchyn, Alexandra V.; Ono, Shuhei; Sivan, Orit; Bosak, Tanja

2017-04-01

Several enzymatic steps in microbial sulfate reduction (MSR) fractionate the isotope ratios of 33S/32S, 34S/32S and 18O/16O in extracellular sulfate, but the effects of different intracellular processes on the isotopic composition of residual sulfate are still not well quantified. We measured combined multiple sulfur (33S/32S, 34S/32S) and oxygen (18O/16O) isotope ratios of sulfate in pure cultures of a marine sulfate reducing bacterium Desulfovibrio sp. DMSS-1 grown on different organic substrates. These measurements are consistent with the previously reported correlations of oxygen and sulfur isotope fractionations with the cell-specific rate of MSR: faster reduction rates produced smaller isotopic fractionations for all isotopes. Combined isotope fractionation of oxygen and multiple sulfur isotopes are also consistent with the relationship between the rate limiting step during microbial sulfate reduction and the availability of the DsrC subunit. These experiments help reconstruct and interpret processes that operate in natural pore waters characterized by high 18O/16O and moderate 34S/32S ratios and suggest that some multiple isotope signals in the environment cannot be explained by microbial sulfate reduction alone. Instead, these signals support the presence of active, but slow sulfate reduction as well as the reoxidation of sulfide.

Global rates of marine sulfate reduction and implications for sub-sea-floor metabolic activities

NASA Astrophysics Data System (ADS)

Bowles, Marshall W.; Mogollón, José M.; Kasten, Sabine; Zabel, Matthias; Hinrichs, Kai-Uwe

2014-05-01

Sulfate reduction is a globally important redox process in marine sediments, yet global rates are poorly quantified. We developed an artificial neural network trained with 199 sulfate profiles, constrained with geomorphological and geochemical maps to estimate global sulfate-reduction rate distributions. Globally, 11.3 teramoles of sulfate are reduced yearly (~15% of previous estimates), accounting for the oxidation of 12 to 29% of the organic carbon flux to the sea floor. Combined with global cell distributions in marine sediments, these results indicate a strong contrast in sub-sea-floor prokaryote habitats: In continental margins, global cell numbers in sulfate-depleted sediment exceed those in the overlying sulfate-bearing sediment by one order of magnitude, whereas in the abyss, most life occurs in oxic and/or sulfate-reducing sediments.

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.

Reduction-sensitive micelles self-assembled from amphiphilic chondroitin sulfate A-deoxycholic acid conjugate for triggered release of doxorubicin.

PubMed

Liu, Hongxia; Wu, Shuqin; Yu, Jingmou; Fan, Dun; Ren, Jin; Zhang, Lei; Zhao, Jianguo

2017-06-01

Reduction-sensitive chondroitin sulfate A (CSA)-based micelles were developed. CSA was conjugated with deoxycholic acid (DOCA) via a disulfide linkage. The bioreducible conjugate (CSA-ss-DOCA) can form self-assembled micelles in aqueous medium. The critical micelle concentration (CMC) of CSA-ss-DOCA conjugate is 0.047mg/mL, and its mean diameter is 387nm. The anticancer drug doxorubicin (DOX) was chosen as a model drug, and was effectively encapsulated into the micelles with high loading efficiency. Reduction-sensitive micelles and reduction-insensitive control micelles displayed similar DOX release behavior in phosphate buffered saline (PBS, pH7.4). Notably, DOX release from the reduction-sensitive micelles in vitro was accelerated in the presence of 20mM glutathione-containing PBS environment. Moreover, DOX-loaded CSA-ss-DOCA (CSA-ss-DOCA/DOX) micelles exhibited intracellular reduction-responsive characteristics in human gastric cancer HGC-27 cells determined by confocal laser scanning microscopy (CLSM). Furthermore, CSA-ss-DOCA/DOX micelles demonstrated higher antitumor efficacy than reduction-insensitive control micelles in HGC-27 cells. These results suggested that reduction-sensitive CSA-ss-DOCA micelles had the potential as intracellular targeted carriers of anticancer drugs. Copyright © 2017 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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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

The use of seaweed and sugarcane bagasse for the biological treatment of metal-contaminated waters under sulfate-reducing conditions.

PubMed

Gonçalves, Márcia Monteiro Machado; de Oliveira Mello, Luiz Antonio; da Costa, Antonio Carlos Augusto

2008-03-01

When wetlands reach maximum treatment capacity to remove heavy metals, removal can still take place through precipitation as sulfide because of the biological reduction of sulfate. To achieve this goal, anaerobic conditions must be attained, a sulfate source must exist, and an adequate substrate for sulfate-reducing bacteria (SRB) is also required. In the present work, two ligneous-cellulosic materials, a brown seaweed and sugarcane bagasse, have been selected as substrates for SRB growth. Experiments were simultaneously conducted in continuous operation in two columns (0.57 L each), one containing the ligneous-cellulosic material plus inoculum and another containing only the ligneous-cellulosic material. In this work, the removal of cadmium and zinc was studied because of their presence in effluents from mining/metallurgy operations. Results obtained indicated that the inoculated reactor was able to treat the effluent more efficiently than the noninoculated reactor considering the time course of the tests.

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...

A ‘rare biosphere’ microorganism contributes to sulfate reduction in a peatland

PubMed Central

Pester, Michael; Bittner, Norbert; Deevong, Pinsurang; Wagner, Michael; Loy, Alexander

2015-01-01

Methane emission from peatlands contributes substantially to global warming but is significantly reduced by sulfate reduction, which is fuelled by globally increasing aerial sulfur pollution. However, the biology behind sulfate reduction in terrestrial ecosystems is not well understood and the key players for this process as well as their abundance remained unidentified. Comparative 16S rRNA gene stable isotope probing in the presence and absence of sulfate indicated that a Desulfosporosinus species, which constitutes only 0.006% of the total microbial community 16S rRNA genes, is an important sulfate reducer in a long-term experimental peatland field site. Parallel stable isotope probing using dsrAB [encoding subunit A and B of the dissimilatory (bi)sulfite reductase] identified no additional sulfate reducers under the conditions tested. For the identified Desulfosporosinus species a high cell-specific sulfate reduction rate of up to 341 fmol SO42− cell−1 day−1 was estimated. Thus, the small Desulfosporosinus population has the potential to reduce sulfate in situ at a rate of 4.0–36.8 nmol (g soil w. wt.)−1 day−1, sufficient to account for a considerable part of sulfate reduction in the peat soil. Modeling of sulfate diffusion to such highly active cells identified no limitation in sulfate supply even at bulk concentrations as low as 10 μM. Collectively, these data show that the identified Desulfosporosinus species, despite being a member of the ‘rare biosphere’, contributes to an important biogeochemical process that diverts the carbon flow in peatlands from methane to CO2 and, thus, alters their contribution to global warming. PMID:20535221

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.

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

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.

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

[Influencing factors in preparation of brucine liposomes by ammonium sulfate transmembrane gradients].

PubMed

Wang, Wei; Chen, Jun; Cai, Bao-Chang; Fang, Yun

2008-09-01

To study the influencing factors in preparation of brucine liposomes by ammonium sulfate transmembrane gradients. The brucine liposomes were separated by Sephadex G-50, and the influence of various factors on the entrapment efficiencies were investigated. The entrapment efficiency was enhanced by increased ammonium sulfate concentration, ethanol volume and PC concentration. Burcine liposomes prepared by ammonium sulfate transmembrance gradients can get a high entrapment efficiency, the main influencing factors were ammonium sulfate concentration, ethanol volume and PC concentration.

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.

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.

Potential for beneficial application of sulfate reducing bacteria in sulfate containing domestic wastewater treatment.

PubMed

van den Brand, T P H; Roest, K; Chen, G H; Brdjanovic, D; van Loosdrecht, M C M

2015-11-01

The activity of sulfate reducing bacteria (SRB) in domestic wastewater treatment plants (WWTP) is often considered as a problem due to H2S formation and potential related odour and corrosion of materials. However, when controlled well, these bacteria can be effectively used in a positive manner for the treatment of wastewater. The main advantages of using SRB in wastewater treatment are: (1) minimal sludge production, (2) reduction of potential pathogens presence, (3) removal of heavy metals and (4) as pre-treatment of anaerobic digestion. These advantages are accessory to efficient and stable COD removal by SRB. Though only a few studies have been conducted on SRB treatment of domestic wastewater, the many studies performed on industrial wastewater provide information on the potential of SRB in domestic wastewater treatment. A key-parameter analyses literature study comprising pH, organic substrates, sulfate, salt, temperature and oxygen revealed that the conditions are well suited for the application of SRB in domestic wastewater treatment. Since the application of SRB in WWTP has environmental benefits its application is worth considering for wastewater treatment, when sulfate is present in the influent.

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

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.

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.

Simultaneous chemical oxygen demand removal, methane production and heavy metal precipitation in the biological treatment of landfill leachate using acid mine drainage as sulfate resource.

PubMed

Li, Yu-Long; Wang, Jin; Yue, Zheng-Bo; Tao, Wei; Yang, Hai-Bin; Zhou, Yue-Fei; Chen, Tian-Hu

2017-07-01

Biological treatment played an important role in the treatment of landfill leachate. In the current study, acid mine drainage (AMD) was used as a source of sulfate to strengthen the anaerobic treatment of landfill leachate. Effects of chemical oxygen demand (COD) and SO 4 2- mass concentration ratio on the decomposition of organic matter, methane production and sulfate reduction were investigated and the microbial community was analyzed using the high throughout methods. Results showed that high removal efficiency of COD, methane production and heavy metal removal was achieved when the initial COD/SO 4 2- ratio (based on mass) was set at 3.0. The relative abundance of anaerobic hydrogen-producing bacteria (Candidatus Cloacamonas) in the experimental group with the addition of AMD was significantly increased compared to the control. Abundance of hydrogenotrophic methanogens of Methanosarcina and Methanomassiliicoccus was increased. Results confirmed that AMD could be used as sulfate resource to strengthen the biological treatment of landfill leachate. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. 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.

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.

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.

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.

Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark

NASA Astrophysics Data System (ADS)

Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.

2014-12-01

Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

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.

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.

Isotopic insights into microbial sulfur cycling in oil reservoirs

PubMed Central

Hubbard, Christopher G.; Cheng, Yiwei; Engelbrekston, Anna; Druhan, Jennifer L.; Li, Li; Ajo-Franklin, Jonathan B.; Coates, John D.; Conrad, Mark E.

2014-01-01

Microbial sulfate reduction in oil reservoirs (biosouring) is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM) is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of −30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters (FW) containing elevated concentrations of volatile fatty acids (VFAs) and injection water (IW) containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures. PMID:25285094

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.

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.

Amyloodiniosis in cultured Dicentrarchus labrax: parasitological and molecular diagnosis, and an improved treatment protocol.

PubMed

Bessat, Mohamed; Fadel, Amr

2018-06-19

Amyloodinium ocellatum, the causative agent of amyloodiniosis (marine velvet, velvet disease), affects marine and brackish fish in various warm and temperate habitats. We recorded disease outbreaks with high morbidity and mortality rates in marine-cultured European seabass Dicentrarchus labrax fry at 2 locations in northwest Egypt. The sudden outbreak, high morbidity and mortality rates, and skin lesions with a velvety appearance in affected fish all indicated A. ocellatum infection. This was further confirmed by microscopic findings of the parasitic stage (trophonts) in skin and gill smears. While ecological factors including water temperature and salinity were all amenable to parasite establishment and propagation, mortality rates differed between the 2 farms, with rates of mortality well correlated with prevalence and intensity of A. ocellatum infections. Characterization by PCR targeting rDNA gene fragments and subsequent DNA sequencing and phylogenetic analysis further confirmed the molecular identity of the A. ocellatum isolate, which was genetically similar to isolates from other geographical locations. Finally, an improved treatment method using dual hyposalination and copper sulfate exposure to increase the efficiency and decrease the toxicity of copper sulfate was tested. The gradual reduction in water salinity coupled with copper sulfate treatment was more efficient at controlling the disease than only applying copper sulfate. To our knowledge, this is the first parasitological and molecular characterization of A. ocellatum in marine cultures in Egypt. The high molecular identity and close phylogenetic relationship further confirmed the monophyletic nature of A. ocellatum isolates.

Energy efficient reconcentration of diluted human urine using ion exchange membranes in bioelectrochemical systems.

PubMed

Tice, Ryan C; Kim, Younggy

2014-11-01

Nutrients can be recovered from source separated human urine; however, nutrient reconcentration (i.e., volume reduction of collected urine) requires energy-intensive treatment processes, making it practically difficult to utilize human urine. In this study, energy-efficient nutrient reconcentration was demonstrated using ion exchange membranes (IEMs) in a microbial electrolysis cell (MEC) where substrate oxidation at the MEC anode provides energy for the separation of nutrient ions (e.g., NH4(+), HPO4(2-)). The rate of nutrient separation was magnified with increasing number of IEM pairs and electric voltage application (Eap). Ammonia and phosphate were reconcentrated from diluted human urine by a factor of up to 4.5 and 3.0, respectively (Eap = 1.2 V; 3-IEM pairs). The concentrating factor increased with increasing degrees of volume reduction, but it remained stationary when the volume ratio between the diluate (urine solution that is diluted in the IEM stack) and concentrate (urine solution that is reconcentrated) was 6 or greater. The energy requirement normalized by the mass of nutrient reconcentrated was 6.48 MJ/kg-N (1.80 kWh/kg-N) and 117.6 MJ/kg-P (32.7 kWh/kg-P). In addition to nutrient separation, the examined MEC reactor with three IEM pairs showed 54% removal of COD (chemical oxygen demand) in 47-hr batch operation. The high sulfate concentration in human urine resulted in substantial growth of both of acetate-oxidizing and H2-oxidizing sulfate reducing bacteria, greatly diminishing the energy recovery and Coulombic efficiency. However, the high microbial activity of sulfate reducing bacteria hardly affected the rate of nutrient reconcentration. With the capability to reconcentrate nutrients at a minimal energy consumption and simultaneous COD removal, the examined bioelectrochemical treatment method with an IEM application has a potential for practical nutrient recovery and sustainable treatment of source-separated human urine. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

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.

Evidence For Volcanic Initiation Of Cretaceous Ocean Anoxic Events (Invited)

NASA Astrophysics Data System (ADS)

Sageman, B. B.; Hurtgen, M. T.; McElwain, J.; Adams, D.; Barclay, R. S.; Joo, Y.

2010-12-01

Increasing evidence from studies of Cretaceous ocean anoxic events (OAE’s) has suggested that major changes in volcanic activity may have played a significant role in their genesis. Numerous specific mechanisms of have been proposed, including increases in atmospheric CO2 and surface temperature, leading to enhanced chemical weathering and terrestrial nutrient release, or increases in reduced trace metal fluxes, leading to oxygen depletion and possibly providing micronutrients for enhanced primary production. An additional pathway by which the byproducts of enhanced volcanic activity may have contributed to OAE genesis involves relationships between the biogeochemical cycles sulfur, iron, and phosphorus. Recent analysis of S-isotope data from carbonate-associated sulfate and pyrite collected across the Cenomanian-Turonian OAE2 in the Western Interior basin suggest that increases in sulfate to an initially sulfate-depleted ocean preceded onset of the event. Modern lake data support the idea that increases in sulfate concentration drive microbial sulfate reduction, leading to more efficient regeneration of P from sedimentary organic matter. If the early Cretaceous opening of the South Atlantic was accompanied by evaporite deposition sufficient to draw down global marine sulfate levels, and widespread anoxia leading to elevated pyrite burial helped maintain these low levels for the succeeding 30 myr, during which most Cretaceous OAE’s are found, perhaps pulses of volcanism that rapidly introduced large volumes of sulfate may have played a key role in OAE initiation. The eventually burial of S in the form of pyrite may have returned sulfate levels to a low background, thus providing a mechanism to terminate the anoxic events. This talk will review the evidence for volcanic initiation of OAE’s in the context of the sulfate-phosphorus regeneration model.

Degradation of TCE, Cr(VI), sulfate, and nitrate mixtures by granular iron in flow-through columns under different microbial conditions.

PubMed

Gandhi, Sumeet; Oh, Byung-Taek; Schnoor, Jerald L; Alvarez, Pedro J J

2002-04-01

Flow-through aquifer columns packed with a middle layer of granular iron (Fe0) were used to study the applicability and limitations of bio-enhanced Fe0 barriers for the treatment of contaminant mixtures in groundwater. Concentration profiles along the columns showed extensive degradation of hexavalent chromium Cr(VI), nitrate, sulfate, and trichloroethene (TCE), mainly in the Fe0 layer. One column was bioaugmented with Shevanella algae BRY, an iron-reducing bacterium that could enhance Fe0 reactivity by reductive dissolution of passivating iron oxides. This strain did not enhance Cr(VI), which was rapidly reduced by iron, leaving little room for improvement by microbial participation. Nevertheless, BRY-enhanced nitrate removal (from 15% to 80%), partly because this strain has a wide range of electron acceptors, including nitrate. Sulfate was removed (55%) only in a column that was bioaugmented with a mixed culture containing sulfate-reducing bacteria. Apparently, these bacteria used H2 (produced by Fe0 corrosion) as electron donor to respire sulfate. Most of the TCE was degraded in the zone containing Fe0 (50-70%), and bioaugmentation with BRY slightly increased the removal efficiency to about 80%. Microbial colonization of the Fe0 surface was confirmed by scanning electron microscopy.

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.

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.

Coupling between sulfur recycling and syndepositional carbonate dissolution: evidence from oxygen and sulfur isotope composition of pore water sulfate, South Florida Platform, U.S.A.

NASA Astrophysics Data System (ADS)

Ku, T. C. W.; Walter, L. M.; Coleman, M. L.; Blake, R. E.; Martini, A. M.

1999-10-01

Sulfur cycling in Fe-poor, organic-rich shelf carbonates, known to have rapid rates of SO4-2 reduction, remains poorly studied despite the volumetric significance of shelf deposits in modern and ancient carbon budgets. We investigated sulfur cycling in modern carbonates of the Florida Platform from end-member depositional environments (muddy sands from the Atlantic reef tract and finer-grained mudbank and island flank deposits from Florida Bay). Relations between pore water chemistry (SO4-2, ΣCO2, Ca-2/Cl-) and oxygen and sulfur stable isotope compositions of SO4-2 require direct coupling between sulfur redox cycling and syndepositional carbonate dissolution. Oxygen isotope compositions of pore water sulfate were remarkably shifted away from the established value for marine SO4-2 (+9.5‰), despite near normal SO4-2/Cl- ratios. Chemical evolution was least in reef tract pore waters and greatest in Florida Bay. Relative to overlying seawater, mudbank sediments exhibited sulfate depletion, with δ18OSO4 and δ34SSO4 values both increasing by about 7‰. More bioturbated island flank sediments, colonized by Thalassia grass, had a 5‰ increase in δ18OSO4, variable δ34SSO4 values (+17.7 to +23.3‰) and exceptionally high Ca+2/Cl- ratios. The large excess of Ca+2 (up to 1.7 mM) requires a much larger acid source than the amounts derived from utilization of dissolved O2 (∼0.3 mM) and small degrees of net SO4-2 reduction (<0.5 mM reduced). A conceptual model was constructed using chemical and isotopic data on natural pore waters and on sulfate isotope fractionation factors obtained from sediment incubation experiments. The model outputs show that pore water compositions can be explained by a redox cycle where microbial SO4-2 reduction is followed by very efficient H2S oxidation, thus maintaining virtually invariant SO4-2/Cl- ratios. The enhanced O2 transport may be driven by associated marine grass rhizome systems and microbial communities established in bioturbated sediments. The net result of the cycle is that the rate of sulfide oxidation, which is largely balanced by the rate of microbial sulfate reduction, is stoichiometrically related to the rate of carbonate dissolution. This is consistent with previously reported rates of carbonate dissolution (∼400 μmol/cm2-yr) and average rates of sulfate reduction (∼200 μmol/cm2-yr) from the Florida Platform and a 2:1 stoichiometry.

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.

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.

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.

Solid phase studies and geochemical modelling of low-cost permeable reactive barriers.

PubMed

Bartzas, Georgios; Komnitsas, Kostas

2010-11-15

A continuous column experiment was carried out under dynamic flow conditions in order to study the efficiency of low-cost permeable reactive barriers (PRBs) to remove several inorganic contaminants from acidic solutions. A 50:50 w/w waste iron/sand mixture was used as candidate reactive media in order to activate precipitation and promote sorption and reduction-oxidation mechanisms. Solid phase studies of the exhausted reactive products after column shutdown, using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD), confirmed that the principal Fe corrosion products identified in the reactive zone are amorphous iron (hydr)oxides (maghemite/magnetite and goethite), intermediate products (sulfate green rust), and amorphous metal sulfides such as amFeS and/or mackinawite. Geochemical modelling of the metal removal processes, including interactions between reactive media, heavy metal ions and sulfates, and interpretation of the ionic profiles was also carried out by using the speciation/mass transfer computer code PHREEQC-2 and the WATEQ4F database. Mineralogical characterization studies as well as geochemical modelling calculations also indicate that the effect of sulfate and silica sand on the efficiency of the reactive zone should be considered carefully during design and operation of low-cost field PRBs. Copyright © 2010 Elsevier B.V. All rights reserved.

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)

Characterization of sulfate reducing bacteria isolated from urban soil

NASA Astrophysics Data System (ADS)

Zhang, Mingliang; Wang, Haixia

2017-05-01

Sulfate reducing bacteria (SRB) was isolated from urban soil and applied for the remediation of heavy metals pollution from acid mine drainage. The morphology and physiological characteristics (e.g. pH and heavy metals tolerance) of SRB was investigated. The SRB was gram-negative bacteria, long rod with slight curve, cell size 0.5× (1.5-2.0) μm. The pH of medium had significant effect on SRB growth and the efficiency of sulfate reduction, and it showed that the suitable pH range was 5-9 and SRB could not survive at pH less than 4. The maximum tolerance of Fe (II), Zn (II), Cd (II), and Cu (II) under acidic condition (pH 5.0) was about 600 mg/L, 150 mg/L, 25 mg/L and 25 mg/L, respectively. The result indicated that SRB isolated in this study could be used for the bioremediation of acid mine drainage (pH>4) within the heavy metals concentrations tolerance.

Preparation, characterization and pharmacokinetics of fluorescence labeled propylene glycol alginate sodium sulfate

NASA Astrophysics Data System (ADS)

Li, Pengli; Li, Chunxia; Xue, Yiting; Zhang, Yang; Liu, Hongbing; Zhao, Xia; Yu, Guangli; Guan, Huashi

2014-08-01

A rapid and sensitive fluorescence labeling method was developed and validated for the microanalysis of a sulfated polysaccharide drug,namely propylene glycol alginate sodium sulfate (PSS), in rat plasma. Fluorescein isothiocyanate (FITC) was selected to label PSS, and 1, 6-diaminohexane was used to link PSS and FITC in order to prepare FITC-labeled PSS (F-PSS) through a reductive amination reaction. F-PSS was identified by UV-Vis, FT-IR and 1H-NMR spectrum. The cell stability and cytotoxicity of F-PSS were tested in Madin-Darby canine kidney (MDCK) cells. The results indicated that the labeling efficiency of F-PSS was 0.522% ± 0.0248% and the absolute bioavailability was 8.39%. F-PSS was stable in MDCK cells without obvious cytotoxicity. The method was sensitive and reliable; it showed a good linearity, precision, recovery and stability. The FITC labeling method can be applied to investigating the absorption and metabolism of PSS and other polysaccharides in biological samples.

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

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

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.

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.

Transformation of Nitrate and Toluene in Groundwater by Sulfur Modified Iron(SMI-III)

NASA Astrophysics Data System (ADS)

Lee, W.; Park, S.; Lim, J.; Hong, U.; Kwon, S.; Kim, Y.

2009-12-01

In Korea, nitrate and benzene, toluene, ethylbenzene, and xylene isomers (BTEX) are frequently detected together as ground water contaminants. Therefore, a system simultaneously treating both nitrate (inorganic compound) and BTEX (organic compounds) is required to utilize groundwater as a water resource. In this study, we investigated the efficiency of Sulfur Modified Iron (SMI-III) in treating both nitrate and BTEX contaminated groundwater. Based on XRD (X-Ray Diffraction) analysis, the SMI-III is mainly composed of Fe3O4, S, and Fe. A series of column tests were conducted at three different empty bed contact times (EBCTs) for each compound. During the experiments, removal efficiency for both nitrate and toluene were linearly correlated with EBCT, suggesting that SMI-III have an ability to transform both nitrate and toluene. The concentration of SO42- and oxidation/reduction potential (ORP) were also measured. After exposed to nitrate contaminated groundwater, the composition of SMI-III was changed to Fe2O3, Fe3O4, Fe, and Fe0.95S1.05. The trends of effluent sulfate concentrations were inversely correlated with effluent nitrate concentrations, while the trends of ORP values, having the minimum values of -480 mV, were highly correlated with effluent nitrate concentrations. XRD analysis before and after exposed to nitrate contaminated groundwater, sulfate production, and nitrite detection as a reductive transformation by-product of nitrate suggest that nitrate is reductively transformed by SMI-III. Interestingly, in the toluene experiments, the trends of ORP values were inversely correlated with effluent toluene concentrations, suggesting that probably degrade through oxidation reaction. Consequently, nitrate and toluene probably degrade through reduction and oxidation reaction, respectively and SMI-III could serve as both electron donor and acceptor.

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.

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.

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.

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

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...

The Microbial Sulfur Cycle at Extremely Haloalkaline Conditions of Soda Lakes

PubMed Central

Sorokin, Dimitry Y.; Kuenen, J. Gijs; Muyzer, Gerard

2011-01-01

Soda lakes represent a unique ecosystem with extremely high pH (up to 11) and salinity (up to saturation) due to the presence of high concentrations of sodium carbonate in brines. Despite these double extreme conditions, most of the lakes are highly productive and contain a fully functional microbial system. The microbial sulfur cycle is among the most active in soda lakes. One of the explanations for that is high-energy efficiency of dissimilatory conversions of inorganic sulfur compounds, both oxidative and reductive, sufficient to cope with costly life at double extreme conditions. The oxidative part of the sulfur cycle is driven by chemolithoautotrophic haloalkaliphilic sulfur-oxidizing bacteria (SOB), which are unique for soda lakes. The haloalkaliphilic SOB are present in the surface sediment layer of various soda lakes at high numbers of up to 106 viable cells/cm3. The culturable forms are so far represented by four novel genera within the Gammaproteobacteria, including the genera Thioalkalivibrio, Thioalkalimicrobium, Thioalkalispira, and Thioalkalibacter. The latter two were only found occasionally and each includes a single species, while the former two are widely distributed in various soda lakes over the world. The genus Thioalkalivibrio is the most physiologically diverse and covers the whole spectrum of salt/pH conditions present in soda lakes. Most importantly, the dominant subgroup of this genus is able to grow in saturated soda brines containing 4 M total Na+ – a so far unique property for any known aerobic chemolithoautotroph. Furthermore, some species can use thiocyanate as a sole energy source and three out of nine species can grow anaerobically with nitrogen oxides as electron acceptor. The reductive part of the sulfur cycle is active in the anoxic layers of the sediments of soda lakes. The in situ measurements of sulfate reduction rates and laboratory experiments with sediment slurries using sulfate, thiosulfate, or elemental sulfur as electron acceptors demonstrated relatively high sulfate reduction rates only hampered by salt-saturated conditions. However, the highest rates of sulfidogenesis were observed not with sulfate, but with elemental sulfur followed by thiosulfate. Formate, but not hydrogen, was the most efficient electron donor with all three sulfur electron acceptors, while acetate was only utilized as an electron donor under sulfur-reducing conditions. The native sulfidogenic populations of soda lakes showed a typical obligately alkaliphilic pH response, which corresponded well to the in situ pH conditions. Microbiological analysis indicated a domination of three groups of haloalkaliphilic autotrophic sulfate-reducing bacteria belonging to the order Desulfovibrionales (genera Desulfonatronovibrio, Desulfonatronum, and Desulfonatronospira) with a clear tendency to grow by thiosulfate disproportionation in the absence of external electron donor even at salt-saturating conditions. Few novel representatives of the order Desulfobacterales capable of heterotrophic growth with volatile fatty acids and alcohols at high pH and moderate salinity have also been found, while acetate oxidation was a function of a specialized group of haloalkaliphilic sulfur-reducing bacteria, which belong to the phylum Chrysiogenetes. PMID:21747784

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.

Performance evaluation and microbial community analysis of the function and fate of ammonia in a sulfate-reducing EGSB reactor.

PubMed

Wang, Depeng; Liu, Bo; Ding, Xinchun; Sun, Xinbo; Liang, Zi; Sheng, Shixiong; Du, Lingfeng

2017-10-01

Ammonia is widely distributed in sulfate-reducing bioreactor dealing with sulfate wastewater, which shows potential effect on the metabolic pathway of sulfate and ammonia. This study investigates the sulfate-reducing efficiency and microbial community composition in the sulfate-reducing EGSB reactor with the increasing ammonia loading. Results indicated that, compared with low ammonia loading (166-666 mg/L), the sulfate and organic matter removal efficiencies were improved gradually with the appropriate ammonia loading (1000-2000 mg/L), which increased from 63.58 ± 3.81 to 71.08 ± 1.36% and from 66.24 ± 1.32 to 81.88 ± 1.83%, respectively. Meanwhile, with the appropriate ratio of ammonia and sulfate (1.5-3.0) and hydraulic retention time (21 h), the sulfate-reducing anaerobic ammonia oxidation (SRAO) process was occurred efficiently, inducing the accumulation of S 0 (270 mg/L) and the simultaneous ammonia removal (70.83%) in EGSB reactor. Moreover, the key sulfate-reducing bacteria (SRB) (Desulfovibrio) and denitrification bacteria (Pseudomonas and Alcaligenes) were responsible for the sulfate and nitrogen removal in these phases, which accounted for 3.66-5.54 and 3.85-9.13%, respectively. However, as the ammonia loading higher than 3000 mg/L (phases 9 and 10), the sulfate-reducing efficiency was decreased to only 28.3 ± 1.26% with the ammonia removal rate of 18.4 ± 3.37% in the EGSB reactor. Meanwhile, the predominant SRB in phases 9 and 10 were Desulfomicrobium (1.22-1.99%) and Desulfocurvus (4.0-5.46%), and the denitrification bacteria accounted for only 0.88% (phase 10), indicating the low nitrogen removal rate.

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.

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.

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.

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.

Study the adsorption of sulfates by high cross-linked polystyrene divinylbenzene anion-exchange resin

NASA Astrophysics Data System (ADS)

Fathy, Mahmoud; Moghny, Th. Abdel; Awadallah, Ahmed E.; El-Bellihi, Abdel-Hameed A.-A.

2017-03-01

In response to rising concerns about the effect of sulfate on water quality, human health, and agriculture, many jurisdictions around the world are imposing tighter regulations for sulfate discharge. This is driving the need for environmental compliance in industries like mining, metal processing, pulp and paper, sewage treatment, and chemical manufacturing. The sulfate removal from synthetic water by high cross-linked polystyrene divinylbenzene resin was studied at batch experiments in this study. The effect of pH, contact time, sulfates concentration, and adsorbent dose on the sulfate sequestration was investigated. The optimum conditions were studied on Saline water as a case study. The results showed that with increasing of the absorbent amount; contact time, and pH improve the efficiency of sulfate removal. The maximum sulfates uptake was obtained in pH and contact time 3.0 and 120 min, respectively. Also, with increasing initial concentration of sulfates in water, the efficiency of sulfate removal decreased. The obtained results in this study were matched with Freundlich isotherm and pseudo-second-order kinetic. The maximum adsorption capacity (Qm) and constant rate were found 0.318 (mg/g) and 0.21 (mg/g.min), respectively. This study also showed that in the optimum conditions, the sulfate removal efficiency from Saline water by 0.1 mg/L sulfates was 65.64 %. Eventually, high cross-linked polystyrene divinylbenzene resin is recommended as a suitable and low cost absorbent to sulfate removal from aqueous solutions.

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.

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

Interconnected nitrogen and sulfur dual-doped porous carbon as efficient electrocatalyst for triiodide reduction in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Li, Zhao; Yang, Wang; Xu, Xiuwen; Tang, Yushu; Zeng, Ziwei; Yang, Fan; Zhang, Liqiang; Ning, Guoqing; Xu, Chunming; Li, Yongfeng

2016-09-01

Exploiting cost-effective and efficient counter electrodes (CEs) for the reduction of triiodide (I3-) has been a persistent objective for the development of dye-sensitized solar cells (DSSCs). Here, we propose a strategy for the synthesis of nitrogen and sulfur dual-doped porous carbon (N/S-PC) via a thermal annealing approach by using melamine as N source, and basic magnesium sulfate (BMS) whiskers as S source and templates. Benefiting from the high surface area, unique interconnected structural feature and synergistic effects of N/S dual-doping, the N/S-PC shows excellent electrocatalytic activity toward I3- reduction, which has simultaneously been confirmed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Tafel polarization measurements. The DSSC devices with N/S-PC CEs exhibit a PCE up to 7.41%, which is higher than that of DSSC devices with single heteroatom (N or S) doped CEs and even Pt CEs (7.14%).

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.

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.

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.

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

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

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.

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.

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

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.

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.

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

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.

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 ...

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.

Reaction kinetics and efficiencies for the hydroxyl and sulfate radical based oxidation of artificial sweeteners in water.

PubMed

Toth, Janie E; Rickman, Kimberly A; Venter, Andre R; Kiddle, James J; Mezyk, Stephen P

2012-10-11

Over the past several decades, the increased use of artificial sweeteners as dietary supplements has resulted in rising concentrations of these contaminants being detected in influent waters entering treatment facilities. As conventional treatments may not quantitatively remove these sweeteners, radical-based advanced oxidation and reduction (AO/RP) treatments could be a viable alternative. In this study, we have established the reaction kinetics for both hydroxyl ((•)OH) and sulfate (SO(4)(•-)) radical reaction with five common artificial sweeteners, as well as their associated reaction efficiencies. Rate constants for acesulfame K, aspartame, rebaudioside A, saccharin, and sucralose were <2 × 10(7), (2.28 ± 0.02) × 10(9), (2.1 ± 0.1) × 10(8), <2 × 10(7), and (1.7 ± 0.1) × 10(8) M(-1) s(-1) for the sulfate radical, and (3.80 ± 0.27) × 10(9), (6.06 ± 0.05) × 10(9), (9.97 ± 0.12) × 10(9), (1.85 ± 0.01) × 10(9), and (1.50 ± 0.01) × 10(9) M(-1) s(-1) for the hydroxyl radical, respectively. These latter values have to be combined with their corresponding reaction efficiencies of 67.9 ± 0.9, 52.2 ± 0.7, 43.0 ± 2.5, 52.7 ± 2.9, and 98.3 ± 3.5% to give effective rate constants for the hydroxyl radical reaction that can be used in the modeling of the AOP based removal of these contaminants.

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.

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.

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.

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.

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.

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.

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.

Sulfated Polysaccharide, Curdlan Sulfate, Efficiently Prevents Entry/Fusion and Restricts Antibody-Dependent Enhancement of Dengue Virus Infection In Vitro: A Possible Candidate for Clinical Application

PubMed Central

Zhang, Li Feng; Chin, Wei Xin; Muschin, Tegshi; Heinig, Lars; Suzuki, Youichi; Nanjundappa, Haraprasad; Yoshinaka, Yoshiyuki; Ryo, Akihide; Nomura, Nobuo; Ooi, Eng Eong; Vasudevan, Subhash G.; Yoshida, Takashi; Yamamoto, Naoki

2013-01-01

Curdlan sulfate (CRDS), a sulfated 1→3-β-D glucan, previously shown to be a potent HIV entry inhibitor, is characterized in this study as a potent inhibitor of the Dengue virus (DENV). CRDS was identified by in silico blind docking studies to exhibit binding potential to the envelope (E) protein of the DENV. CRDS was shown to inhibit the DENV replication very efficiently in different cells in vitro. Minimal effective concentration of CRDS was as low as 0.1 µg/mL in LLC-MK2 cells, and toxicity was observed only at concentrations over 10 mg/mL. CRDS can also inhibit DENV-1, 3, and 4 efficiently. CRDS did not inhibit the replication of DENV subgenomic replicon. Time of addition experiments demonstrated that the compound not only inhibited viral infection at the host cell binding step, but also at an early post-attachment step of entry (membrane fusion). The direct binding of CRDS to DENV was suggested by an evident reduction in the viral titers after interaction of the virus with CRDS following an ultrafiltration device separation, as well as after virus adsorption to an alkyl CRDS-coated membrane filter. The electron microscopic features also showed that CRDS interacted directly with the viral envelope, and caused changes to the viral surface. CRDS also potently inhibited DENV infection in DC-SIGN expressing cells as well as the antibody-dependent enhancement of DENV-2 infection. Based on these data, a probable binding model of CRDS to DENV E protein was constructed by a flexible receptor and ligand docking study. The binding site of CRDS was predicted to be at the interface between domains II and III of E protein dimer, which is unique to this compound, and is apparently different from the β-OG binding site. Since CRDS has already been tested in humans without serious side effects, its clinical application can be considered. PMID:23658845

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.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2013-05-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2 : 1 mixtures of organic polyols (1,2,6-hexanetriol and 1 : 1 1,2,6-hexanetriol + 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicate that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase-separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2012-12-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2:1 mixtures of organic polyols (1,2,6-hexanetriol, and 1:1 1,2,6-hexanetriol +2,2,6,6-tetrakis(hydroxymethyl)cycohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicates that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Selective catalytic reduction system and process using a pre-sulfated zirconia binder

DOEpatents

Sobolevskiy, Anatoly; Rossin, Joseph A.

2010-06-29

A selective catalytic reduction (SCR) process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream with a catalyst system, the catalyst system comprising (ZrO.sub.2)SO.sub.4, palladium, and a pre-sulfated zirconia binder. The inclusion of a pre-sulfated zirconia binder substantially increases the durability of a Pd-based SCR catalyst system. A system for implementing the disclosed process is further provided.

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.

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.

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.

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.

Reduction on the anaerobic biological activity inhibition caused by heavy metals and sulphates in effluents through chemical precipitation with soda and lime.

PubMed

Alves, L de Carvalho; Cammarota, M C; De França, F P

2006-12-01

The School of Chemistry Environmental Technology Laboratory generates 43.4 1 of effluent with low pH (0.7) and high contents of COD (1908 mgO2 l(-1)), phenol (132.1 mg l(-1)), sulfate (36700 mg l(-1)) and heavy metals (28.2 mg Hg l(-1); 82.1 mg Cr(total) l(-1); 30.8 mg Cu l(-1); 57.4 mg Fe(total) l(-1); 16.2 mg Al l(-1)) weekly. These data show that this effluent presents high toxicity for biological treatment, with a physical-chemical step being necessary before a biological step. Preliminary studies showed that the most toxic constituents of the effluent were sulfate, phenol and total chromium. In this work, a chemical precipitation step with sodium hydroxide or lime was evaluated for the toxicity reduction on anaerobic microbial consortium. These experiments were carried out with increasing concentrations of alkalis in the effluent in order to obtain pH initial values of 8-12. Similar results were obtained for COD (15-28%), turbidity (95-98%), phenol (13-24%) and total chromium (99.8-99.9%) removals in each condition studied with soda or lime. Sulfate was only removed by precipitation with lime, obtaining reductions from 84 to 88%. The toxicity on the anaerobic sludge was studied employing specific methanogenic activity (SMA) analysis of raw and treated effluent (after chemical precipitation step). The SMA experiments showed that chemical precipitation at pH 8 reduces the toxic effect of the effluent on anaerobic microbial consortium three times (with soda) and thirteen times (with lime). These results indicate that precipitation with lime is more efficient at toxicity removal, however the produced sludge volume is around two times higher than that produced with soda.

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.

Sulfur capture under periodically changing oxidizing and reducing conditions in PFBC

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

Zevenhoven, R.; Yrjas, P.; Hupa, M.

1999-07-01

During in situ sulfur capture with a calcium-based sorbent in fluidized bed combustion (FBC), a temperature optimum is found, at atmospheric pressure, at {approximately}850 C. The repeated decomposition of sulfated limestone during stages where the gas atmosphere surrounding the sorbent particle is not oxidizing but reducing has been identified to explain this maximum. Under pressurized (PFBC) conditions, an additional aspect is the direct conversion of calcium carbonate (CaCO{sub 3}) without the intermediate calcium oxide (CaO) due to the partial pressure of carbon dioxide (CO{sub 2}). In this work it was evaluated how stable calcium sulfate (CaSO{sub 4}) is in amore » gas atmosphere that periodically changes from oxidizing to reducing and vice versa. Atmospheric as well as elevated pressures are considered. CaO or CaCO{sub 3}, and/or calcium sulfide (CaS) are formed during the reducing stage. Using a pressurized thermogravimetric reactor (PTGR) a limestone was periodically sulfated under oxidizing conditions and decomposed under reducing conditions with carbon monoxide (CO), or with CO + H{sub 2} (hydrogen). Experiments at 1 bar and 15 bar were carried out, at temperatures from 850 C to 950 C, at C O and CO + H{sub 2} concentrations up to 4%-vol. The experimental data were modeled using simple first order (parallel) reaction schemes that allowed for sorbent structure changes. This gave rate parameters for the sulfation and the decomposition reactions, and identified the decomposition products. It was found that 1 bar, CO + H{sub 2} gives a higher reduction of CaSO{sub 4} than CO, at the same total concentration. The rate of decomposition increases faster with temperature than the sulfation, explaining the sulfation efficiency maximum mentioned above. At 15 bar, a different picture is seen. The reductive decomposition rate as well as the sulfation rate are slower, with CO as well as CO with small amounts of H{sub 2} as the reducing species. There is a significant effect of the water which is present in the gas at higher concentrations than H{sub 2}. Thermodynamics indicate that this leads to the decomposition of CaS, releasing H{sub 2}S.« less

Fine-tuning key parameters of an integrated reactor system for the simultaneous removal of COD, sulfate and ammonium and elemental sulfur reclamation.

PubMed

Yuan, Ye; Chen, Chuan; Liang, Bin; Huang, Cong; Zhao, Youkang; Xu, Xijun; Tan, Wenbo; Zhou, Xu; Gao, Shuang; Sun, Dezhi; Lee, Duujong; Zhou, Jizhong; Wang, Aijie

2014-03-30

In this paper, we proposed an integrated reactor system for simultaneous removal of COD, sulfate and ammonium (integrated C-S-N removal system) and investigated the key parameters of the system for a high level of elemental sulfur (S(0)) production. The system consisted of 4 main units: sulfate reduction and organic carbon removal (SR-CR), autotrophic and heterotrophic denitrifying sulfide removal (A&H-DSR), sulfur reclamation (SR), and aerated filter for aerobic nitrification (AN). In the system, the effects of key operational parameters on production of elemental sulfur were investigated, including hydraulic retention time (HRT) of each unit, sulfide/nitrate (S(2-)-S/NO3(-)-N) ratios, reflux ratios between the A&H-DSR and AN units, and loading rates of chemical oxygen demand (COD), sulfate and ammonium. Physico-chemical characteristics of biosulfur were studied for acquiring efficient S(0) recovery. The experiments successfully explored the optimum parameters for each unit and demonstrated 98% COD, 98% sulfate and 78% nitrogen removal efficiency. The optimum HRTs for SR-CR, A&H-DSR and AN were 12h, 3h and 3h, respectively. The reflux ratio of 3 could provide adequate S(2-)-S/NO3(-)-N ratio (approximately 1:1) to the A&H-DSR unit for obtaining maximum sulfur production. In this system, the maximum production of S(0) reached 90%, but only 60% S(0) was reclaimed from effluent. The S(0) that adhered to the outer layer of granules was deposited in the bottom of the A&H-DSR unit. Finally, the microbial community structure of the corresponding unit at different operational stage were analyzed by 16S rRNA gene based high throughput Illumina MiSeq sequencing and the potential function of dominant species were discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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.

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

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.

Synthesis of disulfated peptides corresponding to the N-terminus of chemokines receptors CXCR6 (CXCR6 1-20) and DARC (DARC 8-42) using a sulfate-protecting group strategy.

PubMed

Ali, Ahmed M; Taylor, Scott D

2010-04-01

Tyrosine sulfation is a post translational modification that occurs on integral membrane and secreted proteins, and is required for mediating crucial biological processes. Until recently the synthesis of sTyr peptides, especially those containing multiple sTyr residues, were among the most challenging peptides to prepare. We recently described an efficient strategy for Fmoc-based solid phase synthesis of sTyr peptides in which the sulfate group in the sTyr residue(s) is protected with a DCV group (FmocTyr(SO(3)DCV)OH, 1). After cleavage of the peptide from the support the DCV group is removed by hydrogenolysis. Here we demonstrate that sTyr peptides containing Met or Trp residues can be prepared using our sulfate-protecting group strategy by preparing peptides corresponding to residues 1-20 of chemokine receptor CXCR6 and 8-42 of chemokine receptor DARC. Removing the DCV groups at the end of the syntheses was readily achieved, without any reduction of the indole ring in Trp, by performing the hydrogenolysis in the presence of triethylamine. These conditions were found to be particularly efficient for removing the DCV group and superiour to our original conditions using H(2), ammonium formate, Pd/C. The presence of Met was found not to interfere with the removal of the DCV group. The use of pseudoproline dipeptides and N-backbone protection with the 2,4-dimethoxybenzyl group were found to be very effective tactics for preventing aggregation and aspartimide formation during the synthesis of these peptides. We also report an alternative and more cost effective synthesis of amino acid 1. Copyright (c) 2010 European Peptide Society and John Wiley & Sons, Ltd.

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.

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.

Microbial mineralization of ethene under sulfate-reducing conditions

USGS Publications Warehouse

Bradley, P.M.; Chapelle, F.H.

2002-01-01

A limited investigation of the potential for anaerobic ethylene biodegradation under SO4-reducing conditions was performed. Microorganisms indigenous to a lake-bed sediment completely mineralized [1,2-14C] ethylene to 14CO2 when incubated under SO4-reducing conditions. Reliance on ethylene and/or ethane accumulation as a quantitative indicator of complete reductive dechlorination of chloroethylene contaminants may not be warranted. SO4 addition stimulated SO4 reduction as indicated by decreasing SO4 concentrations (> 40% decrease) and production of dissolved sulfide (880 ??M). SO4 amendment completely suppressed the production of ethane and methane. The concomitant absence of ethane and methane production under SO4-amended conditions was consistent with previous conclusions that reduction of ethylene to ethane occurred under methanogenic conditions. A lack of ethylene accumulation under SO4-reducing conditions may reflect insignificant reductive dechlorination of vinyl chloride or efficient anaerobic mineralization of ethylene to CO2.

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;

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.

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

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

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

Methane Production by Microbial Mats Under Low Sulfate Concentrations

NASA Technical Reports Server (NTRS)

Bebout, Brad M.; Hoehler, Tori M.; Thamdrup, Bo; Albert, Dan; Carpenter, Steven P.; Hogan, Mary; Turk, Kendra; DesMarais, David J.

2003-01-01

Cyanobacterial mats collected in hypersaline salterns were incubated in a greenhouse under low sulfate concentrations ([SO4]) and examined for their primary productivity and emissions of methane and other major carbon species. Atmospheric greenhouse warming by gases such as carbon dioxide and methane must have been greater during the Archean than today in order to account for a record of moderate to warm paleoclemates, despite a less luminous early sun. It has been suggested that decreased levels of oxygen and sulfate in Archean oceans could have significantly stimulated microbial methanogenesis relative to present marine rates, with a resultant increase in the relative importance of methane in maintaining the early greenhouse. We maintained modern microbial mats, models of ancient coastal marine communities, in artificial brine mixtures containing both modern [SO4=] (ca. 70 mM) and "Archean" [SO4] (less than 0.2 mM). At low [SO4], primary production in the mats was essentially unaffected, while rates of sulfate reduction decreased by a factor of three, and methane fluxes increased by up to ten-fold. However, remineralization by methanogenesis still amounted to less than 0.4 % of the total carbon released by the mats. The relatively low efficiency of conversion of photosynthate to methane is suggested to reflect the particular geometry and chemical microenvironment of hypersaline cyanobacterial mats. Therefore, such mats w-ere probably relatively weak net sources of methane throughout their 3.5 Ga history, even during periods of low- environmental levels oxygen and sulfate.

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

Yung, M. M.; Cheah, S.; Kuhn, J. N.

The production of biofuels can proceed via a biomass gasification to produce syngas, which can then undergo catalytic conditioning and reforming reactions prior to being sent to a fuel synthesis reactor. Catalysts used for biomass conditioning are plagued by short lifetimes which are a result of, among other things, poisoning. Syngas produced from biomass gasification may contain between 30-300 ppm H2S, depending on the feedstock and gasification conditions, and H2S is a key catalyst poison. In order to overcome catalyst poisoning, either an H2S-tolerant catalyst or an efficient regeneration protocol should be employed. In this study, sulfur K-edge X-ray absorptionmore » near edge spectroscopy (XANES) was used to monitor sulfur species on spent catalyst samples and the transformation of these species from sulfides to sulfates during steam and air regeneration on a Ni/Mg/K/Al2O3 catalyst used to condition biomass-derived syngas. Additionally, nickel K-edge EXAFS and XANES are used to examine the state of nickel species on the catalysts. Post-reaction samples showed the presence of sulfides on the H2S-poisoned nickel catalyst and 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 H2 reduction led to a partial reduction of sulfates back to sulfides. A proposed reaction sequence is presented and recommended regeneration strategies are discussed.« less

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.

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.

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.

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.

SOx removal by calcined MgAlFe hydrotalcite-like materials: effect of the chemical composition and the cerium incorporation method.

PubMed

Cantú, Manuel; López-Salinas, Esteban; Valente, Jaime S; Montiel, Ramon

2005-12-15

Sulfur oxides are one of the most hazardous atmospheric pollutants since they contribute directly to acid rain formation. Consequently, stringent environmental regulations limit atmospheric SOx emissions, motivating research on efficient ways to reduce them. To supply an alternative to reduce these emissions in fluid catalytic cracking units, this study discloses efficient SOx reducing materials based on calcined MgAlFe hydrotalcite-like compounds (HT's). Thus, HT materials were synthesized by several methods including cerium addition. The adsorption of SO2 was carried out by contacting the calcined solid with a mixture of SO2 (1%) in air at 650 degrees C. It was demonstrated that the isomorphic incorporation of iron increased its reduction capability which was reflected in higher reduction rates and metal sulfate reduction grade at 550 degrees C. Moreover, when cerium was present in the iron-containing materials the saturation rate was improved, because cerium oxide promotes the oxidation of SO2 to SO3. The way cerium is incorporated influences the SO2 adsorption capacity.

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.

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.

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

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...

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.

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.

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.

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.

High Sulfation and a High Molecular Weight Are Important for Anti-hepcidin Activity of Heparin

PubMed Central

Asperti, Michela; Naggi, Annamaria; Esposito, Emiliano; Ruzzenenti, Paola; Di Somma, Margherita; Gryzik, Magdalena; Arosio, Paolo; Poli, Maura

2016-01-01

Heparins are efficient inhibitors of hepcidin expression even in vivo, where they induce an increase of systemic iron availability. Heparins seem to act by interfering with BMP6 signaling pathways that control the expression of liver hepcidin, causing the suppression of SMAD1/5/8 phosphorylation. The anti-hepcidin activity persists also when the heparin anticoagulant property is abolished or reduced by chemical reactions of oxidation/reduction (glycol-split, Gs-Heparins) or by high sulfation (SS-Heparins), but the structural characteristics needed to optimize this inhibitory activity have not been studied in detail. To this aim we analyzed three different heparins (Mucosal Heparin, the Glycol split RO-82, the partially desulfated glycol-split RO-68 and the oversulfated SSLMWH) and separated them in fractions of molecular weight in the range 4–16 kD. Since the distribution of the negative charges in heparins contributes to the activity, we produced 2-O- and 6-O-desulfated heparins. These derivatives were analyzed for the capacity to inhibit hepcidin expression in hepatic HepG2 cells and in mice. The two approaches produced consistent results and showed that the anti-hepcidin activity strongly decreases with molecular weight below 7 kD, with high N-acetylation and after 2-O and 6-O desulfation. The high sulfation and high molecular weight properties for efficient anti-hepcidin activity suggest that heparin is involved in multiple binding sites. PMID:26955355

Comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO2/H2O2 and UV/Fe2+/H2O2 systems.

PubMed

Garcia, J C; Oliveira, J L; Silva, A E C; Oliveira, C C; Nozaki, J; de Souza, N E

2007-08-17

This work investigated the treatability of real textile effluents using several systems involving advanced oxidation processes (AOPs) such as UV/H2O2, UV/TiO2, UV/TiO2/H2O2, and UV/Fe2+/H2O2. The efficiency of each technique was evaluated according to the reduction levels observed in the UV absorbance of the effluents, COD, and organic nitrogen reduction, as well as mineralization as indicated by the formation of ammonium, nitrate, and sulfate ions. The results indicate the association of TiO2 and H2O2 as the most efficient treatment for removing organic pollutants from textile effluents. In spite of their efficiency, Fenton reactions based treatment proved to be slower and exhibited more complicated kinetics than the ones using TiO2, which are pseudo-first-order reactions. Decolorization was fast and effective in all the experiments despite the fact that only H2O2 was used.

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.

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.

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

Producing desulfurized biogas through removal of sulfate in the first-stage of a two-stage anaerobic digestion.

PubMed

Yun, Yeo-Myeong; Sung, Shihwu; Shin, Hang-Sik; Han, Jong-In; Kim, Hyun-Woo; Kim, Dong-Hoon

2017-05-01

In the present work, a two-stage anaerobic digestion system (TSADS) was newly designed to produce biogas with a greatly reduced H 2 S content. The role of first (sulfidogenic)-stage digester was not only acidogenesis but also sulfidogenesis (sulfate reduction to H 2 S), which would minimize the input of H 2 S-producing source in the followed second (methanogenic)-stage digester. For the coexistence of acidogens and sulfate reducing bacteria (SRB) in the sulfidogenic-stage digester, it was found that pH played a crucial role. The acidogenic activity was not affected within a pH range of 4.5-6.0, while it was important to maintain a pH at 5.5 to achieve a sulfate removal efficiency over 70%. The highest sulfate removal attained was 78% at a hydraulic retention time (HRT) of 5 h at pH 5.5 ± 0.1. The H 2 S content in the biogas produced in the conventional single-stage digester (SSAD), used as a control, reached 1,650 ± 25 ppm v . In contrast, the biogas produced in the methanogenic-stage digester of the developed process had an H 2 S content of 200 ± 15 ppm v . Microbial analysis, done by the next generation sequencing technique, clearly showed the changes in community under different operating conditions. Desulfovibrio bastinii (4.9%) played a key role in sulfate removal in the sulfidogenic-stage of the TSADS owing to its characteristics of a short doubling time and growth in an acidic environment. Biotechnol. Bioeng. 2017;114: 970-979. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

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

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

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.

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.

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

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.

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.

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.

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...

[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.

Removal of oxyfluorfen from ex-situ soil washing fluids using electrolysis with diamond anodes.

PubMed

dos Santos, Elisama Vieira; Sáez, Cristina; Martínez-Huitle, Carlos Alberto; Cañizares, Pablo; Rodrigo, Manuel Andres

2016-04-15

In this research, firstly, the treatment of soil spiked with oxyfluorfen was studied using a surfactant-aided soil-washing (SASW) process. After that, the electrochemical treatment of the washing liquid using boron doped diamond (BDD) anodes was performed. Results clearly demonstrate that SASW is a very efficient approach in the treatment of soil, removing the pesticide completely by using dosages below 5 g of sodium dodecyl sulfate (SDS) per Kg of soil. After that, complete mineralization of organic matter (oxyflourfen, SDS and by-products) was attained (100% of total organic carbon and chemical oxygen demand removals) when the washing liquids were electrolyzed using BDD anodes, but the removal rate depends on the size of the particles in solution. Electrolysis of soil washing fluids occurs via the reduction in size of micelles until their complete depletion. Lower concentrations of intermediates are produced (sulfate, chlorine, 4-(trifluoromethyl)-phenol and ortho-nitrophenol) during BDD-electrolyzes. Finally, it is important to indicate that, sulfate (coming from SDS) and chlorine (coming from oxyfluorfen) ions play an important role during the electrochemical organic matter removal. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

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.

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.

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.

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.

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.

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.

Hydrolysis and Sulfation Pattern Effects on Release of Bioactive Bone Morphogenetic Protein-2 from Heparin-Based Microparticles.

PubMed

Tellier, Liane E; Miller, Tobias; McDevitt, Todd C; Temenoff, Johnna S

2015-10-28

Glycosaminoglycans (GAGs) such as heparin are promising materials for growth factor delivery due to their ability to efficiently bind positively charged growth factors including bone morphogenetic protein-2 (BMP-2) through their negatively charged sulfate groups. Therefore, the goal of this study was to examine BMP-2 release from heparin-based microparticles (MPs) after first, incorporating a hydrolytically degradable crosslinker and varying heparin content within MPs to alter MP degradation and second, altering the sulfation pattern of heparin within MPs to vary BMP-2 binding and release. Using varied MP formulations, it was found that the time course of MP degradation for 1 wt% heparin MPs was ~4 days slower than 10 wt% heparin MPs, indicating that MP degradation was dependent on heparin content. After incubating 100 ng BMP-2 with 0.1 mg MPs, most MP formulations loaded BMP-2 with ~50% efficiency and significantly more BMP-2 release (60% of loaded BMP-2) was observed from more sulfated heparin MPs (MPs with ~100% and 80% of native sulfation). Similarly, BMP-2 bioactivity in more sulfated heparin MP groups was at least four-fold higher than soluble BMP-2 and less sulfated heparin MP groups, as determined by an established C2C12 cell alkaline phosphatase (ALP) assay. Ultimately, the two most sulfated 10 wt% heparin MP formulations were able to efficiently load and release BMP-2 while enhancing BMP-2 bioactivity, making them promising candidates for future growth factor delivery applications.

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

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

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

Physical Controls on Biogeochemical Processes in Intertidal Zones of Beach Aquifers

NASA Astrophysics Data System (ADS)

Heiss, James W.; Post, Vincent E. A.; Laattoe, Tariq; Russoniello, Christopher J.; Michael, Holly A.

2017-11-01

Marine ecosystems are sensitive to inputs of chemicals from submarine groundwater discharge. Tidally influenced saltwater-freshwater mixing zones in beach aquifers can host biogeochemical transformations that modify chemical loads prior to discharge. A numerical variable-density groundwater flow and reactive transport model was used to evaluate the physical controls on reactivity for mixing-dependent and mixing-independent reactions in beach aquifers, represented as denitrification and sulfate reduction, respectively. A sensitivity analysis was performed across typical values of tidal amplitude, hydraulic conductivity, terrestrial freshwater flux, beach slope, dispersivity, and DOC reactivity. For the model setup and conditions tested, the simulations demonstrate that denitrification can remove up to 100% of terrestrially derived nitrate, and sulfate reduction can transform up to 8% of seawater-derived sulfate prior to discharge. Tidally driven mixing between saltwater and freshwater promotes denitrification along the boundary of the intertidal saltwater circulation cell in pore water between 1 and 10 ppt. The denitrification zone occupies on average 49% of the mixing zone. Denitrification rates are highest on the landward side of the circulation cell and decrease along circulating flow paths. Reactivity for mixing-dependent reactions increases with the size of the mixing zone and solute supply, while mixing-independent reactivity is controlled primarily by solute supply. The results provide insights into the types of beaches most efficient in altering fluxes of chemicals prior to discharge and could be built upon to help engineer beaches to enhance reactivity. The findings have implications for management to protect coastal ecosystems and the estimation of chemical fluxes to the ocean.

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.

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.

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.

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.

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.

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.

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.

Effective water content reduction in sewage wastewater sludge using magnetic nanoparticles.

PubMed

Lakshmanan, Ramnath; Kuttuva Rajarao, Gunaratna

2014-02-01

The present work compares the use of three flocculants for sedimentation of sludge and sludge water content from sewage wastewater i.e. magnetic iron oxide nanoparticles (MION), ferrous sulfate (chemical) and Moringa crude extract (protein). Sludge water content, wet/dry weight, turbidity and color were performed for, time kinetics and large-scale experiment. A 30% reduction of the sludge water content was observed when the wastewater was treated with either protein or chemical coagulant. The separation of sludge from wastewater treated with MION was achieved in less than 5min using an external magnet, resulted in 95% reduction of sludge water content. Furthermore, MION formed denser flocs and more than 80% reduction of microbial content was observed in large volume experiments. The results revealed that MION is efficient in rapid separation of sludge with very low water content, and thus could be a suitable alternative for sludge sedimentation and dewatering in wastewater treatment processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Field-scale modeling of acidity production and remediation efficiency during in situ reductive dechlorination

NASA Astrophysics Data System (ADS)

Brovelli, A.; Robinson, C. E.; Barry, D. A.; Gerhard, J.

2009-12-01

Enhanced reductive dechlorination is a viable technology for in situ remediation of chlorinated solvent DNAPL source areas. Although in recent years increased understanding of this technology has led to more rapid dechlorination rates, complete dechlorination can be hindered by unfavorable conditions. Hydrochloric acid produced from dechlorination and organic acids generated from electron donor fermentation can lead to significant groundwater acidification. Adverse pH conditions can inhibit the activity of dehalogenating microorganisms and thus slow or stall the remediation process. The extent of acidification likely to occur at a contaminated site depends on a number of factors including (1) the extent of dechlorination, (2) the pH-sensitivity of dechlorinating bacteria, and (3) the geochemical composition of the soil and water, in particular the soil’s natural buffering capacity. The substantial mass of solvents available for dechlorination when treating DNAPL source zones means that these applications are particularly susceptible to acidification. In this study a reactive transport biogeochemical model was developed to investigate the chemical and physical parameters that control the build-up of acidity and subsequent remediation efficiency. The model accounts for the site water chemistry, mineral precipitation and dissolution kinetics, electron donor fermentation, gas phase formation, competing electron-accepting processes (e.g., sulfate and iron reduction) and the sensitivity of microbial processes to pH. Confidence in the model was achieved by simulating a well-documented field study, for which the 2-D field scale model was able to reproduce long-term variations of pH, and the concurrent build up of reaction products. Sensitivity analyses indicated the groundwater flow velocity is able to reduce acidity build-up when the rate of advection is comparable or larger than the rate of dechlorination. The extent of pH change is highly dependent on the presence of calcite in soil, the availability of competing electron acceptors (in particular dissolved sulfates) and the efficiency with which microbes utilize electron donor. This work is part of SABRE (Source Area BioREmediation), a collaborative international research project that aimed to evaluate and improve enhanced bioremediation of chlorinated solvent source zones.

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.

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.

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.

Effect of sodium lauryl sulfate-fumaric Acid coupled addition on the in vitro rumen fermentation with special regard to methanogenesis.

PubMed

Abdl-Rahman, M A; Sawiress, F A R; Abd El-Aty, A M

2010-01-01

The aim of the current study was to evaluate the effect of sodium lauryl sulfate-fumaric acid coupled addition on in vitro methangenesis and rumen fermentation. Evaluation was carried out using in vitro gas production technique. Ruminal contents were collected from five steers immediately after slaughtering and used for preparation of inoculums of mixed rumen microorganisms. Rumen fluid was then mixed with the basal diet of steers and used to generate four treatments, negative control (no additives), sodium lauryl sulfate (SLS) treated, fumaric acid treated, and SLS-fumaric acid coupled addition treated. The results revealed that, relative to control, efficiency in reduction of methanogenesis was as follows: coupled addition > SLS-addition > fumaric acid addition. Both SLS-addition and SLS-fumaric acid coupled addition demonstrated a decremental effect on ammonia nitrogen (NH(3)-N), total short chain volatile fatty acids (SCVFAs) concentrations and the amount of substrate degraded, and an increment effect on microbial mass and microbial yield (Y(ATP)). Nevertheless, fumaric acid did not alter any of the previously mentioned parameters but induced a decremental effect on NH(3)-N. Furthermore, both fumaric acid and SLS-fumaric acid coupled addition increased propionate at the expense of acetate and butyrate, while, defaunation increased acetate at the expense of propionate and butyrate. The pH value was decreased by all treatments relative to control, while, cellulase activity did not differ by different treatments. The current study can be promising strategies for suppressing ruminal methane emissions and improving ruminants feed efficiency.

Effect of Sodium Lauryl Sulfate-Fumaric Acid Coupled Addition on the In Vitro Rumen Fermentation with Special Regard to Methanogenesis

PubMed Central

Abdl-Rahman, M. A.; Sawiress, F. A. R.; Abd El-Aty, A. M.

2010-01-01

The aim of the current study was to evaluate the effect of sodium lauryl sulfate-fumaric acid coupled addition on in vitro methangenesis and rumen fermentation. Evaluation was carried out using in vitro gas production technique. Ruminal contents were collected from five steers immediately after slaughtering and used for preparation of inoculums of mixed rumen microorganisms. Rumen fluid was then mixed with the basal diet of steers and used to generate four treatments, negative control (no additives), sodium lauryl sulfate (SLS) treated, fumaric acid treated, and SLS-fumaric acid coupled addition treated. The results revealed that, relative to control, efficiency in reduction of methanogenesis was as follows: coupled addition > SLS-addition > fumaric acid addition. Both SLS-addition and SLS-fumaric acid coupled addition demonstrated a decremental effect on ammonia nitrogen (NH3–N), total short chain volatile fatty acids (SCVFAs) concentrations and the amount of substrate degraded, and an increment effect on microbial mass and microbial yield (YATP). Nevertheless, fumaric acid did not alter any of the previously mentioned parameters but induced a decremental effect on NH3–N. Furthermore, both fumaric acid and SLS-fumaric acid coupled addition increased propionate at the expense of acetate and butyrate, while, defaunation increased acetate at the expense of propionate and butyrate. The pH value was decreased by all treatments relative to control, while, cellulase activity did not differ by different treatments. The current study can be promising strategies for suppressing ruminal methane emissions and improving ruminants feed efficiency. PMID:20445794

Modeling of Cr(VI) Bioreduction Under Fermentative and Denitrifying Conditions

NASA Astrophysics Data System (ADS)

Molins, S.; Steefel, C.; Yang, L.; Beller, H. R.

2011-12-01

The mechanisms of bioreductive immobilization of Cr(VI) were investigated by reactive transport modeling of a set of flow-through column experiments performed using natural Hanford 100H aquifer sediment. The columns were continuously eluted with 5 μM Cr(VI), 5 mM lactate as the electron donor, and selected electron acceptors (tested individually). Here we focus on the two separate experimental conditions that showed the most removal of Cr(VI) from solution: fermentation and denitrification. In each case, a network of enzymatic and abiotic reaction pathways was considered to interpret the rate of chromate reduction. The model included biomass growth and decay, and thermodynamic limitations on reaction rates, and was constrained by effluent concentrations measured by IC and ICP-MS and additional information from bacterial isolates from column effluent. Under denitrifying conditions, Cr(VI) reduction was modeled as co-metabolic with nitrate reduction based on experimental observations and previous studies on a denitrifying bacterium derived from the Hanford 100H aquifer. The reactive transport model results supported this interpretation of the reaction mechanism and were used to quantify the efficiency of the process. The models results also suggest that biomass growth likely relied on a nitrogen source other than ammonium (e.g. nitrate). Under fermentative conditions and based on cell suspension studies performed on a bacterial isolate from the columns, the model assumes that Cr(VI) reduction is carried out directly by fermentative bacteria that convert lactate into acetate and propionate. The evolution to complete lactate fermentation and Cr(VI) reduction took place over a week's time and simulations were used to determine an estimate for a lower limit of the rate of chromate reduction by calibration with the flow-through column experimental results. In spite of sulfate being added to these columns, sulfate reduction proceeded at a slow rate and was not well constrained.

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.

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.

Biogeochemical Processes Related to Metal Removal and Toxicity Reduction in the H-02 Constructed Wetland, Savannah River Site

NASA Astrophysics Data System (ADS)

Burgess, E. A.; Mills, G. L.; Harmon, M.; Samarkin, V.

2011-12-01

The H-02 wetland system was designed to treat building process water and storm water runoff from multiple sources associated with the Tritium Facility at the DOE-Savannah River Site, Aiken, SC. The wetland construction included the addition of gypsum (calcium sulfate) to foster a sulfate-reducing bacterial population. Conceptually, the wetland functions as follows: ? Cu and Zn initially bind to both dissolved and particulate organic detritus within the wetland. ? A portion of this organic matter is subsequently deposited into the surface sediments within the wetland. ? The fraction of Cu and Zn that is discharged in the wetland effluent is organically complexed, less bioavailable, and consequently, less toxic. ? The Cu and Zn deposited in the surface sediments are eventually sequestered into insoluble sulfide minerals in the wetland. Development of the H-02 system has been closely monitored; sampling began in August 2007, shortly after its construction. This monitoring has included the measurement of water quality parameters, Cu and Zn concentrations in surface water and sediments, as well as, characterization of the prokaryotic (e.g., bacterial) component of wetland biogeochemical processes. Since the beginning of the study, the mean influent Cu concentration was 31.5±12.1 ppb and the mean effluent concentration was 11.9±7.3 ppb, corresponding to an average Cu removal of 64%. Zn concentrations were more variable, averaging 39.2±13.8 ppb in the influent and 25.7±21.3 ppb in the effluent. Average Zn removal was 52%. The wetland also ameliorated high pH values associated with influent water to values similar to those measured at reference sites. Seasonal variations in DOC concentration corresponded to seasonal variations in Cu and Zn removal efficiency. The concentration of Cu and Zn in the surface layer of the sediments has increased over the lifetime of the wetland and, like removal efficiency, demonstrated seasonal variation. Within its first year, the H-02 wetland showed biomarkers for sulfate-reducing bacteria. Sulfate-reduction and methane-oxidation rates in the sediments were determined using radiotracer techniques. Sulfate-reduction was detected in all depths of sediment cores, even in surface detritus layers. Gas measurements from H-02 sediments demonstrated that methane is available to support a methane oxidizing community, and active methane-oxidation was detected in the sediments and overlying water. Our results demonstrate that the H-02 wetlands are functioning successfully to remove Cu and Zn from influent waters. The continued success and long-term sustainability of the functioning H-02 system is predicated on maintaining in situ biogeochemistry. However, the relative importance of various biogeochemical cycles remains unclear. For example, the Cu and Zn deposited in the sediments are associated with organic detritus at the sediment surface; the extent and rate at which the metals will redistribute to more recalcitrant sulfide mineral phases remain to be determined. Thus, the H-02 wetland system is a valuable resource not only for metal removal at SRS, but also can further enhance the understanding of wetland function within the scientific and regulatory communities.

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.

Modulating inhibitors of transthyretin fibrillogenesis via sulfation: polychlorinated biphenyl sulfates as models.

PubMed

Grimm, Fabian A; Lehmler, Hans-Joachim; He, Xianran; Robertson, Larry W; Duffel, Michael W

2015-02-25

Small molecules that bind with high affinity to thyroxine (T4) binding sites on transthyretin (TTR) kinetically stabilize the protein's tetrameric structure, thereby efficiently decreasing the rate of tetramer dissociation in TTR related amyloidoses. Current research efforts aim to optimize the amyloid inhibiting properties of known inhibitors, such as derivatives of biphenyls, dibenzofurans and benzooxazoles, by chemical modification. In order to test the hypothesis that sulfate group substituents can improve the efficiencies of such inhibitors, we evaluated the potential of six polychlorinated biphenyl sulfates to inhibit TTR amyloid fibril formation in vitro. In addition, we determined their binding orientations and molecular interactions within the T4 binding site by molecular docking simulations. Utilizing this combined experimental and computational approach, we demonstrated that sulfation significantly improves the amyloid inhibiting properties as compared to both parent and hydroxylated PCBs. Importantly, several PCB sulfates were of equal or higher potency than some of the most effective previously described inhibitors. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Modulating Inhibitors of Transthyretin Fibrillogenesis via Sulfation: Polychlorinated Biphenyl Sulfates as Models1

PubMed Central

Grimm, Fabian A.; Lehmler, Hans-Joachim; He, Xianran; Robertson, Larry W.; Duffel, Michael W.

2015-01-01

Small molecules that bind with high affinity to thyroxine (T4) binding sites on transthyretin (TTR) kinetically stabilize the protein’s tetrameric structure, thereby efficiently decreasing the rate of tetramer dissociation in TTR related amyloidoses. Current research efforts aim to optimize the amyloid inhibiting properties of known inhibitors, such as derivatives of biphenyls, dibenzofurans and benzooxazoles, by chemical modification. In order to test the hypothesis that sulfate group substituents can improve the efficiencies of such inhibitors, we evaluated the potential of six polychlorinated biphenyl sulfates to inhibit TTR amyloid fibril formation in vitro. In addition, we determined their binding orientations and molecular interactions within the T4 binding site by molecular docking simulations. Utilizing this combined experimental and computational approach, we demonstrated that sulfation significantly improves the amyloid inhibiting properties as compared to both parent and hydroxylated PCBs. Importantly, several PCB sulfates were of equal or higher potency than some of the most effective previously described inhibitors. PMID:25595224

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®

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.

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

Semi-passive in-situ pilot scale bioreactor successfully removed sulfate and metals from mine impacted water under subarctic climatic conditions.

PubMed

Nielsen, Guillaume; Hatam, Ido; Abuan, Karl A; Janin, Amelie; Coudert, Lucie; Blais, Jean Francois; Mercier, Guy; Baldwin, Susan A

2018-04-23

Mine drainage contaminated with metals is a major environmental threat since it is a source of water pollution with devastating effects on aquatic ecosystems. Conventional active treatment technologies are prohibitively expensive and so there is increasing demand to develop reliable, cost-effective and sustainable passive or semi-passive treatment. These are promising alternatives since they leverage the metabolism of microorganisms native to the disturbed site at in situ or close to in situ conditions. Since this is a biological approach, it is not clear if semi-passive treatment would be effective in remote locations with extremely cold weather such as at mines in the subarctic. In this study we tested the hypothesis that sulfate-reducing bacteria, which are microorganisms that promote metal precipitation, exist in subarctic mine environments and their activity can be stimulated by adding a readily available carbon source. An experiment was setup at a closed mine in the Yukon Territory, Canada, where leaching of Zn and Cd occurs. To test if semi-passive treatment could precipitate these metals and prevent further leaching from waste rock, molasses as a carbon source was added to anaerobic bioreactors mimicking the belowground in-situ conditions. Microbial community analysis confirmed that sulfate-reducing bacteria became enriched in the bioreactors upon addition of molasses. The population composition remained fairly stable over the 14 month operating period despite temperature shifts from 17 to 5 °C. Sulfate reduction functionality was confirmed by quantification of the gene for dissimilatory sulfite reductase. Metals were removed from underground mine drainage fed into the bioreactors with Zn removal efficiency varying between 20.9% in winter and 89.3% in summer, and Cd removal efficiency between 39% in winter and 90.5% in summer. This study demonstrated that stimulation of native SRB in MIW was possible and that in situ semi-passive treatment can be effective in removing metals despite the cold climate. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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.

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.

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...

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 ...

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...

Investigation of kinetics and absorption isotherm models for hydroponic phytoremediation of waters contaminated with sulfate.

PubMed

Saber, Ali; Tafazzoli, Milad; Mortazavian, Soroosh; James, David E

2018-02-01

Two common wetland plants, Pampas Grass (Cortaderia selloana) and Lucky Bamboo (Dracaena sanderiana), were used in hydroponic cultivation systems for the treatment of simulated high-sulfate wastewaters. Plants in initial experiments at pH 7.0 removed sulfate more efficiently compared to the same experimental conditions at pH 6.0. Results at sulfate concentrations of 50, 200, 300, 600, 900, 1200, 1500 and 3000 mg/L during three consecutive 7-day treatment periods with 1-day rest intervals, showed decreasing trends of both removal efficiencies and uptake rates with increasing sulfate concentrations from the first to the second to the third 7-day treatment periods. Removed sulfate masses per unit dry plant mass, calculated after 23 days, showed highest removal capacity at 600 mg/L sulfate for both plants. A Langmuir-type isotherm best described sulfate uptake capacity of both plants. Kinetic studies showed that compared to pseudo first-order kinetics, pseudo-second order kinetic models slightly better described sulfate uptake rates by both plants. The Elovich kinetic model showed faster rates of attaining equilibrium at low sulfate concentrations for both plants. The dimensionless Elovich model showed that about 80% of sulfate uptake occurred during the first four days' contact time. Application of three 4-day contact times with 2-day rest intervals at high sulfate concentrations resulted in slightly higher uptakes compared to three 7-day contact times with 1-day rest intervals, indicating that pilot-plant scale treatment systems could be sized with shorter contact times and longer rest-intervals. Copyright © 2017 Elsevier Ltd. All rights reserved.

The effect of formaldehyde and nitrogen-containing compounds on the size and volume of aerosol particles

NASA Astrophysics Data System (ADS)

Millage, K.; Galloway, M. M.; De Haan, D. O.

2012-12-01

Atmospheric aerosol can interact with clouds in many ways, often resulting in the redistribution or absorption of solar energy or changes in precipitation efficiency. Secondary organic aerosol (SOA) in particular has been linked to climate change and a reduction in the number and size of cloud particles. The reactions of nitrogen containing compounds (primary amines, amino acids and ammonium sulfate) with carbonyl compounds (such as formaldehyde and glycolaldehyde) are potential sources of SOA. Aerosol containing formaldehyde and nitrogen-containing compounds (glycine, methylamine, arginine, or ammonium sulfate) was generated from buffered solutions (pH 5.4) using a nebulizer. The aerosol was then equilibrated into a chamber containing humid air (82-84% RH), and particle sizes were measured using a SMPS system over a period of 1 hour in order to examine how the size and volume of the aerosol particles changed. Formaldehyde concentrations were varied over multiple experiments. Arginine displayed a trend of increasing relative particle size with increasing formaldehyde concentration. Ammonium sulfate and formaldehyde displayed a decrease in relative particle sizes from 0:1 to 2:1 ratios of formaldehyde to ammonium sulfate, but then an increase in relative particle sizes with increasing amounts of formaldehyde. Similarly, glycine and methylamine initially displayed decreasing relative particle sizes, until reaching a 1:1 ratio of each to formaldehyde at which point the relative particle sizes steadily increased. These effects were likely caused by the evaporation of first-generation imine products.

Preparation of metal-resistant immobilized sulfate reducing bacteria beads for acid mine drainage treatment.

PubMed

Zhang, Mingliang; Wang, Haixia; Han, Xuemei

2016-07-01

Novel immobilized sulfate-reducing bacteria (SRB) beads were prepared for the treatment of synthetic acid mine drainage (AMD) containing high concentrations of Fe, Cu, Cd and Zn using up-flow anaerobic packed-bed bioreactor. The tolerance of immobilized SRB beads to heavy metals was significantly enhanced compared with that of suspended SRB. High removal efficiencies of sulfate (61-88%) and heavy metals (>99.9%) as well as slightly alkaline effluent pH (7.3-7.8) were achieved when the bioreactor was fed with acidic influent (pH 2.7) containing high concentrations of multiple metals (Fe 469 mg/L, Cu 88 mg/L, Cd 92 mg/L and Zn 128 mg/L), which showed that the bioreactor filled with immobilized SRB beads had tolerance to AMD containing high concentrations of heavy metals. Partially decomposed maize straw was a carbon source and stabilizing agent in the initial phase of bioreactor operation but later had to be supplemented by a soluble carbon source such as sodium lactate. The microbial community in the bioreactor was characterized by denaturing gradient gel electrophoresis (DGGE) and sequencing of partial 16S rDNA genes. Synergistic interaction between SRB (Desulfovibrio desulfuricans) and co-existing fermentative bacteria could be the key factor for the utilization of complex organic substrate (maize straw) as carbon and nutrients source for sulfate reduction. Copyright © 2016 Elsevier Ltd. All rights reserved.

Elemental sulfur and thiosulfate disproportionation by Desulfocapsa sulfoexigens sp. nov., a new anaerobic bacterium isolated from marine surface sediment.

PubMed

Finster, K; Liesack, W; Thamdrup, B

1998-01-01

A mesophilic, anaerobic, gram-negative bacterium, strain SB164P1, was enriched and isolated from oxidized marine surface sediment with elemental sulfur as the sole energy substrate in the presence of ferrihydrite. Elemental sulfur was disproportionated to hydrogen sulfide and sulfate. Growth was observed exclusively in the presence of a hydrogen sulfide scavenger, e.g., ferrihydrite. In the absence of a scavenger, sulfide and sulfate production were observed but no growth occurred. Strain SB164P1 grew also by disproportionation of thiosulfate and sulfite. With thiosulfate, the growth efficiency was higher in ferrihydrite-supplemented media than in media without ferrihydrite. Growth coupled to sulfate reduction was not observed. However, a slight sulfide production occurred in cultures incubated with formate and sulfate. Strain SB164P1 is the first bacterium described that grows chemolithoautotrophically exclusively by the disproportionation of inorganic sulfur compounds. Comparative 16S rDNA sequencing analysis placed strain SB164P1 into the delta subclass of the class Proteobacteria. Its closest relative is Desulfocapsa thiozymogenes, and slightly more distantly related are Desulfofustis glycolicus and Desulforhopalus vacuolatus. This phylogenetic cluster of organisms, together with members of the genus Desulfobulbus, forms one of the main lines of descent within the delta subclass of the Proteobacteria. Due to the common phenotypic characteristics and the phylogenetic relatedness to Desulfocapsa thiozymogenes, we propose that strain SB164P1 be designated the type strain of Desulfocapsa sulfoexigens sp. nov.

Elemental Sulfur and Thiosulfate Disproportionation by Desulfocapsa sulfoexigens sp. nov., a New Anaerobic Bacterium Isolated from Marine Surface Sediment

PubMed Central

Finster, Kai; Liesack, Werner; Thamdrup, Bo

1998-01-01

A mesophilic, anaerobic, gram-negative bacterium, strain SB164P1, was enriched and isolated from oxidized marine surface sediment with elemental sulfur as the sole energy substrate in the presence of ferrihydrite. Elemental sulfur was disproportionated to hydrogen sulfide and sulfate. Growth was observed exclusively in the presence of a hydrogen sulfide scavenger, e.g., ferrihydrite. In the absence of a scavenger, sulfide and sulfate production were observed but no growth occurred. Strain SB164P1 grew also by disproportionation of thiosulfate and sulfite. With thiosulfate, the growth efficiency was higher in ferrihydrite-supplemented media than in media without ferrihydrite. Growth coupled to sulfate reduction was not observed. However, a slight sulfide production occurred in cultures incubated with formate and sulfate. Strain SB164P1 is the first bacterium described that grows chemolithoautotrophically exclusively by the disproportionation of inorganic sulfur compounds. Comparative 16S rDNA sequencing analysis placed strain SB164P1 into the delta subclass of the class Proteobacteria. Its closest relative is Desulfocapsa thiozymogenes, and slightly more distantly related are Desulfofustis glycolicus and Desulforhopalus vacuolatus. This phylogenetic cluster of organisms, together with members of the genus Desulfobulbus, forms one of the main lines of descent within the delta subclass of the Proteobacteria. Due to the common phenotypic characteristics and the phylogenetic relatedness to Desulfocapsa thiozymogenes, we propose that strain SB164P1 be designated the type strain of Desulfocapsa sulfoexigens sp. nov. PMID:9435068

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

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.

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.

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.

Simultaneous Bioreduction of Multiple Oxidized Contaminants Using a Membrane Biofilm Reactor.

PubMed

Li, Haixiang; Lin, Hua; Xu, Xiaoyin; Jiang, Minmin; Chang, Chein-Chi; Xia, Siqing

2017-02-01

  This study tests a hydrogen-based membrane biofilm reactor (MBfR) to investigate simultaneous bioreduction of selected oxidized contaminants, including nitrate (-N), sulfate (), bromate (), chromate (Cr(VI)) and para-chloronitrobenzene (p-CNB). The experiments demonstrate that MBfR can achieve high performance for contaminants bioreduction to harmless or immobile forms in 240 days, with a maximum reduction fluxes of 0.901 g -N/m2·d, 1.573 g /m2·d, 0.009 g /m2·d, 0.022 g Cr(VI)/m2·d, and 0.043 g p-CNB/m2·d. Increasing H2 pressure and decreasing influent surface loading enhanced removal efficiency of the reactor. Flux analysis indicates that nitrate and sulfate reductions competed more strongly than , Cr(VI) and p-CNB reduction. The average H2 utilization rate, H2 flux, and H2 utilization efficiency of the reactor were 0.026 to 0.052 mg H2/cm3·d, 0.024 to 0.046 mg H2/cm2·d, and 97.5% to 99.3% (nearly 100%). Results show the hydrogen-based MBfR may be suitable for removing multiple oxidized contaminants in drinking water or groundwater.

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.

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.

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.

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.

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.

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.

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.

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...

A Novel Approach for Preventing HIV Infection and Reducing Risk to U.S. Military Personnel

DTIC Science & Technology

2012-09-01

polymers suchaschondroitin sulfate , inhibit the ability of semen to enhance HIV infection. Oversulfation of chondroitin sulfate converted this polymer...Deficient in Enhancing HIV Infection We previously demonstrated that the anionic polymers heparin and dextran sulfate , but not less negatively charged...2009). Spermatozoa capture HIV-1 through heparan sulfate and efficiently transmit the virus to dendritic cells. J. Exp. Med. 206, 2717– 2733. de

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 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.

Enhanced removal of Se(VI) from water via pre-corrosion of zero-valent iron using H2O2/HCl: Effect of solution chemistry and mechanism investigation.

PubMed

Shan, Chao; Chen, Jiajia; Yang, Zhe; Jia, Huichao; Guan, Xiaohong; Zhang, Weiming; Pan, Bingcai

2018-04-15

Although the removal of Se(VI) from water by using zero-valent iron (ZVI) is a promising method, passivation of ZVI severely inhibits its performance. To overcome such issue, we proposed an efficient technique to enhance Se(VI) removal via pre-corrosion of ZVI with H 2 O 2 /HCl in a short time (15 min). The resultant pcZVI suspension was weakly acidic (pH 4.56) and contained abundant aqueous Fe 2+ . 57 Fe Mössbauer spectroscopy showed that pcZVI mainly consisted of Fe 0 (66.2%), hydrated ferric oxide (26.3%), and Fe 3 O 4 (7.5%). Efficient removal of Se(VI) from sulfate-rich solution was achieved by pcZVI compared with ZVI (in the absence and presence of H 2 O 2 ) and acid-pretreated ZVI. Moreover, the efficient removal of Se(VI) by pcZVI sustained over a broad pH range (3-9) due to its strong buffering power. The presence of chloride, carbonate, nitrate, and common cations (Na + , K + , Ca 2+ , and Mg 2+ ) posed negligible influence on the removal of Se(VI) by pcZVI, while the inhibitory effect induced by sulfate, silicate, and phosphate indicated the significance of Se(VI) adsorption as a prerequisite step for its removal. The consumption of aqueous Fe 2+ was associated with Se(VI) removal, and X-ray absorption near edge structure revealed that the main pathway for Se(VI) removal by pcZVI was a stepwise reduction of Se(VI) to Se(IV) and then Se 0 as the dominant final state (78.2%). Moreover, higher electron selectivity of pcZVI was attributed to the enhanced enrichment of Se oxyanions prior to their reduction. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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.

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. ...

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 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.

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.

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

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.

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

Participation of 3-O-sulfated heparan sulfates in the protection of macrophages by herpes simplex virus-1 glycoprotein D and cyclophilin B against apoptosis.

PubMed

Delos, Maxime; Hellec, Charles; Foulquier, François; Carpentier, Mathieu; Allain, Fabrice; Denys, Agnès

2017-02-01

Heparan sulfates (HS) are involved in numerous biological processes, which rely on their ability to interact with a large panel of proteins. Although the reaction of 3-O-sulfation can be catalysed by the largest family of HS sulfotransferases, very few mechanisms have been associated with this modification and to date, only glycoprotein D (gD) of herpes simplex virus-1 (HSV-1 gD) and cyclophilin B (CyPB) have been well-described as ligands for 3- O -sulfated HS. Here, we hypothesized that both ligands could induce the same responses via a mechanism dependent on 3- O -sulfated HS. First, we checked that HSV-1 gD was as efficient as CyPB to induce the activation of the same signalling events in primary macrophages. We then demonstrated that both ligands efficiently reduced staurosporin-induced apoptosis and modulated the expression of apoptotic genes. In addition to 3- O -sulfated HS, HSV-1 gD was reported to interact with other receptors, including herpes virus entry mediator (HVEM), nectin-1 and -2. Thus, we decided to identify the contribution of each binding site in the responses triggered by HSV-1 gD and CyPB. We found that knock-down of 3- O -sulfotransferase 2, which is the main 3- O -sulfated HS-generating enzyme in macrophages, strongly reduced the responses induced by both ligands. Moreover, silencing the expression of HVEM rendered macrophages unresponsive to either HSV-1 gD and CyPB, thus indicating that both proteins induced the same responses by interacting with a complex formed by 3- O -sulfated HS and HVEM. Collectively, our results suggest that HSV-1 might hijack the binding sites for CyPB in order to protect macrophages against apoptosis for efficient infection.

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...

Use of Industrial Waste (Al-Dross, Red Mud, Mill Scale) as Fluxing Agents in the Sulfurization of Fe-Ni-Cu-Co Alloy by Carbothermic Reduction of Calcium Sulfate

NASA Astrophysics Data System (ADS)

Heo, Jung Ho; Jeong, Eui Hyuk; Nam, Chul Woo; Park, Kyung Ho; Park, Joo Hyun

2018-06-01

The use of industrial waste [mill scale (MS), red mud (RM), Al-dross (AD)] as fluxing agents in the sulfurization of Fe-Ni-Cu-Co alloy to matte (Fe-Ni-Cu-Co-S) by carbothermic reduction of CaSO4 was investigated at 1673 K (1400 °C). The sulfurization efficiency (SE) was 76 (± 2) pct at RM or AD single fluxing. However, SE drastically increased to approximately 89 pct at a `5AD + 5MS' combination, which was equivalent to reagent-grade chemical `5Al2O3 + 5Fe2O3' fluxing (SE = 88 pct). The present results can be used to improve the cost-effective recovery of rare metals (Ni and Co) from deep sea manganese nodules.

Use of Industrial Waste (Al-Dross, Red Mud, Mill Scale) as Fluxing Agents in the Sulfurization of Fe-Ni-Cu-Co Alloy by Carbothermic Reduction of Calcium Sulfate

NASA Astrophysics Data System (ADS)

Heo, Jung Ho; Jeong, Eui Hyuk; Nam, Chul Woo; Park, Kyung Ho; Park, Joo Hyun

2018-03-01

The use of industrial waste [mill scale (MS), red mud (RM), Al-dross (AD)] as fluxing agents in the sulfurization of Fe-Ni-Cu-Co alloy to matte (Fe-Ni-Cu-Co-S) by carbothermic reduction of CaSO4 was investigated at 1673 K (1400 °C). The sulfurization efficiency (SE) was 76 (± 2) pct at RM or AD single fluxing. However, SE drastically increased to approximately 89 pct at a `5AD + 5MS' combination, which was equivalent to reagent-grade chemical `5Al2O3 + 5Fe2O3' fluxing (SE = 88 pct). The present results can be used to improve the cost-effective recovery of rare metals (Ni and Co) from deep sea manganese nodules.

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.

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

Bioreduction of para-chloronitrobenzene in drinking water using a continuous stirred hydrogen-based hollow fiber membrane biofilm reactor.

PubMed

Xia, Siqing; Li, Haixiang; Zhang, Zhiqiang; Zhang, Yanhao; Yang, Xin; Jia, Renyong; Xie, Kang; Xu, Xiaotian

2011-08-30

para-Chloronitrobenzene (p-CNB) is particularly harmful and persistent in the environment and is one of the priority pollutants. A feasible degradation pathway for p-CNB is bioreduction under anaerobic conditions. Bioreduction of p-CNB using a hydrogen-based hollow fiber membrane biofilm reactor (HFMBfR) was investigated in the present study. The experiment results revealed that p-CNB was firstly reduced to para-chloraniline (p-CAN) as an intermediate and then reduced to aniline that involves nitro reduction and reductive dechlorination with H(2) as the electron donor. The HFMBfR had reduced p-CNB to a major extent with a maximum removal percentage of 99.3% at an influent p-CNB concentration of 2mg/L and a hydraulic residence time of 4.8h, which corresponded to a p-CNB flux of 0.058g/m(2) d. The H(2) availability, p-CNB loading, and the presence of competing electron acceptors affected the p-CNB reduction. Flux analysis indicated that the reduction of p-CNB and p-CAN could consume fewer electrons than that of nitrate and sulfate. The HFMBfR had high average hydrogen utilization efficiencies at different steady states in this experiment, with a maximum efficiency at 98.2%. Copyright © 2011 Elsevier B.V. All rights reserved.

Biogeochemical dynamics of pollutants in Insitu groundwater remediation systems

NASA Astrophysics Data System (ADS)

Kumar, N.; Millot, R.; Rose, J.; Négrel, P.; Battaglia-Brunnet, F.; Diels, L.

2010-12-01

Insitu (bio) remediation of groundwater contaminants has been area of potential research interest in last few decades as the nature of contaminant encountered has also changed drastically. This gives tough challenge to researchers in finding a common solution for all contaminants together in one plume. Redox processes play significant role in pollutant dynamics and mobility in such systems. Arsenic particularly in reduced environments can get transformed into its reduced form (As3+), which is apparently more mobile and highly toxic. Also parallel sulfate reduction can lead to sulfide production and formation of thioarsenic species. On the other hand heavy metals (Zn, Fe, and Cd) in similar conditions will favour more stable metal sulfide precipitation. In the present work, we tested Zero Valent Iron (ZVI) in handling such issues and found promising results. Although it has been well known for contaminants like arsenic and chlorinated compounds but not much explored for heavy metals. Its high available surface area supports precipitation and co -precipitation of contaminants and its highly oxidizing nature and water born hydrogen production helps in stimulation of microbial activities in sediment and groundwater. These sulfate and Iron reducing bacteria can further fix heavy metals as stable metal sulfides by using hydrogen as potential electron donor. In the present study flow through columns (biotic and control) were set up in laboratory to understand the behaviour of contaminants in subsurface environments, also the impact of microbiology on performance of ZVI was studied. These glass columns (30 x 4cm) with intermediate sampling points were monitored over constant temperature (20°C) and continuous groundwater (up)flow at ~1ml/hr throughout the experiment. Simulated groundwater was prepared in laboratory containing sulfate, metals (Zn,Cd) and arsenic (AsV). While chemical and microbial parameters were followed regularly over time, solid phase has been characterized at the end of experiment using synchrotron and other microscopic techniques (SEM, µXRF). Stable isotope signatures have been proved as a critical tool in understanding the redox and microbial processes. We monitored ∂34S, ∂66Zn and ∂56Fe isotope evolution with time to understand the relationship between biogeochemical process and isotope fractionation. We observed Δ34S biotic - abiotic ~6‰ and ∂56Fe variation up to 1.5‰ in our study. ZVI was very efficient in metal removal and also in enhancing sulfate reduction in column sediment. Arsenic reduction and thiarsenic species were also detected in biotic columns showing a positive correlation with sulfide production and Fe speciation. Latest results will be presented with integration of different processes. This multidisciplinary approach will help in deep understanding of contaminants behaviour and also to constrain the efficiency and longitivity of treatment system for different contaminants. “This is contribution of the AquaTrain MRTN (Contract No. MRTN-CT-2006-035420) funded under the European Commission sixth framework programme (2002-2006) Marie Curie Actions, Human Resources & Mobility Activity Area- Research Training Networks”

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.

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.

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.

Distinctive and Complementary MS2 Fragmentation Characteristics for Identification of Sulfated Sialylated N-Glycopeptides by nanoLC-MS/MS Workflow

NASA Astrophysics Data System (ADS)

Kuo, Chu-Wei; Guu, Shih-Yun; Khoo, Kay-Hooi

2018-04-01

High sensitivity identification of sulfated glycans carried on specific sites of glycoproteins is an important requisite for investigation of molecular recognition events involved in diverse biological processes. However, aiming for resolving site-specific glycosylation of sulfated glycopeptides by direct LC-MS2 sequencing is technically most challenging. Other than the usual limiting factors such as lower abundance and ionization efficiency compared to analysis of non-glycosylated peptides, confident identification of sulfated glycopeptides among the more abundant non-sulfated glycopeptides requires additional considerations in the selective enrichment and detection strategies. Metal oxide has been applied to enrich phosphopeptides and sialylated glycopeptides, but its use to capture sulfated glycopeptides has not been investigated. Likewise, various complementary MS2 fragmentation modes have yet to be tested against sialylated and non-sialylated sulfoglycopeptides due to limited appropriate sample availability. In this study, we have investigated the feasibility of sequencing tryptic sulfated N-glycopeptide and its MS2 fragmentation characteristics by first optimizing the enrichment methods to allow efficient LC-MS detection and MS2 analysis by a combination of CID, HCD, ETD, and EThcD on hybrid and tribrid Orbitrap instruments. Characteristic sulfated glyco-oxonium ions and direct loss of sulfite from precursors were detected as evidences of sulfate modification. It is anticipated that the technical advances demonstrated in this study would allow a feasible extension of our sulfoglycomic analysis to sulfoglycoproteomics. [Figure not available: see fulltext.

Human DHEA sulfation requires direct interaction between PAPS synthase 2 and DHEA sulfotransferase SULT2A1.

PubMed

Mueller, Jonathan W; Idkowiak, Jan; Gesteira, Tarsis F; Vallet, Cecilia; Hardman, Rebecca; van den Boom, Johannes; Dhir, Vivek; Knauer, Shirley K; Rosta, Edina; Arlt, Wiebke

2018-06-22

The high-energy sulfate donor 3'-phosphoadenosine-5'-phosphosulfate (PAPS), generated by human PAPS synthase isoforms PAPSS1 and PAPSS2, is required for all human sulfation pathways. Sulfotransferase SULT2A1 uses PAPS for sulfation of the androgen precursor dehydroepiandrosterone (DHEA), thereby reducing downstream activation of DHEA to active androgens. Human PAPSS2 mutations manifest with undetectable DHEA sulfate, androgen excess, and metabolic disease, suggesting that ubiquitous PAPSS1 cannot compensate for deficient PAPSS2 in supporting DHEA sulfation. In knockdown studies in human adrenocortical NCI-H295R1 cells, we found that PAPSS2, but not PAPSS1, is required for efficient DHEA sulfation. Specific APS kinase activity, the rate-limiting step in PAPS biosynthesis, did not differ between PAPSS1 and PAPSS2. Co-expression of cytoplasmic SULT2A1 with a cytoplasmic PAPSS2 variant supported DHEA sulfation more efficiently than co-expression with nuclear PAPSS2 or nuclear/cytosolic PAPSS1. Proximity ligation assays revealed protein-protein interactions between SULT2A1 and PAPSS2 and, to a lesser extent, PAPSS1. Molecular docking studies showed a putative binding site for SULT2A1 within the PAPSS2 APS kinase domain. Energy-dependent scoring of docking solutions identified the interaction as specific for the PAPSS2 and SULT2A1 isoforms. These findings elucidate the mechanistic basis for the selective requirement for PAPSS2 in human DHEA sulfation. © 2018 Mueller et al.

Sulfates in Indiana substrates.

DOT National Transportation Integrated Search

2016-06-01

This study was undertaken to develop modifications for improving cost and time efficiencies without sacrificing accuracy and precision to : the current method employed by the Indiana Department of Transportation (INDOT) for determining sulfate conten...

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 ...

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).

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

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

Towprayoon, S.; Kuntrangwattana, S.

Cutting oil wastewater from an iron and steel factory was applied to the soil windrow. Self-remediation was then compared with remediation with acclimatized indigenous microbes. The incremental reduction rate of the microorganisms and hydrocarbon-degradable microbes was slower in self-remediation than in the latter treatment. Within 30 days, when the acclimatized indigenous microbes were used, there was a significant reduction of the contaminated hydrocarbons, while self-remediation took longer to reduce to the same concentration. Various nitrogen sources were applied to the soil pile, namely, organic compost, chemical fertilizer, ammonium sulfate, and urea. The organic compost induced a high yield of hydrocarbon-degradablemore » microorganisms, but the rate at which the cutting oil in the soil decreased was slower than when other nitrogen sources were used. The results of cutting oil degradation studied by gas chromatography showed the absence of some important hydrocarbons. The increment of the hydrocarbon-degradable microbes in the land treatment ecosystem does not necessarily correspond to the hydrocarbon reduction efficiency. 3 refs., 3 figs.« less

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 atmospheric organosulfates using HILIC chromatography with MS detection

NASA Astrophysics Data System (ADS)

Hettiyadura, A. P. S.; Stone, E. A.; Kundu, S.; Baker, Z.; Geddes, E.; Richards, K.; Humphry, T.

2014-12-01

Measurements of organosulfates in ambient aerosols provide insight to the extent of secondary organic aerosol (SOA) formation from mixtures of biogenic gases and anthropogenic pollutants. Organosulfates have, however, proved analytically challenging to measure. This study presents a sensitive new analytical method for the quantification of organosulfates based upon ultra-performance liquid chromatography with negative electrospray ionization mass spectrometry (UPLC-ESI-MS/MS). The separation is based upon hydrophilic interaction liquid chromatography (HILIC) with an amide stationary phase that provides excellent retention of carboxy-organosulfates and methyltetrol-derived organosulfates. The method is validated using six model compounds: methyl sulfate, ethyl sulfate, benzyl sulfate, hydroxyacetone sulfate, lactic acid sulfate, and glycolic acid sulfate. A straightforward protocol for preparation of highly pure organosulfate potassium salts for use as quantification standards is presented. This highly efficient method of separating and quantifying organosulfates is used to evaluate the efficiency and precision of two methods of ambient PM2.5 sample extraction. Spike recoveries averaged 98 ± 8% for extraction by sonication and 98 ± 10% for extraction by rotary-shaking. Sonication was determined to be the superior method for its better precision. Analysis of ambient PM2.5 samples collected 10-11 July 2013 in Centreville, AL, USA during the Southeast Atmosphere Study (SAS) confirms the presence of hydroxyacetone sulfate in ambient aerosol for the first time. Glycolic acid sulfate was the most abundant compound measured (ranging 8-14 ng m-3), followed by hydroxyl acetone sulfate (2.7-5.8 ng m-3) and lactic acid sulfate (1.4-2.9 ng m-3). Trace amounts of methyl sulfate were detected, while ethyl sulfate and benzyl sulfate were not detected. Future research will focus on the development of additional organosulfates standards, expansion of this UPLC-MS/MS to include more target molecules, and the application of this method to assess temporal variations in organosulfates in ambient environments.

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

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.

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.

Statistical media design for efficient polyhydroxyalkanoate production in Pseudomonas sp. MNNG-S.

PubMed

Saranya, V; Rajeswari, V; Abirami, P; Poornimakkani, K; Suguna, P; Shenbagarathai, R

2016-07-03

Polyhydroxyalkanoate (PHA) is a promising polymer for various biomedical applications. There is a high need to improve the production rate to achieve end use. When a cost-effective production was carried out with cheaper agricultural residues like molasses, traces of toxins were incorporated into the polymer, which makes it unfit for biomedical applications. On the other hand, there is an increase in the popularity of using chemically defined media for the production of compounds with biomedical applications. However, these media do not exhibit favorable characteristics such as efficient utilization at large scale compared to complex media. This article aims to determine the specific nutritional requirement of Pseudomonas sp. MNNG-S for efficient production of polyhydroxyalkanoate. Response surface methodology (RSM) was used in this study to statistically design for PHA production based on the interactive effect of five significant variables (sucrose; potassium dihydrogen phosphate; ammonium sulfate; magnesium sulfate; trace elements). The interactive effects of sucrose with ammonium sulfate, ammonium sulfate with combined potassium phosphate, and trace element with magnesium sulfate were found to be significant (p < .001). The optimization approach adapted in this study increased the PHA production more than fourfold (from 0.85 g L(-1) to 4.56 g L(-1)).

Reduction and Immobilization of Radionuclides and Toxic Metal Ions Using Combined Zero Valent Iron and Anaerobic Bacteria

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

Lenly J. Weathers; Lynn E. Katz

2002-05-29

The use of zero valent iron, permeable reactive barriers (PRBs) for groundwater remediation continues to increase. AN exciting variation of this technology involves introducing anaerobic bacteria into these barriers so that both biological and abiotic pollutant removal processes are functional. This work evaluated the hypothesis that a system combining a mixed culture of sulfate reducing bacteria (SRB) with zero valent iron would have a greater cr(VI) removal efficiency and a greater total Cr(VI) removal capacity than a zero valent iron system without the microorganisms. Hence, the overall goal of this research was to compare the performance of these types ofmore » systems with regard to their Cr(VI) removal efficiency and total Cr(VI) removal capacity. Both batch and continuous flow reactor systems were evaluated.« less

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...

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.

Effects of Lead and Mercury on Sulfate-Reducing Bacterial Activity in a Biological Process for Flue Gas Desulfurization Wastewater Treatment

NASA Astrophysics Data System (ADS)

Zhang, Liang; Lin, Xiaojuan; Wang, Jinting; Jiang, Feng; Wei, Li; Chen, Guanghao; Hao, Xiaodi

2016-07-01

Biological sulfate-reducing bacteria (SRB) may be effective in removing toxic lead and mercury ions (Pb(II) and Hg(II)) from wet flue gas desulfurization (FGD) wastewater through anaerobic sulfite reduction. To confirm this hypothesis, a sulfite-reducing up-flow anaerobic sludge blanket reactor was set up to treat FGD wastewater at metal loading rates of 9.2 g/m3-d Pb(II) and 2.6 g/m3-d Hg(II) for 50 days. The reactor removed 72.5 ± 7% of sulfite and greater than 99.5% of both Hg(II) and Pb(II). Most of the removed lead and mercury were deposited in the sludge as HgS and PbS. The contribution of cell adsorption and organic binding to Pb(II) and Hg(II) removal was 20.0 ± 0.1% and 1.8 ± 1.0%, respectively. The different bioavailable concentration levels of lead and mercury resulted in different levels of lethal toxicity. Cell viability analysis revealed that Hg(II) was less toxic than Pb(II) to the sludge microorganisms. In the batch tests, increasing the Hg(II) feeding concentration increased sulfite reduction rates. In conclusion, a sulfite-reducing reactor can efficiently remove sulfite, Pb(II) and Hg(II) from FGD wastewater.

Effects of Lead and Mercury on Sulfate-Reducing Bacterial Activity in a Biological Process for Flue Gas Desulfurization Wastewater Treatment

PubMed Central

Zhang, Liang; Lin, Xiaojuan; Wang, Jinting; Jiang, Feng; Wei, Li; Chen, Guanghao; Hao, Xiaodi

2016-01-01

Biological sulfate-reducing bacteria (SRB) may be effective in removing toxic lead and mercury ions (Pb(II) and Hg(II)) from wet flue gas desulfurization (FGD) wastewater through anaerobic sulfite reduction. To confirm this hypothesis, a sulfite-reducing up-flow anaerobic sludge blanket reactor was set up to treat FGD wastewater at metal loading rates of 9.2 g/m3-d Pb(II) and 2.6 g/m3-d Hg(II) for 50 days. The reactor removed 72.5 ± 7% of sulfite and greater than 99.5% of both Hg(II) and Pb(II). Most of the removed lead and mercury were deposited in the sludge as HgS and PbS. The contribution of cell adsorption and organic binding to Pb(II) and Hg(II) removal was 20.0 ± 0.1% and 1.8 ± 1.0%, respectively. The different bioavailable concentration levels of lead and mercury resulted in different levels of lethal toxicity. Cell viability analysis revealed that Hg(II) was less toxic than Pb(II) to the sludge microorganisms. In the batch tests, increasing the Hg(II) feeding concentration increased sulfite reduction rates. In conclusion, a sulfite-reducing reactor can efficiently remove sulfite, Pb(II) and Hg(II) from FGD wastewater. PMID:27455890

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.

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 (

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.

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.

The ecophysiology of sulfur isotope fractionation by sulfate reducing bacteria in response to variable environmental conditions

NASA Astrophysics Data System (ADS)

Leavitt, W.; Bradley, A. S.; Johnston, D. T.; Pereira, I. A. C.; Venceslau, S.; Wallace, C.

2014-12-01

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 sulfide produced is depleted in the heavier isotopes of sulfur relative to sulfate. The magnitude of discrimination (fractionation) depends on: i) the cell-specific sulfate reduction rate (csSRR, Kaplan & Rittenberg (1964) Can. J. Microbio.; Chambers et al. (1975) Can. J. Microbio; Sim et al. (2011) GCA; Leavitt et al. (2013) PNAS), ii) the ambient sulfate concentration (Harrison & Thode (1958) Research; Habicht et al. (2002) Science; Bradley et al. in review), iii) both sulfate and electron donor availability, or iv) an intrinsic physiological limitation (e.g. cellular division rate). When neither sulfate nor electron donor limits csSRR a more complex function relates the magnitude of isotope fractionation to cell physiology and environmental conditions. In recent and on-going work we have examined the importance of enzyme-specific fractionation factors, as well as the influence of electron donor or electron acceptor availability under carefully controlled culture conditions (e.g. Leavitt et al. (2013) PNAS). In light of recent advances in MSR genetics and biochemistry we utilize well-characterized mutant strains, along with a continuous-culture methodology (Leavitt et al. (2013) PNAS) to further probe the fractionation capacity of this metabolism under controlled physiological conditions. We present our latest findings on the magnitude of S and D/H isotope fractionation in both wild type and mutant strains. We will discuss these in light of recent theoretical advances (Wing & Halevy (2014) PNAS), examining the mode and relevance of MSR isotope fractionation in the laboratory to modern and ancient environmental settings, particularly anoxic marine sediments.

Impact of salt exposure on N-acetylgalactosamine-4-sulfatase (arylsulfatase B) activity, glycosaminoglycans, kininogen, and bradykinin

PubMed Central

Kotlo, Kumar; Bhattacharyya, Sumit; Yang, Bo; Feferman, Leonid; Tejaskumar, Shah; Linhardt, Robert; Danziger, Robert

2013-01-01

N -acetylgalactosamine-4-sulfatase (Arylsulfatase B; ARSB) is the enzyme that removes sulfate groups from the N-acetylgalactosamine-4-sulfate residue at the non-reducing end of chondroitin-4-sulfate (C4S) and dermatan sulfate (DS). Previous studies demonstrated reduction in cell-bound high molecular weight kininogen in normal rat kidney (NRK) epithelial cells when chondroitin-4-sulfate content was reduced following overexpression of ARSB activity, and chondroitinase ABC produced similar decline in cell-bound kininogen. Reduction in the cell-bound kininogen was associated with increase in secreted bradykinin. In this report, we extend the in vitro findings to in vivo models, and present findings in Dahl salt-sensitive (SS) rats exposed to high (SSH) and low salt (SSL) diets. In the renal tissue of the SSH rats, ARSB activity was significantly less than in the SSL rats, and chondroitin-4-sulfate and total sulfated glycosaminoglycan content were significantly greater. Disaccharide analysis confirmed marked increase in C4S disaccharides in the renal tissue of the SSH rats. In contrast, unsulfated, hyaluronan-derived disaccharides were increased in the rats on the low salt diet. In the SSH rats, with lower ARSB activity and higher C4S levels, cell-bound, high-molecular weight kininogen was greater and urinary bradykinin was lower. ARSB activity in renal tissue and NRK cells declined when exogenous chloride concentration was increased in vitro. The impact of high chloride exposure in vivo on ARSB, chondroitin-4-sulfation, and C4S-kininogen binding provides a mechanism that links dietary salt intake with bradykinin secretion and may be a factor in blood pressure regulation. PMID:23385884

Impact of salt exposure on N-acetylgalactosamine-4-sulfatase (arylsulfatase B) activity, glycosaminoglycans, kininogen, and bradykinin.

PubMed

Kotlo, Kumar; Bhattacharyya, Sumit; Yang, Bo; Feferman, Leonid; Tejaskumar, Shah; Linhardt, Robert; Danziger, Robert; Tobacman, Joanne K

2013-10-01

N-acetylgalactosamine-4-sulfatase (Arylsulfatase B; ARSB) is the enzyme that removes sulfate groups from the N-acetylgalactosamine-4-sulfate residue at the non-reducing end of chondroitin-4-sulfate (C4S) and dermatan sulfate (DS). Previous studies demonstrated reduction in cell-bound high molecular weight kininogen in normal rat kidney (NRK) epithelial cells when chondroitin-4-sulfate content was reduced following overexpression of ARSB activity, and chondroitinase ABC produced similar decline in cell-bound kininogen. Reduction in the cell-bound kininogen was associated with increase in secreted bradykinin. In this report, we extend the in vitro findings to in vivo models, and present findings in Dahl salt-sensitive (SS) rats exposed to high (SSH) and low salt (SSL) diets. In the renal tissue of the SSH rats, ARSB activity was significantly less than in the SSL rats, and chondroitin-4-sulfate and total sulfated glycosaminoglycan content were significantly greater. Disaccharide analysis confirmed marked increase in C4S disaccharides in the renal tissue of the SSH rats. In contrast, unsulfated, hyaluronan-derived disaccharides were increased in the rats on the low salt diet. In the SSH rats, with lower ARSB activity and higher C4S levels, cell-bound, high-molecular weight kininogen was greater and urinary bradykinin was lower. ARSB activity in renal tissue and NRK cells declined when exogenous chloride concentration was increased in vitro. The impact of high chloride exposure in vivo on ARSB, chondroitin-4-sulfation, and C4S-kininogen binding provides a mechanism that links dietary salt intake with bradykinin secretion and may be a factor in blood pressure regulation.

Atmospheric Sulfur Cycle Simulated in The Global Model GOCART: Model Description and Global Properties

NASA Technical Reports Server (NTRS)

Chin, Mian; Rood, Richard B.; Lin, Shian-Jiann; Mueller, Jean-Francois; Thompson, Anne M.

2000-01-01

The Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model is used to simulate the atmospheric sulfur cycle. The model uses the simulated meteorological data from the Goddard Earth Observing System Data Assimilation System (GEOS DAS). Global sulfur budgets from a 6-year simulation for SO2, sulfate, dimethylsulfide (DMS), and methanesulfonic acid (MSA) are presented in this paper. In a normal year without major volcanic perturbations, about 20% of the sulfate precursor emission is from natural sources (biogenic and volcanic) and 80% is anthropogenic: the same sources contribute 339% and 67% respectively to the total sulfate burden. A sulfate production efficiency of 0.41 - 0.42 is estimated in the model, an efficiency which is defined as a ratio of the amount oi sulfate produced to the total amount of SO2 emitted and produced in the atmosphere. This value indicates that less than half of the SO2 entering the atmosphere contributes to the sulfate production, the rest being removed by dry and wet depositions. In a simulation for 1990, we estimate a total sulfate production of 39 Tg S /yr with 36% and 64% respectively from in-air and in-cloud oxidation of SO2. We also demonstrate that major volcanic eruptions, such as the Mt. Pinatubo eruption in 1991, can significantly change the sulfate formation pathways, distributions, abundance, and lifetime. Comparison with other models shows that the parameterizations for wet removal or wet production of sulfate are the most critical factors in determining the burdens of SO2 and sulfate. Therefore, a priority for future research should be to reduce the large uncertainties associated with the wet physical and chemical processes.

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.

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

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.

Fe-C-S systematics in Bengal Fan sediments

NASA Astrophysics Data System (ADS)

Volvoikar, S. P.; Mazumdar, A.; Goswami, H.; Pujari, S.; Peketi, A.

2017-12-01

Global biogeochemical cycles of iron, carbon and sulfur (Fe-C-S) are interrelated. Sulfate reduction in marine sediments is the major factor controlling the cycling and burial of carbon, sulfur and iron. Organoclastic sulfate reduction and anaerobic oxidation of methane (AOM) are the two main processes responsible for sulfate reduction in marine sediments. The amount and reactivity of organic matter, iron minerals and concentrations of dissolved sulfide in pore water control the burial of iron sulfide and organic bound sulfur in marine sediments. Here we investigate the sulfidization process in a sediment core from the western part of upper Bay of Bengal fan characterized by efficient burial of organic matter with siliclastic load. A 30 m long sediment core (MD 161/29, Lat. 170 18.04' N, Long. 870 22.56' E, water depth: 2434m) was collected onboard Marion Dufresne (May, 2007) and studied for Fe-S speciation and organic matter characterization. Buffered dithionite extractable iron (FeD) varies from 0.71 to 1.43 wt % (Avg. 0.79 wt %). FeD represents Fe oxides and oxyhydroxides mainly, ferrihydrite, lepidocrocite, goethite and hematite. Acid volatile sulfur (AVS) varies from 0.0015 to 0.63 wt % (avg: 0.058 wt %), while chromium reducible sulfur (CRS) varies from 0.00047 to 0.29 wt % (avg. 0.054 wt %). Based on the vertical distribution patterns of FeD, AVS and CRS, the core is divided into three zones, the lower (3000 to 1833 cm), middle (1833 to 398 cm) and upper (398 cm to surface) zones. FeD shows higher concentration in the lower zone. FeTR (FeOx + FeD + FeCRS + FeAVS) also exhibit higher concentration in this zone, suggesting higher availability of reactive iron for iron sulfide precipitation. AVS, elemental sulfur, spikes of CRS and gradual enrichment of δ34SAVS and δ34SCRS with sharp peaks in-between is noted in the lower zone. The gradual enrichment of δ34SAVS and δ34SCRS is the outcome of late diagenetic pyritization with higher availability of sulfide (HS- and H2S) from AOM.

Simultaneous and rapid determination of multiple component concentrations in a Kraft liquor process stream

DOEpatents

Li, Jian [Marietta, GA; Chai, Xin Sheng [Atlanta, GA; Zhu, Junyoung [Marietta, GA

2008-06-24

The present invention is a rapid method of determining the concentration of the major components in a chemical stream. The present invention is also a simple, low cost, device of determining the in-situ concentration of the major components in a chemical stream. In particular, the present invention provides a useful method for simultaneously determining the concentrations of sodium hydroxide, sodium sulfide and sodium carbonate in aqueous kraft pulping liquors through use of an attenuated total reflectance (ATR) tunnel flow cell or optical probe capable of producing a ultraviolet absorbency spectrum over a wavelength of 190 to 300 nm. In addition, the present invention eliminates the need for manual sampling and dilution previously required to generate analyzable samples. The inventive method can be used in Kraft pulping operations to control white liquor causticizing efficiency, sulfate reduction efficiency in green liquor, oxidation efficiency for oxidized white liquor and the active and effective alkali charge to kraft pulping operations.

Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

NASA Astrophysics Data System (ADS)

Johnson, Craig A.; Emsbo, Poul; Poole, Forrest G.; Rye, Robert 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 δ 34S versus δ 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 δ 34S versus δ 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 H 2O, 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.

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures.

PubMed

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-04-14

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with Species, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene "painting" on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

PubMed Central

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-01-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene “painting” on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis. PMID:24728289

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

NASA Astrophysics Data System (ADS)

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-04-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene ``painting'' on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

Experimental investigation on thermochemical sulfate reduction by H2S initiation

USGS Publications Warehouse

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

2008-01-01

Hydrogen sulfide (H2S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 ??C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO4 in the presence of variable H2S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H2S occurred under acidic conditions (at pH ???3-3.5). However, sulfate reduction at pH ???5.0 was undetectable even at high initial H2S concentrations. To investigate whether the reaction of H2S(aq) and HSO4- occurs at pH ???3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO4 and variable H2S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO4 reduction was not measurable in the absence of paraffin even with high H2S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H2S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H2S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc. 82, 1911-1916). Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H2S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 ??C and a 0.1-??C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H2S pressure. Thus, we propose that the LSC produced from H2S reaction with HC are most likely the reactive intermediates for H2S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content. ?? 2008 Elsevier Ltd. All rights reserved.

Selective removal of arsenic and monovalent ions from brackish water reverse osmosis concentrate.

PubMed

Xu, Pei; Capito, Marissa; Cath, Tzahi Y

2013-09-15

Concentrate disposal and management is a considerable challenge for the implementation of desalination technologies, especially for inland applications where concentrate disposal options are limited. This study has focused on selective removal of arsenic and monovalent ions from brackish groundwater reverse osmosis (RO) concentrate for beneficial use and safe environmental disposal using in situ and pre-formed hydrous ferric oxides/hydroxides adsorption, and electrodialysis (ED) with monovalent permselective membranes. Coagulation with ferric salts is highly efficient at removing arsenic from RO concentrate to meet a drinking water standard of 10 μg/L. The chemical demand for ferric chloride however is much lower than ferric sulfate as coagulant. An alternative method using ferric sludge from surface water treatment plant is demonstrated as an efficient adsorbent to remove arsenic from RO concentrate, providing a promising low cost, "waste treat waste" approach. The monovalent permselective anion exchange membranes exhibit high selectivity in removing monovalent anions over di- and multi-valent anions. The transport of sulfate and phosphate through the anion exchange membranes was negligible over a broad range of electrical current density. However, the transport of divalent cations such as calcium and magnesium increases through monovalent permselective cation exchange membranes with increasing current density. Higher overall salt concentration reduction is achieved around limiting current density while higher normalized salt removal rate in terms of mass of salt per membrane area and applied energy is attained at lower current density because the energy unitization efficiency decreases at higher current density. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Impacts of stratospheric sulfate geoengineering on tropospheric ozone

NASA Astrophysics Data System (ADS)

Xia, Lili; Nowack, Peer J.; Tilmes, Simone; Robock, Alan

2017-10-01

A range of solar radiation management (SRM) techniques has been proposed to counter anthropogenic climate change. Here, we examine the potential effects of stratospheric sulfate aerosols and solar insolation reduction on tropospheric ozone and ozone at Earth's surface. Ozone is a key air pollutant, which can produce respiratory diseases and crop damage. Using a version of the Community Earth System Model from the National Center for Atmospheric Research that includes comprehensive tropospheric and stratospheric chemistry, we model both stratospheric sulfur injection and solar irradiance reduction schemes, with the aim of achieving equal levels of surface cooling relative to the Representative Concentration Pathway 6.0 scenario. This allows us to compare the impacts of sulfate aerosols and solar dimming on atmospheric ozone concentrations. Despite nearly identical global mean surface temperatures for the two SRM approaches, solar insolation reduction increases global average surface ozone concentrations, while sulfate injection decreases it. A fundamental difference between the two geoengineering schemes is the importance of heterogeneous reactions in the photochemical ozone balance with larger stratospheric sulfate abundance, resulting in increased ozone depletion in mid- and high latitudes. This reduces the net transport of stratospheric ozone into the troposphere and thus is a key driver of the overall decrease in surface ozone. At the same time, the change in stratospheric ozone alters the tropospheric photochemical environment due to enhanced ultraviolet radiation. A shared factor among both SRM scenarios is decreased chemical ozone loss due to reduced tropospheric humidity. Under insolation reduction, this is the dominant factor giving rise to the global surface ozone increase. Regionally, both surface ozone increases and decreases are found for both scenarios; that is, SRM would affect regions of the world differently in terms of air pollution. In conclusion, surface ozone and tropospheric chemistry would likely be affected by SRM, but the overall effect is strongly dependent on the SRM scheme. Due to the health and economic impacts of surface ozone, all these impacts should be taken into account in evaluations of possible consequences of SRM.

Diversity and degradation mechanism of an anaerobic bacterial community treating phenolic wastewater with sulfate as an electron acceptor.

PubMed

Guo, X J; Lu, Z Y; Wang, P; Li, H; Huang, Z Z; Lin, K F; Liu, Y D

2015-10-01

Petrochemical wastewater often contains high concentrations of phenol and sulfate that must be properly treated to meet discharge standards. This study acclimated anaerobic-activated sludge to treat saline phenolic wastewater with sulfate reduction and clarified the diversity and degradation mechanism of the microbial community. The active sludge in an upflow anaerobic sludge blanket (UASB) reactor could remove 90 % of phenol and maintain the effluent concentration of SO4 (2-) below 400 mg/L. Cloning and sequencing showed that Clostridium spp. and Desulfotomaculum spp. were major phenol-degrading bacteria. Phenol was probably degraded through the carboxylation pathway and sulfate reduction catalyzed by adenosine-5'-phosphosulfate (APS) reductase and dissimilatory sulfite reductase (DSR). A real-time polymerase chain reaction (RT-PCR) showed that as phenol concentration increased, the quantities of 16S rRNA gene, dsrB, and mcrA in the sludge all decreased. The relative abundance of dsrB dropped to 12.46 %, while that of mcrA increased to 56.18 %. The change in the electron flow ratio suggested that the chemical oxygen demand (COD) was removed mainly by sulfate-reducing bacteria under a phenol concentration of 420 mg/L, whereas it was removed mainly by methanogens above 630 mg/L.

MICROBIAL SULFATE REDUCTION AND METAL ATTENUATION IN PH 4 ACID MINE WATER

EPA Science Inventory

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 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing...

ADVANCES IN BIOTREATMENT OF ACID MINE DRAINAGE AND BIORECOVERY OF METALS: 2. MEMBRANE BIOREACTOR SYSTEM FOR SULFATE REDUCTION

EPA Science Inventory

Acid-mine drainage (AMD) is a severe pollution problem attributed to past mining activities. AMD is an acidic, metal-bearing wastewater generated by the oxidation of metal sulfides to sulfates by Thiobacillus bacteria in both the active and abandoned mining operations. The wastew...

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.

Sulfur Isotropic Studies of Archean Slate and Graywacke from Northern Minnesota: Evidence for the Existence of Sulfate Reducing Bacteria

NASA Technical Reports Server (NTRS)

Ripley, E. M.; Nicol, D. L.

1979-01-01

Sulfur isotopic studies of pyrite from metasediments in the 2.6 b.y. old Deer Lake greenstone sequence, Minnesota, were conducted in order to evaluate the possible importance of sulfate reducing bacteria in sulfide formation. Pyrite occurs as ovules up to 2 cm in diameter within graphitic slates, and as fine disseminations in metagraywacke units. SEM studies indicate the pyrite is framboidal in morphology. Delta notation values of pyrite from the Deer Lake sediments range from -2.3 to 11.1 0/00, with a peak at approximately +2 o/oo. Isotopic data is consistent with either high temperature inorganic reduction of circulating seawater sulfate, or low temperature bacterial reduction. However, the lack of sulfide bands or massive occurrences in the sediments, the restriction of pyrite mineralization to the sediments, and the absence of evidence for hot spring activity suggest that a diagenetic origin of pyrite is more feasible. Sulfide in such an environment would be produced principally by the action of sulfate reducing bacteria.

Sulfate-mediated electrooxidation of X-ray contrast media on boron-doped diamond anode.

PubMed

Radjenovic, Jelena; Petrovic, Mira

2016-05-01

Recently, electrochemical activation of sulfate ions to sulfate radical species and nonradically activated persulfate has been demonstrated at boron-doped diamond (BDD) anode, which enhanced the electrooxidation kinetics of several persistent contaminants. In this study, we investigated the transformation pathways of two X-ray contrast media (ICM), diatrizoate and iopromide, in electrooxidation at BDD anode using sulfate and inert nitrate anolyte. Sulfate anolyte yielded a seven-fold increase in apparent rate constants for ICM oxidation compared to inert nitrate anolyte, and a two-fold increase for the removal of organic carbon. Higher iodine release was observed in electrooxidation of diatrizoate compared to iopromide. In the case of diatrizoate, around 80% of deiodination efficiency was achieved in both anolytes. Deiodination efficiency of iopromide was somewhat lower in nitrate anolyte (≤75%) and significantly reduced in sulfate anolyte (≤46%) due to a larger steric hindrance of alkyl side chains. Moreover, a considerable lag phase of iopromide deiodination was observed in sulfate anolyte, indicating that initial oxidation reactions took place almost exclusively at the alkyl side chains. Several transformation products (TPs) of ICM were identified in electrooxidation in sulfate anolyte, and only three TPs in the case of nitrate anolyte. The main mechanistic steps in the oxidation of iopromide were H-abstraction and bond cleavage in the alkyl side chains. Diatrizoate was mainly transformed through oxidative cleavage of iodine substituent and inter-molecular cyclization. Two hydroxylamine derivatives of iopromide and a nitro-derivative of diatrizoate were observed in sulfate anolyte. These products have not been reported previously for hydroxyl radical-mediated oxidation of ICM. Given that electron-transfer mechanism is more typical for sulfate than for hydroxyl radicals, formation of hydroxylamine and nitro-derivatives of ICM was assigned to one-electron charge transfer to sulfate radical species and formation of N-centered radicals. Copyright © 2016 Elsevier Ltd. All rights reserved.

REDUCTIVE DEHALOGENATION OF HALOMETHANES IN IRON- AND SULFATE-REDUCING SEDIMENTS. 1. REACTIVITY PATTERN ANALYSIS

EPA Science Inventory

The incorporation of reductive transformations into environmental fate models requires the characterization of natural reductants in well-characterized sediments and aquifer materials. For this purpose, reactivity patterns (i.e., the range and relative order of reactivity) for a...

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

Fang, Howard L.; Wang, Jerry C.; Yu, Robert C.

Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The majormore » concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure. With the use of a disposable SOx trap to remove large portion of the sulfur poisons from the exhaust, the NOx adsorber catalyst can be protected and the numbers of de-sulfation events can be greatly reduced. Spectroscopic techniques, such as DRIFTS and Raman, have been used to monitor the underlying chemical reactions during NOx trapping/ regeneration and de-sulfation periods, and provide a fundamental understanding of NOx storage capacity and catalyst degradation mechanism using model catalysts. This paper examines the sulfur effect on two model NOx adsorber catalysts. The chemistry of SOx/base metal oxides and the sulfation product pathways and their corresponding spectroscopic data are discussed. SAE Paper SAE-2003-01-3245 {copyright} 2003 SAE International. This paper is published on this website with permission from SAE International. As a user of this website, you are permitted to view this paper on-line, download this pdf file and print one copy of this paper at no cost for your use only. The downloaded pdf file and printout of this SAE paper may not be copied, distributed or forwarded to others or for the use of others.« less

Simulating Aqueous-Phase Isoprene-Epoxydiol (IEPOX) ...

EPA Pesticide Factsheets

The lack of statistically robust relationships between IEPOX (isoprene epoxydiol)-derived SOA (IEPOX SOA) and aerosol liquid water and pH observed during the 2013 Southern Oxidant and Aerosol Study (SOAS) emphasizes the importance of modeling the whole system to understand the controlling factors governing IEPOX SOA formation. We present a mechanistic modeling investigation predicting IEPOX SOA based on Community Multiscale Air Quality (CMAQ) model algorithms and a recently introduced photochemical box model, simpleGAMMA. We aim to (1) simulate IEPOX SOA tracers from the SOAS Look Rock ground site, (2) compare the two model formulations, (3) determine the limiting factors in IEPOX SOA formation, and (4) test the impact of a hypothetical sulfate reduction scenario on IEPOX SOA. The estimated IEPOX SOA mass variability is in similar agreement (r2 ∼ 0.6) with measurements. Correlations of the estimated and measured IEPOX SOA tracers with observed aerosol surface area (r2 ∼ 0.5–0.7), rate of particle-phase reaction (r2 ∼ 0.4–0.7), and sulfate (r2 ∼ 0.4–0.5) suggest an important role of sulfate in tracer formation via both physical and chemical mechanisms. A hypothetical 25% reduction of sulfate results in ∼70% reduction of IEPOX SOA formation, reaffirming the importance of aqueous phase chemistry in IEPOX SOA production. The National Exposure Research Laboratory (NERL) Computational Exposure Division (CED) develops and evaluates data, decision-suppor

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 nitrate and sulfate on the performance and bacterial community structure of membrane-less single-chamber air-cathode microbial fuel cells.

PubMed

Seo, Yoonjoo; Kang, Hyemin; Chang, Sumin; Lee, Yun-Yeong; Cho, Kyung-Suk

2018-01-02

Membrane-less, single-chamber, air-cathode, microbial fuel cells (ML-SC MFCs) have attracted attention as being suitable for wastewater treatment. In this study, the effects of nitrate and sulfate on the performance of ML-SC MFCs and their bacterial structures were evaluated. The maximum power density increased after nitrate addition from 8.6 mW·m -2 to 14.0 mW·m -2 , while it decreased after sulfate addition from 11.5 mW·m -2 to 7.7 mW·m -2 . The chemical oxygen demand removal efficiencies remained at more than 90% regardless of the nitrate or sulfate additions. The nitrate was removed completely (93.0%) in the ML-SC MFC, while the sulfate removal efficiency was relatively low (17.6%). Clostridium (23.1%), Petrimonas (20.0%), and unclassified Rhodocyclaceae (6.2%) were dominant on the anode before the addition of nitrate or sulfate. After the addition of nitrate, Clostridium was still the most dominant on the anode (23.6%), but Petrimonas significantly decreased (6.0%) and unclassified Rhodocyclaceae increased (17.1%). After the addition of sulfate, the amount of Clostridium almost doubled in the composition on the anode (43.2%), while Petrimonas decreased (5.5%). The bacterial community on the cathode was similar to that on the anode after the addition of nitrate. However, Desulfovibrio was remarkably dominant on the cathode (32.9%) after the addition of sulfate. These results promote a deeper understanding of the effects of nitrate or sulfate on the ML-SC MFCs' performance and their bacterial community.

Volumetric determination of uranium using titanous sulfate as reductant before oxidimetric titration

USGS Publications Warehouse

Wahlberg, James S.; Skinner, Dwight L.; Rader, Lewis F.

1956-01-01

A new method for determining uranium in samples containing 0.05 percent or more U3O8, using titanous sulfate as reducing agent, is much shorter, faster, and has fewer interferences than conventional methods using reductor columns. The sample is dissolved with sulfuric, nitric, perchloric, and hydrofluoric acids. Elements that would otherwise form insoluble fluorides are kept in solution by complexing the fluoride ion with boric acid. A precipitation is made with cupferron to remove interfering elements. The solution is filtered to remove the precipitated cupferrates instead of extracting them with chloroform as is usually done. Filtration is preferred to extraction because any niobium that may be in solution forms an insoluble cupferrate that may be removed by filtering but is very difficult to extract with chloroform. Excess cupferron is destroyed by oxidizing with nitric and perchloric acids, and evaporating to dense fumes of sulfuric acid. The uranium is reduced to U(IV) by the addition of titanous sulfate, with cupric sulfate used as an indicator of the completeness of the reduction. Metallic copper is formed when all the uranium is reduced. The reduced copper is then reoxidized by the addition of mercuric perchlorate, an excess of ferric sulfate added, and the solution titrated immediately with standard ceric sulfate with ferroin as an indicator. Precision of the method compared favorable with methods in common use, both for uranium ores and for most types of uranium-rich materials.

Fucans, but Not Fucomannoglucuronans, Determine the Biological Activities of Sulfated Polysaccharides from Laminaria saccharina Brown Seaweed

PubMed Central

Ushakova, Natalia A.; Preobrazhenskaya, Marina E.; Piccoli, Antonio; Totani, Licia; Ustyuzhanina, Nadezhda E.; Bilan, Maria I.; Usov, Anatolii I.; Grachev, Alexey A.; Morozevich, Galina E.; Berman, Albert E.; Sanderson, Craig J.; Kelly, Maeve; Di Gregorio, Patrizia; Rossi, Cosmo; Tinari, Nicola; Iacobelli, Stefano; Rabinovich, Gabriel A.; Nifantiev, Nikolay E.

2011-01-01

Sulfated polysaccharides from Laminaria saccharina (new name: Saccharina latissima) brown seaweed show promising activity for the treatment of inflammation, thrombosis, and cancer; yet the molecular mechanisms underlying these properties remain poorly understood. The aim of this work was to characterize, using in vitro and in vivo strategies, the anti-inflammatory, anti-coagulant, anti-angiogenic, and anti-tumor activities of two main sulfated polysaccharide fractions obtained from L. saccharina: a) L.s.-1.0 fraction mainly consisting of O-sulfated mannoglucuronofucans and b) L.s.-1.25 fraction mainly composed of sulfated fucans. Both fractions inhibited leukocyte recruitment in a model of inflammation in rats, although L.s.-1.25 appeared to be more active than L.s.-1.0. Also, these fractions inhibited neutrophil adhesion to platelets under flow. Only fraction L.s.-1.25, but not L.s.-1.0, displayed anticoagulant activity as measured by the activated partial thromboplastin time. Investigation of these fractions in angiogenesis settings revealed that only L.s.-1.25 strongly inhibited fetal bovine serum (FBS) induced in vitro tubulogenesis. This effect correlated with a reduction in plasminogen activator inhibitor-1 (PAI-1) levels in L.s.-1.25-treated endothelial cells. Furthermore, only parent sulfated polysaccharides from L. saccharina (L.s.-P) and its fraction L.s.-1.25 were powerful inhibitors of basic fibroblast growth factor (bFGF) induced pathways. Consistently, the L.s.-1.25 fraction as well as L.s.-P successfully interfered with fibroblast binding to human bFGF. The incorporation of L.s.-P or L.s.-1.25, but not L.s.-1.0 into Matrigel plugs containing melanoma cells induced a significant reduction in hemoglobin content as well in the frequency of tumor-associated blood vessels. Moreover, i.p. administrations of L.s.-1.25, as well as L.s.-P, but not L.s.-1.0, resulted in a significant reduction of tumor growth when inoculated into syngeneic mice. Finally, L.s.-1.25 markedly inhibited breast cancer cell adhesion to human platelet-coated surfaces. Thus, sulfated fucans are mainly responsible for the anti-inflammatory, anticoagulant, antiangiogenic, and antitumor activities of sulfated polysaccharides from L. saccharina brown seaweed. PMID:21387013

Investigation of in vivo toxicity of hydroxylamine sulfate and the efficiency of intoxication treatment by α-tocopherol acetate and methylene blue.

PubMed

Prodanchuk, Mykola G; Tsatsakis, Aristidis M; Prodanchuk, Georgiy M; Tsakalof, Andreas K

2013-11-01

Investigation of hydroxylamine sulfate toxicity mechanism in vivo and estimation of α-tocopherol acetate and methylene blue efficiency in poisoning treatments. In vivo experiments were conducted on 102 Wistar Han rats. The experiments investigated the hematotoxic and oxidative stress effects of hydroxylamine sulfate in acute and subacute toxicity treatment of animals. Electron Spin Resonance was used for quantitative determination of blood and liver tissue parameters alterations after intoxication. The osmotic fragility of erythrocytes, lipid peroxidation intensity and level of SH-groups in liver of rats were determined by established biochemical assays. Hydroxylamine sulfate cause an acute hematotoxicity and oxidative stress in vivo as demonstrated by the appearance of free oxidized iron in blood, reduced glutathione content and increased lipid peroxidation in liver. The experimental studies showed the formation of Hb-NO, MetHb in erythrocytes and as well of stable complex of reduced iron (Fe(2+)) with hydroxylamine sulfate. Methylene blue treatment does not reduce the Hb-NO or MetHb levels in intoxicated animals while administration of α-tocopherol acetate reduces substantially lipid peroxidation. Oxidative stress is a key mechanism of acute hematotoxicity caused by hydroxylamine sulfate. Methylene blue is not suitable antidote in case of hydroxylamine intoxication. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Effects of the addition of different nitrogen sources in the tequila fermentation process at high sugar concentration.

PubMed

Arrizon, J; Gschaedler, A

2007-04-01

To study the effect of the addition of different nitrogen sources at high sugar concentration in the tequila fermentation process. Fermentations were performed at high sugar concentration (170 g l(-1)) using Agave tequilana Weber blue variety with and without added nitrogen from different sources (ammonium sulfate; glutamic acid; a mixture of ammonium sulfate and amino acids) during the exponential phase of growth. All the additions increased the fermentation rate and alcohol efficiency. The level of synthesis of volatile compounds depended on the source added. The concentration of amyl alcohols and isobutanol were decreased while propanol and acetaldehyde concentration increased. The most efficient nitrogen sources for fermentation rate were ammonium sulfate and the mixture of ammonium sulfate and amino acids. The level of volatile compounds produced depended upon types of nitrogen. The synthesis of some volatile compounds increased while others decreased with nitrogen addition. The addition of nitrogen could be a strategy for improving the fermentation rate and efficiency in the tequila fermentation process at high sugar Agave tequilana concentration. Furthermore, the sensory quality of the final product may change because the synthesis of the volatile compounds is modified.

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.

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

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.

Dissimilatory arsenate and sulfate reduction in sediments of two hypersaline, arsenic-rich soda lakes: Mono and Searles Lakes, California

USGS Publications Warehouse

Kulp, T.R.; Hoeft, S.E.; Miller, L.G.; Saltikov, C.; Murphy, J.N.; Han, S.; Lanoil, B.; Oremland, R.S.

2006-01-01

A radioisotope method was devised to study bacterial respiratory reduction of arsenate in sediments. The following two arsenic-rich soda lakes in California were chosen for comparison on the basis of their different salinities: Mono Lake (???90 g/liter) and Searles Lake (???340 g/liter). Profiles of arsenate reduction and sulfate reduction were constructed for both lakes. Reduction of [73As] arsenate occurred at all depth intervals in the cores from Mono Lake (rate constant [k] = 0.103 to 0.04 h-1) and Searles Lake (k = 0.012 to 0.002 h-1), and the highest activities occurred in the top sections of each core. In contrast, [35S] sulfate reduction was measurable in Mono Lake (k = 7.6 ?? 104 to 3.2 ?? 10-6 h-1) but not in Searles Lake. Sediment DNA was extracted, PCR amplified, and separated by denaturing gradient gel electrophoresis (DGGE) to obtain phylogenetic markers (i.e., 16S rRNA genes) and a partial functional gene for dissimilatory arsenate reduction (arrA). The amplified arrA gene product showed a similar trend in both lakes; the signal was strongest in surface sediments and decreased to undetectable levels deeper in the sediments. More arrA gene signal was observed in Mono Lake and was detectable at a greater depth, despite the higher arsenate reduction activity observed in Searles Lake. A partial sequence (about 900 bp) was obtained for a clone (SLAS-3) that matched the dominant DGGE band found in deeper parts of the Searles Lake sample (below 3 cm), and this clone was found to be closely related to SLAS-1, a novel extremophilic arsenate respirer previously cultivated from Searles Lake. Copyright ?? 2006, American Society for Microbiology. All Rights Reserved.

An Eco-Friendly Improved Protocol for the Synthesis of Bis(3-indolyl)methanes Using Poly(4-vinylpyridinium)hydrogen Sulfate as Efficient, Heterogeneous, and Recyclable Solid Acid Catalyst

PubMed Central

Banothu, Janardhan; Gali, Rajitha; Velpula, Ravibabu; Bavantula, Rajitha; Crooks, Peter A.

2013-01-01

Highly efficient and eco-friendly protocol for the synthesis of bis(3-indolyl)methanes by the electrophilic substitution reaction of indole with aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate was described. Excellent yields, shorter reaction times, simple work-up procedure, avoiding hazardous organic solvents, and reusability of the catalyst are the most obvious advantages of this method. PMID:24052864

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.

Specific growth rate of sulfate reducing bacteria in the presence of manganese and cadmium.

PubMed

Medírcio, Sílvia N; Leão, Versiane A; Teixeira, Mônica C

2007-05-08

The development of technologies based on the use of sulfate-reducing bacteria (SRB) to treat sulfate contaminated wastewaters has produced a cost-effective route to precipitate metals. In this work the effects of cadmium and manganese in the SRB growth rates were assessed. It was observed that duplication time is 50h in the presence of cadmium and 6h in the presence of manganese, thus showing that the SRB growth rate was more affected by the presence of cadmium. A low sulfate reduction (maximum 25%) occurred which was sufficient for metal precipitation. The results are discussed considering their implications for metal precipitation in acid mining drainage.

Impact of elevated nitrate on sulfate-reducing bacteria: A comparative study of Desulfovibrio vulgaris

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

He, Q.; He, Z.; Joyner, D.C.

2010-07-15

Sulfate-reducing bacteria have been extensively studied for their potential in heavy-metal bioremediation. However, the occurrence of elevated nitrate in contaminated environments has been shown to inhibit sulfate reduction activity. Although the inhibition has been suggested to result from the competition with nitrate-reducing bacteria, the possibility of direct inhibition of sulfate reducers by elevated nitrate needs to be explored. Using Desulfovibrio vulgaris as a model sulfate-reducing bacterium, functional genomics analysis reveals that osmotic stress contributed to growth inhibition by nitrate as shown by the upregulation of the glycine/betaine transporter genes and the relief of nitrate inhibition by osmoprotectants. The observation thatmore » significant growth inhibition was effected by 70 mM NaNO{sub 3} but not by 70 mM NaCl suggests the presence of inhibitory mechanisms in addition to osmotic stress. The differential expression of genes characteristic of nitrite stress responses, such as the hybrid cluster protein gene, under nitrate stress condition further indicates that nitrate stress response by D. vulgaris was linked to components of both osmotic and nitrite stress responses. The involvement of the oxidative stress response pathway, however, might be the result of a more general stress response. Given the low similarities between the response profiles to nitrate and other stresses, less-defined stress response pathways could also be important in nitrate stress, which might involve the shift in energy metabolism. The involvement of nitrite stress response upon exposure to nitrate may provide detoxification mechanisms for nitrite, which is inhibitory to sulfate-reducing bacteria, produced by microbial nitrate reduction as a metabolic intermediate and may enhance the survival of sulfate-reducing bacteria in environments with elevated nitrate level.« less

Higher Novel L-Cys Degradation Activity Results in Lower Organic-S and Biomass in Sarcocornia than the Related Saltwort, Salicornia.

PubMed

Kurmanbayeva, Assylay; Bekturova, Aizat; Srivastava, Sudhakar; Soltabayeva, Aigerim; Asatryan, Armine; Ventura, Yvonne; Khan, Mohammad Suhail; Salazar, Octavio; Fedoroff, Nina; Sagi, Moshe

2017-09-01

Salicornia and Sarcocornia are almost identical halophytes whose edible succulent shoots hold promise for commercial production in saline water. Enhanced sulfur nutrition may be beneficial to crops naturally grown on high sulfate. However, little is known about sulfate nutrition in halophytes. Here we show that Salicornia europaea (ecotype RN) exhibits a significant increase in biomass and organic-S accumulation in response to supplemental sulfate, whereas Sarcocornia fruticosa (ecotype VM) does not, instead exhibiting increased sulfate accumulation. We investigated the role of two pathways on organic-S and biomass accumulation in Salicornia and Sarcoconia : the sulfate reductive pathway that generates Cys and l-Cys desulfhydrase that degrades Cys to H 2 S, NH 3 , and pyruvate. The major function of O -acetyl-Ser-(thiol) lyase (OAS-TL; EC 2.5.1.47) is the formation of l-Cys, but our study shows that the OAS-TL A and OAS-TL B of both halophytes are enzymes that also degrade l-Cys to H 2 S. This activity was significantly higher in Sarcocornia than in Salicornia , especially upon sulfate supplementation. The activity of the sulfate reductive pathway key enzyme, adenosine 5'-phosphosulfate reductase (APR, EC 1.8.99.2), was significantly higher in Salicornia than in Sarcocornia These results suggest that the low organic-S level in Sarcocornia is the result of high l-Cys degradation rate by OAS-TLs, whereas the greater organic-S and biomass accumulation in Salicornia is the result of higher APR activity and low l-Cys degradation rate, resulting in higher net Cys biosynthesis. These results present an initial road map for halophyte growers to attain better growth rates and nutritional value of Salicornia and Sarcocornia . © 2017 American Society of Plant Biologists. All Rights Reserved.

Influences of man-made emissions and climate changes on tropospheric ozone, methane, and sulfate at 2030 from a broad range of possible futures

NASA Astrophysics Data System (ADS)

Unger, Nadine; Shindell, Drew T.; Koch, Dorothy M.; Amann, Markus; Cofala, Janusz; Streets, David G.

2006-06-01

We apply the Goddard Institute for Space Studies composition-climate model to an assessment of tropospheric O3, CH4, and sulfate at 2030. We compare four different anthropogenic emissions forecasts: A1B and B1 from the Intergovernmental Panel on Climate Change Special Report on Emissions Scenarios and Current Legislation (CLE) and Maximum Feasible Reduction (MFR) from the International Institute for Applied Systems Analysis. The projections encompass a wide range of possible man-made emissions changes. The A1B, B1, and CLE forecasts all suggest large increases in surface O3 and sulfate baseline pollution at tropical and subtropical latitudes, especially over the Indian subcontinent, where the pollution increases may be as large as 100%. The ranges of annual mean regional ground level O3 and sulfate changes across all scenarios are -10 to +30 ppbv and -1200 to +3000 pptv, respectively. Physical climate changes reduce future surface O3, but tend to increase ground level sulfate locally over North Africa because of an enhancement of aqueous-phase SO2 oxidation. For all examined future scenarios the combined sum of the CH4, O3, and sulfate radiative forcings is positive, even for the MFR scenario, because of the large reduction in sulfate. For A1B the forcings are as much as half of that of the preindustrial to present-day forcing for each species. For MFR the sign of the forcing for each species is reversed with respect to the other scenarios. At 2030, global changes in climate-sensitive natural emissions of CH4 from wetlands, NOx from lightning, and dimethyl sulfide from the ocean appear to be small (<5%).

Higher Novel L-Cys Degradation Activity Results in Lower Organic-S and Biomass in Sarcocornia than the Related Saltwort, Salicornia1[OPEN

PubMed Central

Kurmanbayeva, Assylay; Bekturova, Aizat; Soltabayeva, Aigerim; Asatryan, Armine; Ventura, Yvonne; Salazar, Octavio; Fedoroff, Nina

2017-01-01

Salicornia and Sarcocornia are almost identical halophytes whose edible succulent shoots hold promise for commercial production in saline water. Enhanced sulfur nutrition may be beneficial to crops naturally grown on high sulfate. However, little is known about sulfate nutrition in halophytes. Here we show that Salicornia europaea (ecotype RN) exhibits a significant increase in biomass and organic-S accumulation in response to supplemental sulfate, whereas Sarcocornia fruticosa (ecotype VM) does not, instead exhibiting increased sulfate accumulation. We investigated the role of two pathways on organic-S and biomass accumulation in Salicornia and Sarcoconia: the sulfate reductive pathway that generates Cys and l-Cys desulfhydrase that degrades Cys to H2S, NH3, and pyruvate. The major function of O-acetyl-Ser-(thiol) lyase (OAS-TL; EC 2.5.1.47) is the formation of l-Cys, but our study shows that the OAS-TL A and OAS-TL B of both halophytes are enzymes that also degrade l-Cys to H2S. This activity was significantly higher in Sarcocornia than in Salicornia, especially upon sulfate supplementation. The activity of the sulfate reductive pathway key enzyme, adenosine 5′-phosphosulfate reductase (APR, EC 1.8.99.2), was significantly higher in Salicornia than in Sarcocornia. These results suggest that the low organic-S level in Sarcocornia is the result of high l-Cys degradation rate by OAS-TLs, whereas the greater organic-S and biomass accumulation in Salicornia is the result of higher APR activity and low l-Cys degradation rate, resulting in higher net Cys biosynthesis. These results present an initial road map for halophyte growers to attain better growth rates and nutritional value of Salicornia and Sarcocornia. PMID:28743765

Seasonal and event variations in δ34S values of stream sulfate in a Vermont forested catchment: Implications for sulfur sources and cycling

USGS Publications Warehouse

Shanley, James B.; Mayer, Bernhard; Mitchell, Myron J.; Bailey, Scott W.

2008-01-01

Stable sulfur (S) isotope ratios can be used to identify the sources of sulfate contributing to streamwater. We collected weekly and high-flow stream samples for S isotopic analysis of sulfate through the entire water year 2003 plus the snowmelt period of 2004. The study area was the 41-ha forested W-9 catchment at Sleepers River Research Watershed, Vermont, a site known to produce sulfate from weathering of sulfide minerals in the bedrock. The δ34S values of streamwater sulfate followed an annual sinusoidal pattern ranging from about 6.5‰ in early spring to about 10‰ in early fall. During high-flow events, δ34S values typically decreased by 1 to 3‰ from the prevailing seasonal value. The isotopic evidence suggests that stream sulfate concentrations are controlled by: (1) an overall dominance of bedrock-derived sulfate (δ34S ~ 6–14‰); (2) contributions of pedogenic sulfate (δ34S ~ 5–6‰) during snowmelt and storms with progressively diminishing contributions during base flow recession; and (3) minor effects of dissimilatory bacterial sulfate reduction and subsequent reoxidation of sulfides. Bedrock should not be overlooked as a source of S in catchment sulfate budgets.

Precipitation chemistry affected by differences in location of collection sites and storage methods

NASA Astrophysics Data System (ADS)

Mahendrappa, M. K.

An investigation was carried out to evaluate rigorously the possible differences in measured concentrations of hydrogen, nitrate and sulfate ions in 'bulk' precipitation samples that may be caused by variations in location of rain collectors, and duration and temperature of storage. Storage of precipitation samples, up to 1 month, both in the coldroom and in the field resulted in a significant reduction in the concentration of hydrogen ions. Only field storage caused a statistically significant reduction in the concentration of nitrate in the precipitation samples. Levels of sulfate ions were not found to be significantly affected by storage either in the field or in coldrooms. Samples collected from a rain gage located on a building roof were more acidic than those collected in open spaces in forests. Though all samples showed similar seasonal patterns in the concentrations of sulfate and nitrate, the individual values consistently differed from each other.

Biphasic Role of Chondroitin Sulfate in Cardiac Differentiation of Embryonic Stem Cells through Inhibition of Wnt/β-Catenin Signaling

PubMed Central

Prinz, Robert D.; Willis, Catherine M.; van Kuppevelt, Toin H.; Klüppel, Michael

2014-01-01

The glycosaminoglycan chondroitin sulfate is a critical component of proteoglycans on the cell surface and in the extracellular matrix. As such, chondroitin sulfate side chains and the sulfation balance of chondroitin play important roles in the control of signaling pathways, and have a functional importance in human disease. In contrast, very little is known about the roles of chondroitin sulfate molecules and sulfation patterns during mammalian development and cell lineage specification. Here, we report a novel biphasic role of chondroitin sulfate in the specification of the cardiac cell lineage during embryonic stem cell differentiation through modulation of Wnt/beta-catenin signaling. Lineage marker analysis demonstrates that enzymatic elimination of endogenous chondroitin sulfates leads to defects specifically in cardiac differentiation. This is accompanied by a reduction in the number of beating cardiac foci. Mechanistically, we show that endogenous chondroitin sulfate controls cardiac differentiation in a temporal biphasic manner through inhibition of the Wnt/beta-catenin pathway, a known regulatory pathway for the cardiac lineage. Treatment with a specific exogenous chondroitin sulfate, CS-E, could mimic these biphasic effects on cardiac differentiation and Wnt/beta-catenin signaling. These results establish chondroitin sulfate and its sulfation balance as important regulators of cardiac cell lineage decisions through control of the Wnt/beta-catenin pathway. Our work suggests that targeting the chondroitin biosynthesis and sulfation machinery is a novel promising avenue in regenerative strategies after heart injury. PMID:24667694

Biphasic role of chondroitin sulfate in cardiac differentiation of embryonic stem cells through inhibition of Wnt/β-catenin signaling.

PubMed

Prinz, Robert D; Willis, Catherine M; van Kuppevelt, Toin H; Klüppel, Michael

2014-01-01

The glycosaminoglycan chondroitin sulfate is a critical component of proteoglycans on the cell surface and in the extracellular matrix. As such, chondroitin sulfate side chains and the sulfation balance of chondroitin play important roles in the control of signaling pathways, and have a functional importance in human disease. In contrast, very little is known about the roles of chondroitin sulfate molecules and sulfation patterns during mammalian development and cell lineage specification. Here, we report a novel biphasic role of chondroitin sulfate in the specification of the cardiac cell lineage during embryonic stem cell differentiation through modulation of Wnt/beta-catenin signaling. Lineage marker analysis demonstrates that enzymatic elimination of endogenous chondroitin sulfates leads to defects specifically in cardiac differentiation. This is accompanied by a reduction in the number of beating cardiac foci. Mechanistically, we show that endogenous chondroitin sulfate controls cardiac differentiation in a temporal biphasic manner through inhibition of the Wnt/beta-catenin pathway, a known regulatory pathway for the cardiac lineage. Treatment with a specific exogenous chondroitin sulfate, CS-E, could mimic these biphasic effects on cardiac differentiation and Wnt/beta-catenin signaling. These results establish chondroitin sulfate and its sulfation balance as important regulators of cardiac cell lineage decisions through control of the Wnt/beta-catenin pathway. Our work suggests that targeting the chondroitin biosynthesis and sulfation machinery is a novel promising avenue in regenerative strategies after heart injury.

Use of a Ferrous Sulfate - Sodium Dithionite Blend to Treat a Dissolved Phase Cr(VI) Plume

EPA Science Inventory

A field study was conducted to evaluate the use of a combination of sodium dithionite and ferrous sulfate in creating an in situ redox zone for treatment of a dissolved phase Cr(VI) plume at a former industrial site. The reductant blend was injected into the path of a dissolved ...

NONLINEARITIES IN THE SULFATE SECONDARY FINE PARTICULATE RESPONSE TO NOX EMISSIONS REDUCTIONS AS MODELED BY THE REGIONAL ACID DEPOSITION MODEL

EPA Science Inventory

Attention is increasingly being devoted to the health effects of fine particulates. In regions that have a large production of sulfate, sulfuric acid and nitric acid compete for the available ammonia to form aerosols. In addition, the available nitric acid is the result of ur...

Application of acidic calcium sulfate and e-polylysine to pre-rigor beef rounds for reduction of pathogens

USDA-ARS?s Scientific Manuscript database

Foodborne illness continues to be a serious public health problem and is a major concern for the United States food industry. This study evaluated the effectiveness of warm solutions of acidic calcium sulfate (ACS), lactic acid (LA), episolon-polylysine (EPL), ACS plus EPL, and sterile distilled wa...

Synthesis and foaming properties of new anionic surfactants based on a renewable building block: sodium dodecyl isosorbide sulfates.

PubMed

Lavergne, Aurélie; Zhu, Ying; Pizzino, Aldo; Molinier, Valérie; Aubry, Jean-Marie

2011-08-15

Two agro-based anionic surfactants containing an isosorbide moiety have been synthesized and their amphiphilic properties evaluated. Since isosorbide is now considered as an important platform chemical of the starch industry, these compounds could represent bio-sourced alternatives to the alkyl ether sulfates (notably lauryl ether sulfate, LES) that are based on petroleum-derived ethylene oxides. As isosorbide is an asymmetric diol, two isomers can be prepared (2-O-dodecyl isosorbide sulfate and 5-O-dodecyl isosorbide sulfate) that show significantly different aqueous properties as regards to their Krafft temperatures and critical micellar concentrations. 5-O-dodecyl isosorbide sulfate is the most soluble and the most efficient surfactant. It possesses a much lower critical micelle concentration (cmc) than sodium dodecyl sulfate, SDS, leading to comparable foaming properties with a three times lower concentration. Its behavior compares well with the one of pure diethoxylated dodecyl sulfate that has also been prepared and evaluated in this work. Copyright © 2011 Elsevier Inc. All rights reserved.

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.

Chondroitin Lyase from a Marine Arthrobacter sp. MAT3885 for the Production of Chondroitin Sulfate Disaccharides.

PubMed

Kale, Varsha; Friðjónsson, Ólafur; Jónsson, Jón Óskar; Kristinsson, Hörður G; Ómarsdóttir, Sesselja; Hreggviðsson, Guðmundur Ó

2015-08-01

Chondroitin sulfate (CS) saccharides from cartilage tissues have potential application in medicine or as dietary supplements due to their therapeutic bioactivities. Studies have shown that depolymerized CS saccharides may display enhanced bioactivity. The objective of this study was to isolate a CS-degrading enzyme for an efficient production of CS oligo- or disaccharides. CS-degrading bacteria from marine environments were enriched using in situ artificial support colonization containing CS from shark cartilage as substrate. Subsequently, an Arthrobacter species (strain MAT3885) efficiently degrading CS was isolated from a CS enrichment culture. The genomic DNA from strain MAT3885 was pyro-sequenced by using the 454 FLX sequencing technology. Following assembly and annotation, an orf, annotated as family 8 polysaccharide lyase genes, was identified, encoding an amino acid sequence with a similarity to CS lyases according to NCBI blastX. The gene, designated choA1, was cloned in Escherichia coli and expressed downstream of and in frame with the E. coli malE gene for obtaining a high yield of soluble recombinant protein. Applying a dual-tag system (MalE-Smt3-ChoA1), the MalE domain was separated from ChoA1 with proteolytic cleavage using Ulp1 protease. ChoA1 was defined as an AC-type enzyme as it degraded chondroitin sulfate A, C, and hyaluronic acid. The optimum activity of the enzyme was at pH 5.5-7.5 and 40 °C, running a 10-min reaction. The native enzyme was estimated to be a monomer. As the recombinant chondroitin sulfate lyase (designated as ChoA1R) degraded chondroitin sulfate efficiently compared to a benchmark enzyme, it may be used for the production of chondroitin sulfate disaccharides for the food industry or health-promoting products.

Aryl imidazylates and aryl sulfates as electrophiles in metal-free ArS(N)1 reactions.

PubMed

Qrareya, Hisham; Protti, Stefano; Fagnoni, Maurizio

2014-12-05

Some oxygen-bonded substituents were investigated as leaving groups in photoinduced ArS(N)1 reactions. Irradiation of aryl imidazylates and of the corresponding imidazolium salts mainly caused homolysis of the ArO-S bond. However, previously unexplored trifluoroethoxy aryl sulfates were found to undergo efficient metal-free arylation. The sulfates were conveniently generated in situ by dissolving the corresponding imidazolium salts in basic 2,2,2-trifluoroethanol.

Role of sectoral and multi-pollutant emission control strategies in improving atmospheric visibility in the Yangtze River Delta, China.

PubMed

Huang, Kan; Fu, Joshua S; Gao, Yang; Dong, Xinyi; Zhuang, Guoshun; Lin, Yanfen

2014-01-01

The Community Multi-scale Air Quality modeling system is used to investigate the response of atmospheric visibility to the emission reduction from different sectors (i.e. industries, traffic and power plants) in the Yangtze River Delta, China. Visibility improvement from exclusive reduction of NOx or VOC emission was most inefficient. Sulfate and organic aerosol would rebound if NOx emission was exclusively reduced from any emission sector. The most efficient way to improve the atmospheric visibility was proven to be the multi-pollutant control strategies. Simultaneous emission reductions (20-50%) on NOx, VOC and PM from the industrial and mobile sectors could result in 0.3-1.0 km visibility improvement. And the emission controls on both NOx (85%) and SO2 (90%) from power plants gained the largest visibility improvement of up to 4.0 km among all the scenarios. The seasonal visibility improvement subject to emission controls was higher in summer while lower in the other seasons. Copyright © 2013 Elsevier Ltd. All rights reserved.

Influence of nitrate, sulfate and operational parameters on the bioreduction of perchlorate using an up-flow packed bed reactor at high salinity.

PubMed

Chung, J; Shin, S; Oh, J

2010-05-01

In this study we have investigated whether electron acceptors, such as nitrate or sulphate ions, competitively inhibit the reduction of perchlorate in brine in continuous up-flow packed bed bioreactors. The effect of pH and hydraulic retention time (HRT) on the reduction of perchlorate at high salinity has also been examined. Reduction of perchlorate was found to be only moderately influenced by nitrate (under 163 mg N L-'), implying that there was no significant microbial competition for electron acceptors. As a result of microbial diversity, there were few differences between microbial communities fed with a variety of media, suggesting that most nitrate-reducing bacteria are able to reduce perchlorate at high salinity. Reduction of perchlorate was almost complete at relatively high sulfate levels (1000 mg L(-1)), neutral pH (6-8) and relatively long HRTs (> 10 h).

Simultaneous anaerobic transformation of tetrachloroethene and carbon tetrachloride in a continuous flow column

NASA Astrophysics Data System (ADS)

Azizian, Mohammad F.; Semprini, Lewis

2016-07-01

Tetrachloroethene (PCE) and carbon tetrachloride (CT) were simultaneously transformed in a packed column that was bioaugmented with the Evanite culture (EV). The data presented here have been obtained over a period of 1930 days. Initially the column was continuously fed synthetic groundwater with PCE (0.1 mM), sulfate (SO42 -) (0.2 mM) and formate (2.1 mM) or lactate (1.1 mM), but not CT. In these early stages of the study the effluent H2 concentrations ranged from 7 to 19 nM, and PCE was transformed to ethene (ETH) (81 to 85%) and vinyl chloride (VC) (11 to 17%), and SO42 - was completely reduced when using either lactate or formate as electron donors. SO42 - reduction occurred concurrently with cis-DCE and VC dehalogenation. Formate was a more effective substrate for promoting dehalogenation based on electron donor utilization efficiency. Simultaneous PCE and CT tests found CT (0.015 mM) was completely transformed with 20% observed as chloroform (CF) and trace amounts of chloromethane (CM) and dichloromethane (DCM), but no methane (CH4) or carbon disulfide (CS2). PCE transformation to ETH improved with CT addition in response to increases in H2 concentrations to 160 nM that resulted from acetate formation being inhibited by either CT or CF. Lactate fermentation was negatively impacted after CT transformation tests, with propionate accumulating, and H2 concentrations being reduced to below 1 nM. Under these conditions both SO42 - reduction and dehalogenation were negatively impacted, with sulfate reduction not occurring and PCE being transformed to cis-dichloroethene (c-DCE) (52%) and VC (41%). Upon switching to formate, H2 concentrations increased to 40 nM, and complete SO42 - reduction was achieved, while PCE was transformed to ETH (98%) and VC (1%), with no acetate detected. Throughout the study PCE dehalogenation to ethene was positively correlated with the effluent H2 concentrations.

Effect of phosphate, iron and sulfate reduction on arsenic dynamics and bioaccumulation in constructed wetlands

NASA Astrophysics Data System (ADS)

Zhang, Z.; Moon, H. S.; Myneni, S.; Jaffe, P. R.

2016-12-01

Constructed wetlands are economically viable and highly efficient in the treatment of high As waters discharged from smelting process in the mining industry. However, arsenic (As) dynamics and bioaccumulation in constructed wetlands coupled to nutrients loading and associated biogeochemical changes are confounding and not well understood. In this study, we investigated the effect of phosphate, iron and sulfate reduction on As dynamics in the wetland rhizosphere and its bioaccumulation in plants using greenhouse mesocosms. Results show that high Fe (50µM ferrihydrite/g soil) and SO42- (5mM) treatments are most favorable for As sequestration in soils in the presence of wetland plants (Scirpus actus), probably because the biodegradable plant exudates released into the rhizosphere facilitates the microbial reduction of Fe(III), SO42- and As(V) to sequester As by precipitation/coprecipitation. Whereas, from the transition of oxidizing to reducing conditions, the loading of high phosphate (100µM) enhances the As release into groundwater and its accumulation in the plants, due to the competitive sorption between phosphate and arsenate as well as the reductive dissolution of Fe and As. As retention in soils and accumulation in plants were mainly controlled by SO42- rather than Fe levels. Compared with low SO42- (0.1mM) treatment, high SO42- resulted in 2 times more As in soils, 30 times more As in roots, and 49% less As in leaves. The As levels in soils are negatively correlated with the As levels in plant roots. An As speciation analysis in pore water indicated that 19% more dissolved As was reduced under high SO42- than low SO42- levels, and 30% more As(III) was detected under high PO43- than low PO43- levels, which is consistent with the fact that more dissimilatory arsenate-respiring bacteria were found under high SO42- and high PO43- levels.

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.

An Efficient Approach to Sulfate Metabolites of Polychlorinated Biphenyls

PubMed Central

Li, Xueshu; Parkin, Sean; Duffel, Michael W.; Robertson, Larry W.; Lehmler, Hans-Joachim

2009-01-01

Polychlorinated biphenyls (PCBs), a major class of persistent organic pollutants, are metabolized to hydroxylated PCBs. Several hydroxylated PCBs are substrates of cytosolic phase II enzymes, such as phenol and hydroxysteroid (alcohol) sulfotransferases; however, the corresponding sulfation products have not been isolated and characterized. Here we describe a straightforward synthesis of a series of ten PCB sulfate monoesters from the corresponding hydroxylated PCBs. The hydroxylated PCBs were synthesized by coupling chlorinated benzene boronic acids with appropriate brominated (chloro-)anisoles, followed by demethylation with boron tribromide. The hydroxylated PCBs were sulfated with 2,2,2-trichloroethyl chlorosulfate using DMAP as base. Deprotection with zinc powder/ammonium formate yielded the ammonium salts of the desired PCB sulfate monoesters in good yields when the sulfated phenyl ring contained no or one chlorine substituent. However, no PCB sulfate monoesters were isolated when two chlorines were present ortho to the sulfated hydroxyl group. To aid with future quantitative structure activity relationship studies, the structures of two 2,2,2-trichloroethyl-protected PCB sulfates were verified by X-ray diffraction. PMID:19345419

Stability of niosomes with encapsulated vitamin D3 and ferrous sulfate generated using a novel supercritical carbon dioxide method.

PubMed

Wagner, Michael E; Spoth, Katherine A; Kourkoutis, Lena F; Rizvi, Syed S H

2016-12-01

Niosomes were prepared using a novel supercritical carbon dioxide based method to simultaneously encapsulate ferrous sulfate and vitamin D3 as hydrophilic and hydrophobic cargo, respectively. Vesicle particle size was determined to be bimodal with peak diameters of 1.44 ± 0.16 μm and 7.21 ± 0.64 μm, with the smaller peak comprising 98.8% of the total niosomal volume. Encapsulation efficiency of ferrous sulfate was 25.1 ± 0.2% and encapsulation efficiency of vitamin D3 was 95.9 ± 1.47%. Physical stability of the produced niosomes was assessed throughout a storage period of 21 days. Niosomes showed good physical stability at 20 °C, but storage at 4 °C showed an initial burst release, indicating possible rupture of the niosomal membrane. The Korsmeyer-Peppas equation was used to model the release of ferrous sulfate over time at both storage temperatures.

Sulfur biogeochemistry of cold seeps in the Green Canyon region of the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Formolo, Michael J.; Lyons, Timothy W.

2013-10-01

Cold seeps in the Gulf of Mexico provide a natural laboratory to study biogeochemical cycling of sulfur, carbon, and oxygen at hydrate- and hydrocarbon-rich deep marine settings with obvious additional relevance to studies of diverse modern and ancient seeps. Of particular interest are the sulfur isotope signatures of microbial sulfate reduction coupled to anaerobic oxidation of methane and other non-methane liquid and gaseous hydrocarbons. Whereas most of the published sulfur isotope data from cold seep systems pertain to pore-water species, our study integrates both solid and dissolved sulfur: acid-volatile sulfides (SAVS), pyrite (Spy), elemental sulfur (S°), dissolved sulfate and ΣH2S. Modeled and 35SO42- reduction rates and δ13C and δ18O data for authigenic carbonates are integrated within this sulfur framework. Our results indicate extreme variability over narrow spatial and temporal scales within short distances (meters) from active seeps. High rates of microbial sulfate reduction can lead to complete consumption of the sulfate within the upper few centimeters of burial, while meters away the sulfate profile shows little depletion. Such small-scale variability must reflect the structure and temporal dynamics of hydrocarbon migration in the presence of low amounts of background organic matter. Our past work demonstrated that electron donors other than methane drive significant levels of microbial activity at these seeps, and very recent work has demonstrated that oxidation of higher chain volatile hydrocarbons can contribute to the high levels of microbial activity. These findings are consistent with our new results. Elevated concentrations of pyrite and diagenetic carbonate relative to background sediments are diagnostic of active seepage, yet the S isotopes tell more complex stories. Low levels of the transient, 'instantaneous' products of S cycling-AVS and S°-show high δ34S values that increase with depth. Most of the pyrite formation, however, seems to be very early as limited by the availability of reactive Fe phases. As such, δ34S values for pyrite at ancient seeps can show consistently low δ34S values that undersell the full intensity of microbial sulfate reduction. Low sedimentation rates, and the resulting low detrital iron fluxes, may in fact limit our ability to recognize seeps in the geologic record using only δ34S compositions for pyrite.

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

Nitrogen Fixation in Thermophilic Chemosynthetic Microbial Communities Depending on Hydrogen, Sulfate, and Carbon Dioxide

PubMed Central

Nishihara, Arisa; Haruta, Shin; McGlynn, Shawn E.; Thiel, Vera; Matsuura, Katsumi

2018-01-01

The activity of nitrogen fixation measured by acetylene reduction was examined in chemosynthetic microbial mats at 72–75°C in slightly-alkaline sulfidic hot springs in Nakabusa, Japan. Nitrogenase activity markedly varied from sampling to sampling. Nitrogenase activity did not correlate with methane production, but was detected in samples showing methane production levels less than the maximum amount, indicating a possible redox dependency of nitrogenase activity. Nitrogenase activity was not affected by 2-bromo-ethane sulfonate, an inhibitor of methanogenesis. However, it was inhibited by the addition of molybdate, an inhibitor of sulfate reduction and sulfur disproportionation, suggesting the involvement of sulfate-reducing or sulfur-disproportionating organisms. Nitrogenase activity was affected by different O2 concentrations in the gas phase, again supporting the hypothesis of a redox potential dependency, and was decreased by the dispersion of mats with a homogenizer. The loss of activity that occurred from dispersion was partially recovered by the addition of H2, sulfate, and carbon dioxide. These results suggested that the observed activity of nitrogen fixation was related to chemoautotrophic sulfate reducers, and fixation may be active in a limited range of ambient redox potential. Since thermophilic chemosynthetic communities may resemble ancient microbial communities before the appearance of photosynthesis, the present results may be useful when considering the ancient nitrogen cycle on earth. PMID:29367473

New insights into the rate dependence of sulfur isotope fractionation during dissimilatory sulfate reduction

NASA Astrophysics Data System (ADS)

Giannetta, M.; Druhan, J. L.; Sanford, R. A.

2016-12-01

The vast majority of experiments concerning the isotope partitioning of sulfate reducing bacteria (SRB) are conducted under artificially optimized growth conditions. In contrast, many natural environments supporting SRB reflect limited nutrient availability. In this study, we couple the cell-specific reduction rate of a common SRB to the characteristic partitioning of stable sulfur isotopes. However, our method is novel in that we regulate the addition of electron donor such that cell growth is minimized and cell-specific reduction rates are constant, thus simulating the low reactivity characteristic of natural conditions. Anoxic bioreactors containing equal amounts of Desulfovibrio vulgariswere continuously injected with formate to control the rate of dissimilatory sulfate reduction (DSR). Cell growth was minimized through two means, (1) a high initial culture density ensured the ratio of nutrients per cell was low; (2) the oxidation state of carbon in formate is unfavorable to cell biomass accumulation. Negligible cell growth was verified by flow cytometry. Four controlled DSR rates ranging from 0.32 to 1.8 µmole/hour exhibited fractionation factor (ɛ) values ranging from 9‰ to 4‰ over 1200 to 300 hours, respectively. These results demonstrate a unique value of ɛ for each rate of DSR, where larger S isotope partitioning is characteristic of a slower cell-specific rate of sulfate reduction. The results of this study provide a unique dataset that can be used to constrain variations in ɛ as a function of DSR rate. Specifically, the dataset offers a foundation to test recently proposed analytical models and predict variations in observed ɛ as a result of a multi-step reactive pathway. Based on these results, we suggest a novel rate expression for incorporation into reactive transport models. Such a rate law supports extrapolation of experimental behavior into natural conditions over modern to geologic timescales.

Comparison of normal and asthmatic subjects' responses to sulfate pollutant aerosols

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

Utell, M.J.; Morrow, P.E.; Hyde, R.W.

Epidemiological studies support an association between elevated levels of sulfates and acute respiratory disease. To determine if these pollutants produce airway hyperreactivity, 16 normal and 17 asthmatic subjects inhaled a control NaCl aerosol and the following sulfates: ammonium sulfate, sodium bisulfate, ammonium bisulfate, and sulfuric acid. A Lovelace generator produced particles with an average MMAD of approx. 1.0 ..mu..m (sigma/sub g/ approx. = 2.0) and concentrations of 0.1 and 1.0 mg/m/sup 3/. By double-blind randomization, all subjects breathed these aerosols for a 16-minute period. To determine if sulfate inhalation caused increased reactivity to a known bronchoconstrictor, all subjects inhaled carbacholmore » following each 16-minute exposure. Before, during, and after exposure, pulmonary function studies were performed. When compared to NaCl, sulfate (1 mg/m/sup 3/) produced significant reductions in airway conductance and flow rates in asthmatics. The two most sensitive asthmatics demonstrated changes even at 0.1 mg/m/sup 3/ sulfate. To a far more significant degree, the bronchoconstrictor action of carbachol was potentiated by sulfates more or less in relation to their acidity in normals and asthmatics.« less

Bipyrrole-Strapped Calix[4]pyrroles: Strong Anion Receptors That Extract the Sulfate Anion

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

Kim, Sung Kuk; Lee, Juhoon; Williams, Neil J

Cage-type calix[4]pyrroles 2 and 3 bearing two additional pyrrole groups on the strap have been synthesized. Compared with the parent calix[4]pyrrole (1), they were found to exhibit remarkably enhanced affinities for anions, including the sulfate anion (TBA+ salts), in organic media (CD2Cl2). This increase is ascribed to participation of the bipyrrole units in anion binding. Receptors 2 and 3 extract the hydrophilic sulfate anion (as the methyltrialkyl(C8-10)ammonium (A336+) salt)) from aqueous media into a chloroform phase with significantly improved efficiency (>10-fold relative to calix[4]pyrrole 1). These two receptors also solubilize into chloroform the otherwise insoluble sulfate salt, (TMA)2SO4 (tetramethylammonium sulfate).

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.

Sulfated and pyruvylated disaccharide alditols obtained from a red seaweed galactan: ESIMS and NMR approaches.

PubMed

Gonçalves, Alan G; Ducatti, Diogo R B; Duarte, M Eugênia R; Noseda, Miguel D

2002-11-29

The water-soluble acid agaran isolated from Acanthophora spicifera (Rhodophyta) was submitted to alkaline treatment for the complete cyclization of alpha-L-Galp 6-sulfate to 3,6-An-alpha-L-Galp units. The modified agaran was then partially depolymerized using partial reductive hydrolysis. The resulting oligosaccharide mixture was fractionated by adsorption and ion-exchange chromatography. Fractions were purified by gel-filtration chromatography and studied by ESIMS and NMR spectroscopy, including 1D 1H, 13C, DEPT and 2D 1H, 1H COSY, TOCSY and 1H, 13C HMQC procedures. The following neutral, pyruvylated, sulfated and sulfated/pyruvylated disaccharide alditols were obtained: beta-D-Galp-(1-->4)-3,6-An-L-GalOH; 4,6-O-(1-carboxyethylidene)-beta-D-Galp-(1-->4)-3,6-An-L-GalOH; beta-D-Galp 2-sulfate-(1-->4)-3,6-An-L-GalOH and 4,6-O-(1-carboxyethylidene)-beta-D-Galp 2-sulfate-(1-->4)-3,6-An-L-GalOH.

Intracellular metabolite levels shape sulfur isotope fractionation during microbial sulfate respiration

PubMed Central

Wing, Boswell A.; Halevy, Itay

2014-01-01

We present a quantitative model for sulfur isotope fractionation accompanying bacterial and archaeal dissimilatory sulfate respiration. By incorporating independently available biochemical data, the model can reproduce a large number of recent experimental fractionation measurements with only three free parameters: (i) the sulfur isotope selectivity of sulfate uptake into the cytoplasm, (ii) the ratio of reduced to oxidized electron carriers supporting the respiration pathway, and (iii) the ratio of in vitro to in vivo levels of respiratory enzyme activity. Fractionation is influenced by all steps in the dissimilatory pathway, which means that environmental sulfate and sulfide levels control sulfur isotope fractionation through the proximate influence of intracellular metabolites. Although sulfur isotope fractionation is a phenotypic trait that appears to be strain specific, we show that it converges on near-thermodynamic behavior, even at micromolar sulfate levels, as long as intracellular sulfate reduction rates are low enough (<<1 fmol H2S⋅cell−1⋅d−1). PMID:25362045

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.

Sulfate and nitrate in Asian dust particles observed in desert, coastal and marine air

NASA Astrophysics Data System (ADS)

Zhang, D.; Wu, F.; Junji, C.

2016-12-01

Sulfate and nitrate in dust particles are believed to be two key species which can largely alter the physical and chemical properties of the particles in the atmosphere, in particular under humid conditions. Their occurrence in the particles has usually been considered to be the consequence of particles' aging during their long-distance travel in the air although they are present in some crustal minerals. Our observations at two deserts in China during dust episodes revealed that there were soil-derived sulfate and background-like nitrate in atmospheric dust samples. Sulfate in dust samples was proportional to samples' mass and comprised at steady mass percentages in differently sized samples. In contrast, nitrate concentration was approximately stable and independent from dust loading. Our observations at inland and coastal areas of China during dust episodes revealed that sulfate and nitrate were hardly produced on the surface of dust particles that were originated from the deserts areas in northwestern China. This is because the dust particles were in the postfrontal air, where the temperature was low and the relative humidity was small due to the adiabatic properties of the air mass. There are a number studies reporting that sulfate and nitrate had been efficiently produced on mineral particles in inland areas of China. However, those mineral particles were more likely from the local areas rather than from the desert areas. Our observations in the coastal areas of Japan, which is located in the downstream areas of the Asian continent and surrounded by sea areas revealed that dust particles appearing there frequently contained sulfate and nitrate, indicating sulfate and nitrate had been efficiently produced on the surface of the particles when the particles traveled in the marine air between China and Japan.

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

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.

The Effects of Low Sulfate Concentrations on Modern Microbial Mat Communities: A Long Term Manipulation

NASA Technical Reports Server (NTRS)

Bebout, Brad; Carpenter, Steve; DesMarais, David J.; Discipulo, Mykell; Hogan, Mary; Turk, Kendra

2002-01-01

Microbial mats were widespread during the first ca. 2 Ga. of our biosphere's history. To better understand microbial ecosystems and their biomarkers under the low sulfate levels present in early oceans, we attempted a long-term (ca. 1 year) manipulation of sulfate in modem mats. Mats collected from salt ponds at Guerrero Negro, Baja Calif. Sur were incubated in a Greenhouse "Collaboratory" at Ames. Mats were maintained in artificial seawater brine containing either: 1) sulfate levels normal for these mats (70 mM), or 2) brine in which sulfate was replaced by chloride. Sulfate concentrations in the "low sulfate" brine gradually approached their lowest (to date) value of 0. 1 mM as sulfate was consumed and/or diffused out of the mat over a period of ca. 4 months. During that period of time, a number of differences between the treatments emerged. Relative to the "low sulfate" mats, "normal sulfate" mats had: 1) lower consumption of oxygen in the lower levels of the mat, 2) higher efficiencies of oxygenic photosynthesis, and 3) higher rates of nitrogen fixation. Rates of methane production by the mats increased greatly as sulfate concentrations fell below ca. 0.2 mM. In contrast, "low" and "normal" sulfate mats had similar net rates of exchange of O2 and dissolved inorganic C between the mats and overlying water. Reduced sulfate levels have diverse impacts upon these ecosystems.

Influence of Bicarbonate, Sulfate, and Electron Donors on Biological reduction of Uranium and Microbial Community Composition

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

Luo, Wensui; Zhou, Jizhong; Wu, Weimin

2007-01-01

A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 mM or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonatemore » (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and geoundwater geochemistry alter microbial communities responsible for U(VI) reduction.« less

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.

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.

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

Draft Genome Sequence of the Obligately Alkaliphilic Sulfate-Reducing Bacterium Desulfonatronum thiodismutans Strain MLF1

PubMed Central

Trubitsyn, Denis; Geurink, Corey; Pikuta, Elena; Lefèvre, Christopher T.; McShan, W. Michael; Gillaspy, Allison F.

2014-01-01

Desulfonatronum thiodismutans strain MLF1, an alkaliphilic bacterium capable of sulfate reduction, was isolated from Mono Lake, California. Here we report the 3.92-Mb draft genome sequence comprising 34 contigs and some results of its automated annotation. These data will improve our knowledge of mechanisms by which bacteria withstand extreme environments. PMID:25081260

Passive bioremediation technology incorporating lignocellulosic spent mushroom compost and limestone for metal- and sulfate-rich acid mine drainage.

PubMed

Muhammad, Siti Nurjaliah; Kusin, Faradiella Mohd; Md Zahar, Mohd Syakirin; Mohamat Yusuff, Ferdaus; Halimoon, Normala

2017-08-01

Passive bioremediation of metal- and sulfate-containing acid mine drainage (AMD) has been investigated in a batch study. Multiple substrates were used in the AMD remediation using spent mushroom compost (SMC), limestone, activated sludge (AS), and woodchips (WC) under anoxic conditions suitable for bacterial sulfate reduction (BSR). Limestones used were of crushed limestone (CLS) and uncrushed limestone, provided at two different ratios in mixed substrates treatment and varied by the proportion of SMC and limestone. The SMC greatly assisted the removals of sulfate and metals and also acted as an essential carbon source for BSR. The mixed substrate composed of 40% CLS, 30% SMC, 20% AS, and 10% WC was found to be effective for metal removal. Mn, Cu, Pb, and Zn were greatly removed (89-100%) in the mixed substrates treatment, while Fe was only removed at 65%. Mn was found to be removed at a greatly higher rate than Fe, suggesting important Mn adsorption onto organic materials, that is, greater sorption affinity to the SMC. Complementary with multiple treatment media was the main mechanism assisting the AMD treatment through microbial metal reduction reactions.

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.

Sulfate reducing bacteria in microbial mats: Changing paradigms, new discoveries

NASA Astrophysics Data System (ADS)

Baumgartner, L. K.; Reid, R. P.; Dupraz, C.; Decho, A. W.; Buckley, D. H.; Spear, J. R.; Przekop, K. M.; Visscher, P. T.

2006-03-01

Sulfate reducing bacteria (SRB) have existed throughout much of Earth's history and remain major contributors to carbon cycling in modern systems. Despite their importance, misconceptions about SRB are prevalent. In particular, SRB are commonly thought to lack oxygen tolerance and to exist only in anoxic environments. Through the last two decades, researchers have discovered that SRB can, in fact, tolerate and even respire oxygen. Investigations of microbial mat systems have demonstrated that SRB are both abundant and active in the oxic zones of mats. Additionally, SRB have been found to be highly active in the lithified zones of microbial mats, suggesting a connection between sulfate reduction and mat lithification. In the present paper, we review recent research on SRB distribution and present new preliminary findings on both the diversity and distribution of δ-proteobacterial SRB in lithifying and non-lithifying microbial mat systems. These preliminary findings indicate the unexplored diversity of SRB in a microbial mat system and demonstrate the close microspatial association of SRB and cyanobacteria in the oxic zone of the mat. Possible mechanisms and further studies to elucidate mechanisms for carbonate precipitation via sulfate reduction are also discussed.

High-throughput protein concentration and buffer exchange: comparison of ultrafiltration and ammonium sulfate precipitation.

PubMed

Moore, Priscilla A; Kery, Vladimir

2009-01-01

High-throughput protein purification is a complex, multi-step process. There are several technical challenges in the course of this process that are not experienced when purifying a single protein. Among the most challenging are the high-throughput protein concentration and buffer exchange, which are not only labor-intensive but can also result in significant losses of purified proteins. We describe two methods of high-throughput protein concentration and buffer exchange: one using ammonium sulfate precipitation and one using micro-concentrating devices based on membrane ultrafiltration. We evaluated the efficiency of both methods on a set of 18 randomly selected purified proteins from Shewanella oneidensis. While both methods provide similar yield and efficiency, the ammonium sulfate precipitation is much less labor intensive and time consuming than the ultrafiltration.

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.

Anaerobic oxidation of acetylene by estuarine sediments and enrichment cultures

USGS Publications Warehouse

Culbertson, Charles W.; Zehnder, Alexander J. B.; Oremland, Ronald S.

1981-01-01

Acetylene disappeared from the gas phase of anaerobically incubated estuarine sediment slurries, and loss was accompanied by increased levels of carbon dioxide. Acetylene loss was inhibited by chloramphenicol, air, and autoclaving. Addition of 14C2H2 to slurries resulted in the formation of 14CO2 and the transient appearance of 14C-soluble intermediates, of which acetate was a major component. Acetylene oxidation stimulated sulfate reduction; however, sulfate reduction was not required for the loss of C2H2 to occur. Enrichment cultures were obtained which grew anaerobically at the expense of C2H2.

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.

The effect of a confining unit on the geochemical evolution of ground water in the Upper Floridan aquifer system

USGS Publications Warehouse

Wicks, C.M.; Herman, J.S.

1994-01-01

In west-central Florida, sections of the Upper Floridan aquifer system range in character from confined to leaky to unconfined. The confining unit is the Hawthorn Formation, a clay-rich sequence. The presence or absence of the Hawthorn Formation affects the geochemical evolution of the ground water in the Upper Floridan aquifer system. Mass-balance and mass-transfer models suggest that, in unconfined areas, the geochemical reactions are dolomite dissolution, ion exchange (Mg for Na, K), sulfate reduction, calcite dissolution, and CO2 exchange. In the areas in which the Hawthorn Formation is leaky, the evolution of the ground water is accounted for by ion exchange, sulfate reduction, calcite dissolution, and CO2 exchange. In the confined areas, no ion exchange and only limited sulfate reduction occur, and the chemical character of the ground water is consistent with dolomite and gypsum dissolution, calcite precipitation, and CO2 ingassing. The Hawthorn Formation acts both as a physical barrier to the transport of CO2 and organic matter and as a source of ion-exchange sites, but the carbonate-mineral reactions are largely unaffected by the extent of confinement of the Upper Floridan aquifer. ?? 1994.

Biochemical passive reactors for treatment of acid mine drainage: Effect of hydraulic retention time on changes in efficiency, composition of reactive mixture, and microbial activity.

PubMed

Vasquez, Yaneth; Escobar, Maria C; Neculita, Carmen M; Arbeli, Ziv; Roldan, Fabio

2016-06-01

Biochemical passive treatment represents a promising option for the remediation of acid mine drainage. This study determined the effect of three hydraulic retention times (1, 2, and 4 days) on changes in system efficiency, reactive mixture, and microbial activity in bioreactors under upward flow conditions. Bioreactors were sacrificed in the weeks 8, 17 and 36, and the reactive mixture was sampled at the bottom, middle, and top layers. Physicochemical analyses were performed on reactive mixture post-treatment and correlated with sulfate-reducing bacteria and cellulolytic and dehydrogenase activity. All hydraulic retention times were efficient at increasing pH and alkalinity and removing sulfate (>60%) and metals (85-99% for Fe(2+) and 70-100% for Zn(2+)), except for Mn(2+). The longest hydraulic retention time (4 days) increased residual sulfides, deteriorated the quality of treated effluent and negatively impacted sulfate-reducing bacteria. Shortest hydraulic retention time (1 day) washed out biomass and increased input of dissolved oxygen in the reactors, leading to higher redox potential and decreasing metal removal efficiency. Concentrations of iron, zinc and metal sulfides were high in the bottom layer, especially with 2 day of hydraulic retention time. Sulfate-reducing bacteria, cellulolytic and dehydrogenase activity were higher in the middle layer at 4 days of hydraulic retention time. Hydraulic retention time had a strong influence on overall performance of passive reactors. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enhanced Removal of a Human Norovirus Surrogate from Fresh Vegetables and Fruits by a Combination of Surfactants and Sanitizers▿

PubMed Central

Predmore, Ashley; Li, Jianrong

2011-01-01

Fruits and vegetables are major vehicles for transmission of food-borne enteric viruses since they are easily contaminated at pre- and postharvest stages and they undergo little or no processing. However, commonly used sanitizers are relatively ineffective for removing human norovirus surrogates from fresh produce. In this study, we systematically evaluated the effectiveness of surfactants on removal of a human norovirus surrogate, murine norovirus 1 (MNV-1), from fresh produce. We showed that a panel of surfactants, including sodium dodecyl sulfate (SDS), Nonidet P-40 (NP-40), Triton X-100, and polysorbates, significantly enhanced the removal of viruses from fresh fruits and vegetables. While tap water alone and chlorine solution (200 ppm) gave only <1.2-log reductions in virus titer in all fresh produce, a solution containing 50 ppm of surfactant was able to achieve a 3-log reduction in virus titer in strawberries and an approximately 2-log reduction in virus titer in lettuce, cabbage, and raspberries. Moreover, a reduction of approximately 3 logs was observed in all the tested fresh produce after sanitization with a solution containing a combination of 50 ppm of each surfactant and 200 ppm of chlorine. Taken together, our results demonstrate that the combination of a surfactant with a commonly used sanitizer enhanced the efficiency in removing viruses from fresh produce by approximately 100 times. Since SDS is an FDA-approved food additive and polysorbates are recognized by the FDA as GRAS (generally recognized as safe) products, implementation of this novel sanitization strategy would be a feasible approach for efficient reduction of the virus load in fresh produce. PMID:21622782

Efflux transport of chrysin and apigenin sulfates in HEK293 cells overexpressing SULT1A3: The role of multidrug resistance-associated protein 4 (MRP4/ABCC4).

PubMed

Li, Wan; Sun, Hua; Zhang, Xingwang; Wang, Huan; Wu, Baojian

2015-11-01

Efflux transport is a critical determinant to the pharmacokinetics of sulfate conjugates. Here we aimed to establish SULT1A3 stably transfected HEK293 cells, and to determine the contributions of BCRP and MRP transporters to excretion of chrysin and apigenin sulfates. The cDNA of SULT1A3 was stably introduced into HEK293 cells using a lentiviral vector, generating a sulfonation active cell line (i.e., SULT293 cells). Identification of sulfate transporters was achieved through chemical inhibition (using chemical inhibitors) and biological inhibition (using short-hairpin RNAs (shRNAs)) methods. Sulfated metabolites were rapidly generated and excreted upon incubation of SULT293 cells with chrysin and apigenin. Ko143 (a selective BCRP inhibitor) did not show inhibitory effects on sulfate disposition, whereas the pan-MRP inhibitor MK-571 caused significant reductions (38.5-64.3%, p<0.001) in sulfate excretion and marked elevations (160-243%, p<0.05) in sulfate accumulation. Further, two efflux transporters (BCRP and MRP4) expressed in the cells were knocked-down by shRNA-mediated silencing. Neither sulfate excretion nor sulfate accumulation was altered in BCRP knocked-down cells as compared to scramble cells. By contrast, MRP4 knock-down led to moderate decreases (17.1-20.6%, p<0.05) in sulfate excretion and increases (125-135%, p<0.05) in sulfate accumulation. In conclusion, MRP4 was identified as an exporter for chrysin and apigenin sulfates. The SULT1A3 modified HEK293 cells were an appropriate tool to study SULT1A3-mediated sulfonation and to characterize BCRP/MRP4-mediated sulfate transport. Copyright © 2015 Elsevier Inc. All rights reserved.

Direct Identification of Tyrosine Sulfation by using Ultraviolet Photodissociation Mass Spectrometry

PubMed Central

Robinson, Michelle R.; Moore, Kevin L.; Brodbelt, Brodbelt

2014-01-01

Sulfation is a common post-translational modification of tyrosine residues in eukaryotes; however, detection using traditional liquid chromatography-mass spectrometry (LC-MS) methods is challenging based on poor ionization efficiency in the positive ion mode and facile neutral loss upon collisional activation. In the present study, 193 nm ultraviolet photodissociation (UVPD) is applied to sulfopeptide anions to generate diagnostic sequence ions which do not undergo appreciable neutral loss of sulfate even using higher energy photoirradiation parameters. At the same time, neutral loss of sulfate is observed from the precursor and charge reduced precursor ions, a spectral feature that is useful for differentiating tyrosine sulfation from the nominally isobaric tyrosine phosphorylation. LC-MS detection limits for UVPD analysis in the negative mode were determined to be around 100 fmol for three sulfated peptides, caerulein, cionin, and leu-enkephalin. The LC-UVPD-MS method was applied for analysis of bovine fibrinogen, and its key sulfated peptide was confidently identified. PMID:24845354

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.

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.

Effect of sulfate ions on growth and pollutants removal of self-flocculating microalga Chlorococcum sp. GD in synthetic municipal wastewater.

PubMed

Lv, Junping; Guo, Junyan; Feng, Jia; Liu, Qi; Xie, Shulian

2017-06-01

Sulfate is a primary sulfur source and can be available in wastewaters. Nevertheless, effect of sulfate ions on growth and pollutants removal of microalgae seems to be less investigated. At the present study, self-flocculating microalga Chlorococcum sp. GD was grown in synthetic municipal wastewater with different sulfate concentrations. Results indicated that Chlorococcum sp. GD grew better in synthetic municipal wastewater with 18, 45, 77, 136 and 271mg/L SO 4 2- than in wastewater without SO 4 2- . Chlorococcum sp. GD had also excellent removal efficiencies of nitrogen and phosphorus and effectively flocculated in sulfate wastewater. Sulfate deprivation weakened the growth, pollutants removal and self-flocculation of Chlorococcum sp. GD in wastewater. Antioxidative enzymes activity significantly increased and photosynthetic activity significantly decreased when Chlorococcum sp. GD was cultivated in sulfate-free wastewater. Sulfate deprivation probably reduced cell activity of growth, pollutants removal and flocculation via inducing the over-accumulation of reactive oxygen species (ROS). Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand.

PubMed

Seipp, Charles A; Williams, Neil J; Custelcean, Radu

2016-09-08

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, 1,4-benzene-bis(iminoguanidinium) (BBIG), is demonstrated. The ligand is synthesized as the chloride salt (BBIG-Cl) by in situ imine condensation of terephthalaldehyde with aminoguanidinium chloride in water, followed by crystallization as the sulfate salt (BBIG-SO4). Alternatively, BBIG-Cl is synthesized ex situ in larger scale from ethanol. The sulfate separation ability of the BBIG ligand is demonstrated by selective and quantitative crystallization of sulfate from seawater. The ligand can be recycled by neutralization of BBIG-SO4 with aqueous NaOH and crystallization of the neutral bis-iminoguanidine, which can be converted back into BBIG-Cl with aqueous HCl and reused in another separation cycle. Finally, (35)S-labeled sulfate and β liquid scintillation counting are employed for monitoring the sulfate concentration in solution. Overall, this protocol will instruct the user in the necessary skills to synthesize a ligand, employ it in the selective crystallization of sulfate from aqueous solutions, and quantify the separation efficiency.

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand

DOE PAGES

Seipp, Charles A.; Williams, Neil J.; Custelcean, Radu

2016-01-01

One simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, 1,4-benzene-bis(iminoguanidinium) (BBIG), is demonstrated. The ligand is synthesized as the chloride salt (BBIG-Cl) by in situ imine condensation of terephthalaldehyde with aminoguanidinium chloride in water, followed by crystallization as the sulfate salt (BBIG-SO4). Alternatively, BBIG-Cl is synthesized ex situ in larger scale from ethanol. Furthermore, the sulfate separation ability of the BBIG ligand is demonstrated by selective and quantitative crystallization of sulfate from seawater. These ligands can then be recycled by neutralization of BBIG-SO4 with aqueous NaOH and crystallization of the neutralmore » bis-iminoguanidine, which can be converted back into BBIG-Cl with aqueous HCl and reused in another separation cycle. Finally, 35S-labeled sulfate and β liquid scintillation counting are employed for monitoring the sulfate concentration in solution. Overall, this protocol will instruct the user in the necessary skills to synthesize a ligand, employ it in the selective crystallization of sulfate from aqueous solutions, and quantify the separation efficiency.« less

Investigation and optimization of the novel UASB-MFC integrated system for sulfate removal and bioelectricity generation using the response surface methodology (RSM).

PubMed

Zhang, Baogang; Zhang, Jing; Yang, Qi; Feng, Chuanping; Zhu, Yuling; Ye, Zhengfang; Ni, Jinren

2012-11-01

COD/sulfate ratio and hydraulic residence time (HRT), both of which influence sulfate loadings jointly, are recognized as the most two important affecting factors for sulfate removal and bioelectricity generation in the novel up-flow anaerobic sludge blanket reactor-microbial fuel cell (UASB-MFC) integrated system. The response surface methodology (RSM) was employed for the optimization of this system and the optimum condition with COD/sulfate ratio of 2.3 and HRT of 54.3h was obtained with the target of maximizing the power output. In terms of maximizing the total sulfate removal efficiency, the obtained optimum condition was COD/sulfate ratio of 3.7 and HRT of 55.6h. Experimental results indicated the undistorted simulation and reliable optimized results. These demonstrated that RSM was effective to evaluate and optimize the UASB-MFC system for sulfate removal and energy recovery, providing a promising guide to further improvement of the system for potential applications. Copyright © 2012 Elsevier Ltd. All rights reserved.

Method of removing arsenic and other anionic contaminants from contaminated water using enhanced coagulation

DOEpatents

Teter, David M.; Brady, Patrick V.; Krumhansl, James L.; Khandaker, Nadim R.

2006-11-21

An improved water decontamination process comprising contacting water containing anionic contaminants with an enhanced coagulant to form an enhanced floc, which more efficiently binds anionic species (e.g., arsenate, arsenite, chromate, fluoride, selenate, and borate, and combinations thereof) predominantly through the formation of surface complexes. The enhanced coagulant comprises a trivalent metal cation coagulant (e.g., ferric chloride or aluminum sulfate) mixed with a divalent metal cation modifier (e.g., copper sulfate or zinc sulfate).

Effect of ammonium sulfate and urea on PCDD/F formation from active carbon and possible mechanism of inhibition.

PubMed

Yan, Mi; Qi, Zhifu; Yang, Jie; Li, Xiaodong; Ren, Jianli; Xu, Zhang

2014-11-01

The effect of ammonium sulfate ((NH4)2SO4) and urea (CO(NH2)2) on polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) formation from active carbon was investigated in this study. Both additives could significantly inhibit PCDD/F formation, and PCDD/F (TEQ) generation was reduced to 98.5% (98%) or 64.5% (77.2%) after 5% (NH4)2SO4 or CO(NH2)2 was added into model ash, respectively. The inhibition efficiency of PCDDs was higher than the value of PCDFs, however, the reduction of PCDD/F yield was mainly from PCDFs decreasing. In addition, the solid-phase products were reduced more than the gas-phase compounds by inhibitors. By the measurement of chlorine emission in the phase of ion (Cl[Cl(-)]) and molecule gas (Cl[Cl2]), it was observed that both Cl[Cl(-)] and Cl[Cl2] were reduced after inhibitors were added into ash. Cl[Cl2] was reduced to 51.0% by urea addition, which was supposed as one possible mechanism of PCDD/F inhibition. Copyright © 2014. Published by Elsevier B.V.

The smog-fog-smog cycle and acid deposition

NASA Astrophysics Data System (ADS)

Pandis, Spyros N.; Seinfeld, John H.; Pilinis, Christodoulos

1990-10-01

A model including descriptions of aerosol and droplet microphysics, gas and aqueous-phase chemistry, and deposition is used to study the transformation of aerosol to fog droplets and back to aerosol in an urban environment. Fogs in polluted environments have the potential to increase aerosol sulfate concentrations but at the same time to cause reductions in the aerosol concentration of nitrate, chloride, ammonium and sodium and well as in the total aerosol mass concentration. The sulfate produced during fog episodes favors the aerosol particles that have access to most of the fog liquid water which are usually the large particles. Aerosol scavenging efficiencies of around 80 percent are calculated for urban fogs. Sampling and subsequent mixing of fog droplets of different sizes may result in measured concentrations that are not fully representative of the fogwater chemical composition and can introduce errors in the reported values of the ionic species deposition velocities. Differences in the major ionic species deposition velocities can be explained by their distribution over the droplet size spectrum and can be correlated with the species average diameter. Two different expressions are derived for use in fog models for the calculation of the liquid water deposition velocity during fog growth and dissipation stages.

Synthesis of potassium ferrate using residual ferrous sulfate as iron bearing material

NASA Astrophysics Data System (ADS)

Kanari, N.; Filippov, L.; Diot, F.; Mochón, J.; Ruiz-Bustinza, I.; Allain, E.; Yvon, J.

2013-03-01

This paper summarizes the results obtained during potassium ferrate (K2FeVIO4) synthesis which is a high added value material. This compound that contains iron in the rare hexavalent state is becoming a substance of growing importance for the water and effluent treatment industries. This is due to its multi-functional nature (oxidation, flocculation, elimination of heavy metals, decomposition of organic matter, etc.). The most well known synthesis methods for potassium ferrate synthesis are those involving the chemical and/or electrochemical oxidation of iron (II) and (III) from aqueous solutions having a high alkali concentration. These methods are generally characterized by a low FeVI efficiency due to the reaction of the potassium ferrate with water, leading to the reduction of FeVI into FeIII. Concerning the work pertinent to this paper, the synthesis of K2FeVIO4 was achieved by a simultaneous reaction of two solids (iron sulfate and KOH) and one gaseous oxidant (chlorine). The synthesis process is performed in a rotary reactor at room temperature and the global synthesis reaction is exothermic. The effects of different experimental parameters on the potassium ferrate synthesis are investigated to determine the optimal conditions for the process.

Monoalkyl sulfates as alkylating agents in water, alkylsulfatase rate enhancements, and the “energy-rich” nature of sulfate half-esters

PubMed Central

Wolfenden, Richard; Yuan, Yang

2007-01-01

Alkyl sulfate monoesters are involved in cell signaling and structure. Alkyl sulfates are also present in many commercial detergents. Here, we show that monomethyl sulfate acts as an efficient alkylating agent in water, reacting spontaneously with oxygen nucleophiles >100-fold more rapidly than do alkylsulfonium ions, the usual methyl donors in living organisms. These reactions of methyl sulfate, which are much more rapid than its hydrolysis, are insensitive to the nature of the attacking nucleophile, with a Brønsted βnuc value of −0.01. Experiments at elevated temperatures indicate a rate constant of 2 × 10−11 s−1 for the uncatalyzed hydrolysis of methyl sulfate at 25°C (t1/2 = 1,100 y), corresponding to a rate enhancement of ≈1011-fold by a human alkylsulfatase. Equilibria of formation of methyl sulfate from methanol and sodium hydrogen sulfate indicate a group transfer potential (ΔG′pH7) of −8.9 kcal/mol for sulfate ester hydrolysis. The magnitude of that value, involving release of the strong acid HSO4−, helps to explain the need for harnessing the free energy of hydrolysis of two ATP molecules in activating sulfate for the biosynthesis of sulfate monoesters. The “energy-rich” nature of monoalkyl sulfate esters, coupled with their marked resistance to hydrolysis, renders them capable of acting as sulfating or alkylating agents under relatively mild conditions. These findings raise the possibility that, under appropriate circumstances, alkyl groups may undergo transfer from alkyl sulfate monoesters to biological target molecules. PMID:17182738

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.

Draft Genome Sequence of the Obligately Alkaliphilic Sulfate-Reducing Bacterium Desulfonatronum thiodismutans Strain MLF1.

PubMed

Trubitsyn, Denis; Geurink, Corey; Pikuta, Elena; Lefèvre, Christopher T; McShan, W Michael; Gillaspy, Allison F; Bazylinski, Dennis A

2014-07-31

Desulfonatronum thiodismutans strain MLF1, an alkaliphilic bacterium capable of sulfate reduction, was isolated from Mono Lake, California. Here we report the 3.92-Mb draft genome sequence comprising 34 contigs and some results of its automated annotation. These data will improve our knowledge of mechanisms by which bacteria withstand extreme environments. Copyright © 2014 Trubitsyn et al.

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.

The ecology of fiddler crab Uca forcipata in mangrove forest

NASA Astrophysics Data System (ADS)

Mokhtari, Mohammad; Ghaffar, Mazlan Abd; Usup, Gires; Cob, Zaidi Che

2013-11-01

Fiddler crab burrows increase oxygen dispersion in anoxic mangrove sediment and promote iron reduction and nitrification process over sulfate reduction in subsurface sediment. Therefore it is expected to accelerate decomposition rate under oxic and suboxic conditions. In this study the effect of environmental parameters on the local distribution of U. forcipata and subsequently the effect of crab burrows on sediment characteristics were investigated. Our result indicated that U. forcipata prefers to live in the open mudflats under the shade of mangrove trees. The most important factors determining their presence were sediment texture, porosity, organic content, water content, carbon content and temperature. Measurement of redox potential and iron pools clearly indicated a distinct oxidized layer around burrows although sediment porosity, organic and water content did not differ significantly between burrowed and non-burrowed mudflats and even among the burrow profiles. This result implies the oxidation created by burrowing activity of U .forcipata was not efficient to change physical properties of mangrove sediments.

Improved Procedure for Direct Coupling of Carbohydrates to Proteins via Reductive Amination

PubMed Central

Gildersleeve, Jeffrey C.; Oyelaran, Oyindasola; Simpson, John T.; Allred, Benjamin

2009-01-01

Carbohydrate-protein conjugates are utilized extensively in basic research and as immunogens in a variety of bacterial vaccines and cancer vaccines. As a result, there have been significant efforts to develop simple and reliable methods for the construction of these conjugates. While direct coupling via reductive amination is an appealing approach, the reaction is typically very inefficient. In this paper, we report improved reaction conditions providing an approximately 500% increase in yield. In addition to optimizing a series of standard reaction parameters, we found that addition of 500 mM sodium sulfate improves the coupling efficiency. To illustrate the utility of these conditions, a series of high mannose BSA conjugates were produced and incorporated into a carbohydrate microarray. Ligand binding to ConA could be observed and apparent affinity constants (Kds) measured using the array were in good agreement with values reported by surface plasmon resonance. The results show that the conditions are suitable for microgram scale reactions, are compatible with complex carbohydrates, and produce biologically active conjugates. PMID:18597509