Sulfate-reducing Activity Research Articles

Early diagenetic processes in an iron-dominated marine depositional system

The early diagenetic interplay between reactive iron, sulfur, and organic matter in the bathymetrically isolated Santa Monica Basin (SMB) sediments are investigated in this study. We explore solid-phase and porewater profiles from the basin, supplemented with a transect from 71 to 907 m water depth that includes oxygenated (>60 μM O2) bottom waters near the coast and oxygen-deficient waters (∼4 µM O2) in the basin. The geochemical data of the basin sediments are further scrutinized by means of reactive transport modeling.The results show that the basin sediments do not follow the traditional geochemical signatures of oxygen-deficient settings. A lack of dissolved sulfide accumulation and sulfurized iron persists despite the sediments being deposited under reducing conditions (without bioturbation/bioirrigation), strong organic carbon input (TOC up to 5.0 wt%), and active dissimilatory sulfate reduction. Not only did we find an exceptional enrichment in highly reactive Fe in the surface sediments (∼45 % of total Fe), but the enrichment of reactive Fe, including ferrihydrite, persists downcore and coexists with high levels of dissolved Fe. The enhanced preservation of Fe oxides and lack of iron-sulfide precipitation is in part explained by detection via Mössbauer spectra of iron oxides bounded to organic matter (Fe[III]-OM coprecipitates).The modeled Fe budget shows that most of the Fe oxides in the surface sediments are internally recycled by upward diffusion and subsequent oxidation of Fe2+. Sulfide oxidation coupled to Fe reduction effectively precludes sulfide accumulation while enhancing build-up of dissolved Fe, fueling the Fe cycle within the first 5 cm depth. Continuous reoxidation of Fe2+ enhances the formation of Fe(III)-OM coprecipitates, limiting the amount of reactive organic matter. In the unavailability of labile organic matter, other than within the uppermost layers, the organic-rich sediment profiles are dominated by Fe cycling that limits the production and preservation of sulfides and enhances the preservation of Fe oxides and organic carbon. This study highlights key local controls on Fe availability in marginal basins and describes an intricate biogeochemical C-Fe-S cycling in modern and possibly ancient marine systems with important implications for Fe availability in the marine realm.

Pyrites in a salt marsh-ria system: Quantification, morphology, and mobilization

Galician Rias are among the most productive ecosystems in the world. Consequently, the soils of their salt marshes and sediments of the intertidal flats show high organic matter contents, reactive Fe, and sulfate, which promote pyrite synthesis and accumulation, using sulfate for organic matter decomposition. This work studies the morphological variability and concentration of pyrites (individual crystals and framboids) in different geochemical environments found in the Ria de Ortigueira (salt marsh soils and bottom sediments in the inner, middle, and outer section), addressing their dynamics in the marsh-ria system in relation to the hydrodynamic characteristics defined by tides and river discharges. Framboidal pyrites were the dominant morphology in marsh soils and sediments in the middle and inner sections of the Ria, while isolated crystals dominated its outer section. The results showed that lower marsh soils (colonized by Spartina) are the most favorable environment for pyrite synthesis, showing high pyritic Fe concentrations and high degrees of pyritization, largely exceeding the values observed in sediments from Galician Rias and from most sedimentary environments worldwide. However, the amount of framboidal pyrites present in the lower marsh (SPE: 4–5 × 104 framboids) was clearly lower than in bottom sediments of the inner and middle part of the Ria de Ortigueira (∼2–7 × 106 framboids), mainly due to the fact that pyrites were found to form large framboids in lower salt marsh soils. Thus, the amount of framboidal pyrites does not seem to be a good indicator of redox conditions in modern marine sediments. Pyrite crystals found in the sediments of the Ria showed poorly defined vertices and facets, indicating their degradation and suggesting that a significant amount of the pyrites found in the middle and inner sections derive from marsh collapse. Finally, the output of framboidal pyrites towards the outer Ria de Ortigueira reflects the low intensity of residual flows in this Ria. Therefore, the pyrites observed in the outer section consisted only of isolated crystals, presumably formed in situ under low sulfate-reducing activity conditions.

Dynamic sulfur and carbon cycles related to microbial sulfate reduction and volcanic activity during the Hirnantian glaciation in the Upper Yangtze Basin, South China

Parallel positive excursions of organic carbon (δ13Corg) and pyrite sulfur (δ34Spy) isotopes occurred globally during the Hirnantian glacial period. However, the reasons for these isotope excursions and their relationship with paleoenvironmental dynamics are not fully understood. This study presents a high-resolution geochemical investigation of the Tianlin section of the Upper Yangtze Basin, South China. The total organic carbon (TOC), iron speciation, trace elements, δ13Corg, and δ34Spy were analyzed and compared with published results from the other four sections in the same basin. A negative relationship was observed for the sulfate reduction index (SRI) with TOC and organic carbon accumulation rate. This suggests that the abundance of sedimentary organic matter was not the main factor inhibiting microbial sulfate reduction (MSR). The significant positive correlations of SRI with pyrite and δ34Spy showed that MSR promoted the formation of pyrite and that the availability of sulfate was the main limiting factor for the δ34Spy change. The negative excursions of δ13Corg and δ34Spy during the pre-glacial and post-glacial periods were coupled with dense segments of bentonite, indicating that volcanism was the main driving force for the negative excursions of C and S isotopes. Moreover, the sulfate input of rivers, restored at the post-glacial period, was the main reason for the continued negative excursion of S isotopes. Our results emphasize the key role of MSR and volcanic activity in C and S isotope excursions and their corresponding environmental changes in semi-restricted basins during the Hirnantian glaciation.

Effects of sulfate concentration on anaerobic treatment of wastewater containing monoethanolamine using an up-flow anaerobic sludge blanket reactor

Monoethanolamine (MEA), a toxic organic chemical, is widely used in industries and is found in their wastewater. Anaerobic MEA degradation is an appropriate strategy to reduce energy and cost for treatment. Industry wastewaters also contain sulfate, but information on the effects of sulfate on MEA degradation is limited. Here, an up-flow anaerobic sludge blanket (UASB) for MEA-containing wastewater treatment was operated under psychrophilic conditions (18–20 ºC) to investigate the effects of sulfate on the microbial characteristics of the retained sludge. To acclimatize the sludge, the proportion of MEA in the influent (containing sucrose, acetate, and propionate) was increased from 15% to 100% of total COD (1500 mg L–1); sulfate was then added to the influent. The COD removal efficiency remained above 95% despite the increase in MEA and sulfate. However, granular sludge disintegration was observed when sulfate was increased from 20 to 330 mg L–1. Batch tests revealed that propionate and acetate were produced as the metabolites of MEA degradation. In response to sulfate acclimation, methane-producing activities for propionate and hydrogen declined, while sulfate-reducing activities for MEA, propionate, and hydrogen increased. Accordingly, acclimation and changes in dominant microbial groups promoted the acetogenic reaction of propionate by sulfate reduction.

Variability of sulfur isotopes and trace metals in pyrites from the upper oceanic crust of the South China Sea basin, implications for sulfur and trace metal cycling in subsurface

The circulation of seawater within the oceanic crust promotes cycling of metals and sulfur, as well as development of the subsurface biosphere. Characterization of the full spectrum of sulfide geochemistry in the altered oceanic crust is critical for a complete understanding of global cycling of sulfur and metals, while those in off-axis hydrothermal circulation have received less attention. This study applied a combination of in-situ sulfur isotopic and trace metal analyses to study the pyrite geochemical features in altered basalts of the South China Sea basin. This contribution unravels a detailed picture of the cycling of sulfur and metals in the subsurface. Such cycling is likely to be co-controlled by the hydrothermal and microbial activities when oceanic crusts transit from on-axis to off-axis hydrothermal systems.A total of five groups of pyrites associated with distinct mineral assemblages, morphologies, trace metal enrichment and sulfur isotopic values were observed in altered basalts. Pyrite disseminated (type 1) within the background hydrothermal alteration is characterized by δ34S values close to zero, with relative enrichment of trace metals (> 500 ppm), such as Ni, Co, and Cu. This type of pyrite is most likely to precipitate from upwelling high-temperature hydrothermal fluids when they ascended towards the seafloor. Sulfur was mainly derived from magmatic sulfides. Linear regression analyses of trace metal contents in disseminated pyrite show various strong positive correlations between trace metals reflecting a series of metal mobility processes, including incorporation into pyrite and leaching directly from sulfides or silicate minerals. Additionally, a population of pyrite has δ34S values ranging from +4 to +8 ‰ and low trace element contents, which reveals precipitation conditions where the ascending high-temperature hydrothermal fluids have mixed with significant amounts of seawater-sourced fluids. This group of pyrites is either formed by the replacement of silicates as patchy texture (type 2) or are exclusively associated with epidote‑carbonate veins (type 3). Furthermore, strongly positive δ34S signatures are observed within framboidal pyrite (type 4) (δ34S up to +57 ‰) and within overgrown euhedral pyrite (type 5) (δ34S up to +24 ‰). These unprecedented isotopically-heavy framboidal pyrite in modern oceanic crust presents a well-preserved organic matter framework, which is interpreted as a consequence of microbial sulfate reduction activities based on current observations. The extremely positive values of the sulfur isotopes could be produced by Rayleigh isotopic fractionation when ~77% sulfate (assumed with an initial seawater sulfate δ34S of 21%) is consumed by microorganisms in closed systems, in this case, the cavities in the altered basalt. The microorganisms meanwhile may enhance the sequestration of trace metals into pyrite, possibly through microbial metabolisms or detoxification processes. The positive δ34S values of overgrown euhedral pyrite (type 5) are interpreted to be mainly introduced by the involvement of seawater-derived sulfur or inherited from the framboidal pyrite.The various isotopic and elemental signatures in these five types of pyrites could be linked to either the hydrothermal or microbial processes occurring within the upper oceanic crust in the South China Sea basin. Both processes are critical to the metal and sulfur cycling in subsurface and should be considered jointly in future studies. Additionally, our results exemplify the potential roles of microorganisms, not only in accumulating trace metals in sulfides in the subsurface but also as a potential biosignature to reveal microbial activities in similar environments in the early Earth.

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

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

Role of the substrate on Ni inhibition in biological sulfate reduction

In treating mine-impacted waters using sulfate-reducing bacteria (SRB), metal inhibition and substrate selection are important factors affecting the efficiency of the bioprocess. This work investigated the role of the substrate (i.e. lactate, formate, glycerol and glucose) on Ni inhibition to SRB with sulfate-reducing activity tests at initial pH 5, 7 and 9 and 100 mg/L of Ni. Results indicated that the type of substrate was a significant factor affecting Ni inhibition in SRB, which was the most negligible in the lactate system, followed by glycerol, glucose, and formate. Although less significant, Ni inhibition also varied with the pH, leading for instance, to a reduction of 77% in the sulfate reducing activity for the formate system, but only of 28% for lactate at pH 5. The added substrate also influenced the precipitation kinetics and the characteristics of the precipitates, reaching Ni precipitation extents above 95%, except for glucose (83.2%).

Desulphurization of FGD wastewater through bacterial sulfate reduction process with agricultural incineration bottom ash as an amendment

Coal-fired power plants produce a large amount of sulfate-laden flue gas desulphurization (FGD) wastewater, while a sustainable amount of incineration ash was produced as solid waste in biomass power plants. Both FGD wastewater and incineration ash led to serious environmental problems without proper treatment. Sulfate reduction was an efficient technology for FGD wastewater treatment, however, the carbon source was insufficient for reducing sulfate in FGD wastewater which needed to be replenished. In this study, pyrolyzed incineration bottom ash (PIA) was introduced to sulfate reducers for FGD wastewater treatment. Sulfate-reducing activity increased (up to 2.9-fold) with PIA300 (incineration ash pyrolyzed under 300 °C) addition. Remarkably increasing abundance of Clostridium (12-fold) and Paraclostridium sp. (79-fold) bacteria were observed in sulfate-reducing sludge with PIA300 addition. Pyrolyzed incineration ash not only acted as a carrier for sulfate reducers, but also provided additional carbon, alkalinity and trace elements (Fe, K, Ca, etc.) for sulfate reduction. Incineration ash was partially degraded by sulfate-reducing bacteria (up to 39.4%), meanwhile, heavy metals (Mg, Al, Cr, Co, Ni, Cu, Zn, etc.) leached from ash and existed in FGD wastewater were efficiently co-removed (95–100%). Addition of PIA to sulfate reducers led to increased formation of extracellular polymeric substances, which might enhance the biotransformation and degradation of organic matters in both ash and FGD wastewater. Thus, a promising FGD wastewater treatment technology was established in this study, to achieve simultaneous FGD wastewater reclaim and solid waste utilization.

Transformation of inherent microorganisms in Wyoming-type bentonite and their effects on structural iron

Bentonite is one of the materials used to construct engineered barriers in high-level radioactive nuclear waste geological disposal with its many advantageous features such as low hydraulic conductivity, self-sealing ability, durability, adsorption and immobilization of metals and radionuclides and reduction of microbial activity. Many of these properties are linked with the bentonite swelling capability. Transformations of indigenous microorganism communities from Wyoming-type bentonite and the Finnish repository site groundwater and their effects on the bentonite structural iron over five years were studied in repository relevant anoxic and oxic slurry conditions. Active sulfate reduction (0.06 nmol mL−1 day−1) was detected in the anoxic microcosm waters after a year, however after two years sulfate reduction was not active anymore. Microbial numbers determined by quantitative PCR in the bentonite slurry of both experiment types supported the finding of decrease of overall microbial activity after a year of incubation that was not maintained anymore by the dissolving organic carbon from the bentonite. Regular electron donor additions (final concentration of 2 mM for formate and acetate each, three times per year) activated the microbiome resulting in increasing numbers of bacterial 16S rRNA gene copies and sulfate reducers (dsrB gene copies) as well as detection of sulfide in the water phase of both experiment types. After 4.9 years the structural iron in the fine portion of the montmorillonite had become completely reduced in all microbial microcosms and minor smectite illitization was detected especially in anoxic microcosms. Dominating bacterial groups at the end of the experiment were mainly known sulfur/sulfate and iron reducers. Archaea and fungi constituted a minor part of the microbiomes. In originally oxic microcosms, the bacterial 16S RNA and dsrB gene copy numbers were lower than in the anoxic experiment but started to significantly increase after the electron donor additions. Microorganisms originating from the repository environment could reduce the bentonite structural iron in a few years to an extent likely to affect the bentonite swelling ability if sufficient amounts of suitable electron donors are available in localized areas where bentonite is not at high density and pressure in the geological disposal.

Biological Sulfate Reduction in Deep Subseafloor Sediment of Guaymas Basin

Sulfate reduction is the quantitatively most important process to degrade organic matter in anoxic marine sediment and has been studied intensively in a variety of settings. Guaymas Basin, a young marginal ocean basin, offers the unique opportunity to study sulfate reduction in an environment characterized by organic-rich sediment, high sedimentation rates, and high geothermal gradients (100–958°C km−1). We measured sulfate reduction rates (SRR) in samples taken during the International Ocean Discovery Program (IODP) Expedition 385 using incubation experiments with radiolabeled 35SO42− carried out at in situ pressure and temperature. The highest SRR (387 nmol cm−3 d−1) was recorded in near-surface sediments from Site U1548C, which had the steepest geothermal gradient (958°C km−1). At this site, SRR were generally over an order of magnitude higher than at similar depths at other sites (e.g., 387–157 nmol cm−3 d−1 at 1.9 mbsf from Site U1548C vs. 46–1.0 nmol cm−3 d−1 at 2.1 mbsf from Site U1552B). Site U1546D is characterized by a sill intrusion, but it had already reached thermal equilibrium and SRR were in the same range as nearby Site U1545C, which is minimally affected by sills. The wide temperature range observed at each drill site suggests major shifts in microbial community composition with very different temperature optima but awaits confirmation by molecular biological analyses. At the transition between the mesophilic and thermophilic range around 40°C–60°C, sulfate-reducing activity appears to be decreased, particularly in more oligotrophic settings, but shows a slight recovery at higher temperatures.

Treatment system integrated a reactor with sulfate-reducing activity and a constructed wetland for contaminant removal

Treatment system integrated a reactor with sulfate-reducing activity and a constructed wetland for contaminant removal

Biological, geological and chemical effects of oxygen injection in underground gas storage aquifers in the setting of biomethane deployment

The last few years have seen the proliferation of anaerobic digestion plants to produce biomethane. Oxygen (O2) traces added to biogas during the desulfurization process are co-injected in the gas network and can be stored in Underground Gas Storage (UGS). However, there are no data available for the undesirable effects of O2 on these anoxic environments, especially on deep aquifers. In addition to mineral alteration, O2 can have an impact on the anaerobic autochthonous microbial life. In our study, the storage conditions of an UGS aquifer were reproduced in a high-pressure reactor and bio-geo-chemical interactions between the aqueous, gas and solid phases were studied. Sulfate was depleted from the liquid phase for three consecutive times during the first 130 days of incubation reproducing the storage conditions (36 °C, 60 bar, methane with 1% CO2). Sulfate-reducers, such as Desulfovibrionaceae, were identified from the high-pressure system. Simulations with PHREEQC were used to determine the thermodynamic equilibrium to confirm any gas consumption. CO2 quantities decreased in the gas phase, suggesting its use as carbon source by microbial life. Benzene and toluene, hydrocarbons found in traces and known to be biodegradable in storages, were monitored and a decrease of toluene was revealed and associated to the Peptococcaceae family. Afterwards, O2 was added as 1% of the gas phase, corresponding to the maximum quantity found in biomethane after desulfurization process. Re-oxidation of sulfide to sulfate was observed along with the end of sulfate reducing activity and toluene biodegradation and the disappearance of most of the community. H2 surprisingly appeared and accumulated as soon as hydrogenotrophic sulfate-reducers decreased. H2 would be produced via the necromass fermentation accomplished by microorganisms able to resist the oxic conditions of 4.42·10-4 mol.Kgw-1 of O2. The solid phase composed essentially of quartz, presented no remarkable changes.

Effects of combined tannic acid/fluoride on sulfur transformations and methanogenic pathways in swine manure.

Livestock manure emits reduced sulfur compounds and methane, which affect nature and the climate. These gases are efficiently mitigated by addition of a tannic acid-sodium fluoride combination inhibitor (TA-NaF), and to some extent by acidification. In this paper, TA-NaF treatment was performed on swine manure to study the treatment influence on methanogenic pathways and sulfur transformation pathways in various laboratory experiments. Stable carbon isotope labeling revealed that both untreated and TA-NaF treated swine manures were dominated by hydrogenotrophic methanogenesis. However, in supplementary experiments in wastewater sludge, TA-NaF clearly inhibited acetoclastic methanogenesis, whereas acidification inhibited hydrogenotrophic methanogenesis. In swine manure, TA-NaF inhibited s-amino acid catabolism to a larger extent than sulfate reduction. Conversely, acidification reduced sulfate reduction activity more than s-amino acid degradation. TA-NaF treatment had no significant effect on methanogenic community structure, which was surprising considering clear effects on isotope ratios of methane and carbon dioxide. Halophile sulfate reducers adapted well to TA-NaF treatment, but the community change also depended on temperature. The combined experimental work resulted in a proposed inhibition scheme for sulfur transformations and methanogenic pathways as affected by TA-NaF and acidification in swine manure and in other inocula.

Active microbial sulfate reduction in fluids of serpentinizing peridotites of the continental subsurface

Serpentinization of peridotites in Earth’s mantle is associated with the generation of hydrogen and low molecular weight organics that could support subsurface life. Studies of microbial metabolisms in peridotite-hosted environments have focused primarily on methanogenesis, yet DNA sequences, isotopic composition of sulfides and thermodynamic calculations suggest there is potential for microbial sulfate reduction too. Here, we use a sulfate radiotracer-based method to quantify microbial sulfate reduction rates in serpentinization fluids recovered from boreholes in the Samail Ophiolite, Oman and the California Coast Range Ophiolite, USA. We find that low levels of sulfate reduction occur at pH up to 12.3. These low levels could not be stimulated by addition of hydrogen, methane or small organic acids, which indicates that this metabolism is limited by factors other than substrate availability. Cellular activity drops at pH > 10.5 which suggests that high fluid pH exerts a strong control on sulfate-reducing organisms in peridotites.

Deciphering cryptic methane cycling: Coupling of methylotrophic methanogenesis and anaerobic oxidation of methane in hypersaline coastal wetland sediment

Methanogenesis has recently been shown to fuel anaerobic oxidation of methane (AOM) within the sulfate-reducing zone of marine sediments, coining the term “cryptic methane cycle”. Here we present research on the relationship between methanogenesis and AOM in a shallow hypersaline pool (∼130 PSU) within a southern California coastal wetland. Sediment (top 20 cm) was subjected to geochemical analyses, in-vitro slurry experiments, and radiotracer incubations using 35S-SO42−, 14C-mono-methylamine, and 14C-CH4, to study sulfate reduction, methylotrophic methanogenesis, and AOM. An adapted radioisotope method was used to follow cryptic methane cycling in 14C-mono-methylamine labeling incubations with increasing incubation times (1 hour to three weeks). Results showed peaks in AOM (max 13 nmol cm−3 d−1) and sulfate reduction activity (max 728 nmol cm−3 d−1) within the top 6 cm. Below 6 cm, AOM activity continued (max 15 nmol cm−3 d−1), while sulfate reduction was absent despite 67 mM sulfate, suggesting AOM was coupled to the reduction of iron. Methane concentrations were low (<50 nM) throughout the sediment. Batch sediment slurry incubations with methylated substrates (mono-methylamine and methanol) stimulated methanogenesis, pointing to the presence of methylotrophic methanogens. Incubations with 14C-mono-methylamine revealed the simultaneous activity of methanogenesis and coupled AOM through the stepwise transfer of 14C from mono-methylamine to CO2 via methane. Our results suggest that AOM is a crucial process in coastal wetland sediments to prevent the buildup of methane in the sulfate-reducing zone. We propose that cryptic methane cycling has been largely overlooked in coastal wetlands resulting in incomplete understanding of carbon cycling in this environment.

Synergistic approach to control reservoir souring in the moderately thermophilic oil fields of western India

Souring, the increase in sulfide concentration in production fluid, exists in the moderately high temperature oil fields of western India located in state of Rajasthan. The source water for oil production is taken from an underground aquifer that has high salinity and sulfate concentration. The reduction of this sulfate to sulfide was initiated above-ground when this source water was mixed with produced water. Current research revealed that high temperature (55 °C) and low salinity are the factors that influence souring in these fields. It was observed that the microbial community of the produced water has a significant proportion of thermophilic SRB and the active sulfate reduction takes place only after produced water was mixed with source water for reinjection. To stop sulfate reduction at these sites, six combinations of biocides and metabolic inhibitors were screened. Out of these combinations, nitrate and benzalkonium chloride (BAC) showed a maximum synergistic inhibitory effect on SRB growth.

Preservation of organic matter in shale linked to bacterial sulfate reduction (BSR) and volcanic activity under marine and lacustrine depositional environments

Black organic-rich shale is a sedimentary product of strongly reducing environmental water bodies, and is the main source of shale oil and gas. During its formation, the presence of sulfate promotes bacterial sulfate reduction (BSR), but little attention has been paid to how BSR affects the preservation of organic matter (OM) in different sedimentary environments. In this study, the Wufeng-Longmaxi Formations from the Sichuan Basin, the Chang-7 Member (the seventh member of the Triassic Yanchang Formation) from the Ordos Basin, the Qingshankou and Nenjiang Formations in the Songliao Basin, as well as the New Albany shale from the Appalachian Basin are selected for investigation. Results show that there is a positive correlation between total sulfur (TS) and total organic carbon (TOC) contents, and the sulfate reduction index (SRI) and TOC show two-stage exponential changes. When the SRI is higher than 1.375, the overall TOC content is low, indicating that a large amount of organic matter is consumed through intense BSR. When the SRI is lower than 1.375, the TOC content is significantly higher, indicating that weak BSR has relatively little effect on organic matter degradation.In the normal marine sedimentary environment for the New Albany shale in North America, the high concentration of sulfate was conducive to BSR, but the increased input of terrestrial OM compensated for the marine OM consumption by BSR, resulting in a high TOC value in the shale. Volcanic activity provides additional sulfates into the water column and triggers BSR occurrence, but the high concentration of nutrients brought by volcanic activity in the shales of the Wufeng-Longmaxi Formations and the Chang-7 Member promoted paleoproductivity, offset the effect of OM consumption by BSR, and resulted in the high TOC values seen in these shales. When a large amount of sulfate was input into terrestrial lakes through volcanic activity or marine transgression, there were significantly different effects on the preservation of organic matter in lacustrine shales. Nutrients from the volcanic activity increased the paleoproductivity of lakes during the Chang-7 period, while decreasing the impact of BSR on OM, resulting in a high TOC value in the Chang-7 Member shale. However, when the lacustrine basin was subjected to marine transgression, paleoproductivity weakly increased and BSR consumed a larger proportion of the OM, reducing the TOC values and forming the relatively low TOC shale of the Qingshankou and Nenjiang Formations in the Songliao Basin.

Assimilatory and dissimilatory sulfate reduction in the bacterial diversity of biofoulant from a full-scale biofilm-membrane bioreactor for textile wastewater treatment

Assimilatory and dissimilatory sulfate reduction (ASR and DSR) are the core bacterial sulfate-reducing pathways involved in wastewater treatment. It has been reported that sulfate-reducing activities could happen within biofoulants of membrane bioreactors during wastewater treatment. Biofoulants are mainly microbial products contributing membrane fouling and subsequent rising energy consumption in driving membrane filtration. Biofoulants from a full-scale biofilm-membrane bioreactor (biofilm-MBR) treating textile wastewater were investigated in this study. During a 10-month operation, sulfate concentrations in the effluent of the biofilm-MBR gradually decreased alongside with the creeping up sulfite concentrations when biofoulants were also building up on membrane modules. Sulfide had no apparent increases in the effluent during this period. Metagenomic analysis revealed diverse microbial communities residing in the biofoulants. Further analysis on their genetic traits revealed abundant ASR's and DSR's functional genes. A plethora of sulfate-reduction bacteria (SRB), including the well-known Desulfovibrio, Desulfainum, Desulfobacca, Desulfobulbus, Desulfococcus, Desulfonema, Desulfosarcina, Desulfobacter, Desulfobacula, Desulfofaba, Desulfotigum, Desulfatibacillum, Desulfatitalea, Desulfobacterium, were detected in the biofoulants. They were believed to play some important carbon and sulfur-cycling roles in our study. Based on metagenomic analysis, we also deduced that ASR was a functionally more important sulfate-reducing route because of the high abundance of assimilatory sulfate reductases detected. Also, the “AMP (adenosine monophosphate)→sulfite” step was a key reaction shared by both ASR and DSR in the biofoulant. This step might be responsible for the sulfite accumulation in the biofilm-MBR effluent. Overall, ASR functional genes in the biofoulants were more abundant. But the bacteria possessing complete DSR pathways caused the sulfide production in the biofilm-MBR.

Modelling the Effects of Non-Steady State Transport Dynamics on the Sulfur and Oxygen Isotope Composition of Sulfate in Sedimentary Pore Fluids

We present the results of an isotope-enabled reactive transport model of a sediment column undergoing active microbial sulfate reduction to explore the response of the sulfur and oxygen isotopic composition of sulfate under perturbations to steady state. In particular, we test how perturbations to steady state influence the cross plot of δ34S and δ18O for sulfate. The slope of the apparent linear phase (SALP) in the cross plot of δ34S and δ18O for sulfate has been used to infer the mechanism, or metabolic rate, of microbial metabolism, making it important that we understand how transient changes might influence this slope. Tested perturbations include changes in boundary conditions and changes in the rate of microbial sulfate reduction in the sediment. Our results suggest that perturbations to steady state influence the pore fluid concentration of sulfate and the δ34S and δ18O of sulfate but have a minimal effect on SALP. Furthermore, we demonstrate that a constant advective flux in the sediment column has no measurable effect on SALP. We conclude that changes in the SALP after a perturbation are not analytically resolvable after the first 5% of the total equilibration time. This suggests that in sedimentary environments the SALP can be interpreted in terms of microbial metabolism and not in terms of environmental parameters.

Interevaporitic deposits of Las Minas Gypsum Unit: A record of Late Tortonian marine incursions and dolomite precipitation in Las Minas Basin (eastern Betic Cordillera, SE Spain)

The Las Minas Gypsum Unit consists of more than 100 m of alternations of gypsum, carbonates and marls in Las Minas Basin (Betic Cordillera). Although this unit has been previously described as lacustrine, a marine influence in the basin has been suggested. This study provides new geochemical and paleontological data supporting the marine influence during the interevaporitic episodes, allowing to refine the palaeogeography of the eastern Betic Seaway during the Late Tortonian.87Sr/86Sr ratios in gypsum (0.70797 to 0.70825) suggest recycling of Triassic evaporites. The sulphate isotopic values in gypsum (11.5 < δ34SVCDT < 21.9‰; 16.6 < δ18OVSMOW < 28.1‰) are indicative of microbial sulfate-reduction activity. Carbonates are mainly composed of dolomite formed by subspherical crystal aggregates related to bio-mediated processes. The 87Sr/86Sr values in the interevaporitic carbonates (0.70823 to 0.70851) are higher than those expected for Triassic marine authigenic carbonates but lower than expected for the Late Miocene ones, suggesting a mixing of continental and marine water contributions. The ‘non-marine’ isotopic values in gypsum and carbonates contrast with an abundant content of marine siliceous fossils (radiolarians, diatoms, porifera, etc.) in the marls and carbonates that reveals marine incursions into the basin between periods of gypsum precipitation. A tephra layer identified in Las Minas and in the nearby El Cenajo Basin, located in a more inland position, allows a precise correlation between both basins, showing marine fossils in Las Minas and lacustrine in El Cenajo. In El Cenajo Basin, marine microfossils have been found but only in some levels, while others show lacustrine diatoms. A new palaeogeographic model of evaporitic lakes with temporal marine connections is proposed for the latest Tortonian in this region, when the uplift of the Betic Cordillera was very active accelerating the palaeogeographic evolution.