Biogenic Sulfide Research Articles

Mercury Immobilization without Methylation in Sulfidogenic Systems Dominated by Sulfur Disproportionating Bacteria.

The sulfidogenic process mediated by sulfate-reducing bacteria (SRB) is not ideal for treating mercury (Hg)-bearing wastewater due to the risk of methylmercury (MeHg) production. Addressing this challenge, our study demonstrated that, under S0-rich conditions and without organic additives, sulfidogenic communities dominated by sulfur-disproportionating bacteria (SDB) can effectively remove Hg(II) and prevent MeHg production. Using various inocula, we successfully established biological sulfidogenic systems driven separately by SDB and SRB. Batch experiments revealed that SDB cultures completely removed Hg(II) from the solution as HgS. Remarkably, no MeHg production was observed in the SDB cultures, while an average concentration of 0.32 μg/L of MeHg was detected in the SRB cultures. The absence of MeHg production in the SDB cultures could be mainly attributed to the cultivation conditions that reshaped the microbial community, resulting in a rapid decline of SRB-dominated Hg-methylating microorganisms. Consequently, the average abundance of the hgcA gene was 28 times lower than the levels before cultivation. Additionally, we found that the enriched Dissulfurimicrobium sp. bin121 can produce biogenic sulfide through sulfur disproportionation but lacks the hgcA gene, rendering it incapable of methylating Hg. Overall, we propose a novel biotechnology driven by SDB that can safely and sustainably treat Hg-bearing wastewater.

Acidophilic sulphate-reducing bacteria: Diversity, ecophysiology, and applications.

Acidophilic sulphate-reducing bacteria (aSRB) are widespread anaerobic microorganisms that perform dissimilatory sulphate reduction and have key adaptations to tolerate acidic environments (pH <5.0), such as proton impermeability and Donnan potential. This diverse prokaryotic group is of interest from physiological, ecological, and applicational viewpoints. In this review, we summarize the interactions between aSRB and other microbial guilds, such as syntrophy, and their roles in the biogeochemical cycling of sulphur, iron, carbon, and other elements. We discuss the biotechnological applications of aSRB in treating acid mine drainage (AMD, pH <3), focusing on their ability to produce biogenic sulphide and precipitate metals, particularly in the context of utilizing microbial consortia instead of pure isolates. Metal sulphide nanoparticles recovered after AMD treatment have multiple potential technological uses, including in electronics and biomedicine, contributing to a cost-effective circular economy. The products of aSRB metabolisms, such as biominerals and isotopes, could also serve as biosignatures to understand ancient and extant microbial life in the universe. Overall, aSRB are active components of the sulphur and carbon cycles under acidic conditions, with potential natural and technological implications for the world around us.

Biogenic Sulfide-Mediated Iron Reduction at Low pH

Acid mine drainage (AMD) pollutes natural waters, but some impacted systems show natural attenuation. We sought to identify the biogeochemical mechanisms responsible for the natural attenuation of AMD. We hypothesized that biogenic sulfide-mediated iron reduction is one mechanism and tested this in an experimental model system. We found sulfate reduction occurred under acidic conditions and identified a suite of sulfate-reducing bacteria (SRB) belonging to the groups Desulfotomaculum, Desulfobacter, Desulfovibrio, and Desulfobulbus. Iron reduction was not detected in microcosms when iron-reducing bacteria or SRB were selectively inhibited. SRB also did not reduce iron enzymatically. Rather, the biogenic sulfide produced by SRB was found to be responsible for the reduction of iron at low pH. Addition of organic substrates and nutrients stimulated iron reduction and increased the pH. X-ray diffraction and an electron microprobe analysis revealed that the polycrystalline, black precipitate from SRB bioactive samples exhibited a greater diversity of iron chalcogenide minerals with reduced iron oxidation states, and minerals incorporating multiple metals compared to abiotic controls. The implication of this study is that iron reduction mediated by biogenic sulfide may be more significant than previously thought in acidic environments. This study not only describes an additional mechanism by which SRB attenuate AMD, which has practical implications for AMD-impacted sites, but also provides a link between the biogeochemical cycling of iron and sulfur.

Biochar-Sulfate Reducing Bacteria synergy: A green approach for antimony removal and recovery from high-concentrated waters

Environments with elevated antimony (Sb) levels often result from industrial and mining activities, causing harm to ecosystems due to the inherent toxicity. Traditional treatments aim to eliminate or decrease Sb toxicity, yet they often result in the generation of secondary pollution. This study explores a novel approach for enhancing biological sulfate-reduction by biochar addition to cope with high Sb concentrations. Moreover, this research postulates sulfate-reduction bioprocess as a feasible alternative to obtain valuable antimony sulfide. The findings indicate that sulfate reduction effectively removes antimony, particularly at high concentrations, using a non-specialized inoculum. Biochar plays a pivotal role in enhancing sulfate-reduction rates, reducing lag-phase periods, and enriching the microorganisms responsible for sulfate reduction.Interestingly, lower concentrations of Sb(III) (5–40 mg/L) and Sb(V) (5–100 mg/L) exhibited a lower removal percentage compared to higher concentrations of Sb(III) (80–500 mg/L) and Sb(V) (200–1000 mg/L). This phenomenon was attributed to the excess sulfide hindering the equilibrium of the first-order reaction at lower concentrations, while at higher concentrations, the reaction proceeded more rapidly. A combination of biochemical and physicochemical reactions facilitated the removal of >95 % Sb(III) and >97 % Sb(V) using biochar.Furthermore, various taxa displayed a significant logarithmic rate of change in their abundance, influenced by the application of biochar or the introduction of distinct antimony species. The biogenic sulfide generated through the sulfate reduction process reacted with the Sb species, resulting in the precipitation of stibnite (Sb2S3), Na3SbS3, and Na3SbS4. These precipitates are considered crucial precursors in electronic applications.In conclusion, this study constitutes a pioneering exploration of elevated antimony (Sb) concentrations under sulfate-reducing conditions, significantly contributing to an advancement of knowledge in the application of biological processes.

Microbial influence in Spanish bentonite slurry microcosms: Unveiling a-year long geochemical evolution and early-stage copper corrosion related to nuclear waste repositories

The deep geological repository (DGR) concept consists of storing radioactive waste in metal canisters, surrounded by compacted bentonite, and placed deeply into a geological formation. Here, bentonite slurry microcosms with copper canisters, inoculated with bacterial consortium and amended with acetate, lactate and sulfate were set up to investigate their geochemical evolution over a year under anoxic conditions. The impact of microbial communities on the corrosion of the copper canisters in an early-stage (45 days) was also assessed. The amended bacterial consortium and electron donors/acceptor accelerated the microbial activity, while the heat-shocked process had a retarding effect. The microbial communities partially oxidize lactate to acetate, which is subsequently consumed when the lactate is depleted. Early-stage microbial communities showed that the bacterial consortium reduced microbial diversity with Pseudomonas and Stenotrophomonas dominating the community. However, sulfate-reducing bacteria such as Desulfocurvibacter, Anaerosolibacter, and Desulfosporosinus were enriched coupling oxidation of lactate/acetate with reduction of sulfates. The generated biogenic sulfides, which could mediate the conversion of copper oxides (possibly formed by trapped oxygen molecules on the bentonite or driven by the reduction of H2O) to copper sulfide (Cu2S), were identified by X-ray photoelectron spectroscopy (XPS). Overall, these findings shed light on the ideal geochemical conditions that would affect the stability of DGR barriers, emphasizing the impact of the SRB on the corrosion of the metal canisters, the gas generation, and the interaction with components of the bentonite.

A novel approach for the lifetime prediction and structural health monitoring of concrete sewer systems exposed to biogenic sulphide corrosion

A novel, combined experimental-modelling approach is presented for the estimation of the corrosion depth, load bearing capacity and lifetime of unreinforced concrete sewer pipes exposed to prolonged biogenic sulphide corrosion. The biogenic sulphide corrosion process is mimicked through two types of representative chemical experiments, namely: (i) long-term experiments performed under moderately controlled pH conditions, where dry-cast concrete cube samples are exposed to monthly refreshed sulphuric acid solutions with initial pH values of 3, 2 and 1 for a period of 12 months, and (ii) short-term experiments carried out under highly controlled pH conditions, in which dry-cast concrete disk samples are subjected to sulphuric acid solutions with almost constant pH values of 2, 1 and 0.5 for a period of two months. By applying X-ray diffraction, optical microscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy analyses, insight into the micro-scale morphology and elemental composition of the corrosion profile is obtained. In addition, the corrosion front and depth characteristics are measured by conducting phenolphthalein tests and analyses of surface colour and texture of macro-scale samples. From the experimental results, the time course of the corrosion depth is calibrated with a model for sulphate attack under a constant pH level. The model formulation is combined with detailed finite element method results from the literature to predict the long-term load bearing capacity of a concrete sewer pipe. The model is subsequently generalised for sulphate corrosion under a varying pH level. When combined with the installation of pH measuring devices on the inside of sewer pipes, the current engineering model may serve as an excellent practical tool for continuously monitoring the structural health and predicting the lifetime of in-situ sewer systems subject to sulphate attack under random acidity fluctuations.

Enhanced bioremediation of acid mine-influenced groundwater with micro-sized emulsified corn oil droplets (MOD) and sulfate-reducing bacteria (Desulfovibrio vulgaris) in a microcosm assay

High concentrations of metals and sulfates in acid mine drainage (AMD) are the cause of the severe environmental hazard that mining operations pose to the surrounding ecosystem. Little study has been conducted on the cost-effective biological process for treating high AMD. The current research investigated the potential of the proposed carbon source and sulfate reduction bacteria (SRB) culture in achieving the bioremediation of sulfate and heavy metals. This work uses individual and combinatorial bioaugmentation and bio-stimulation methods to bioremediate acid-mine-influenced groundwater in batch microcosm experiments. Bioaugmentation and bio-stimulation methods included pure culture SRB (Desulfovibrio vulgaris) and microsized oil droplet (MOD) by emulsifying corn oil. The research tested natural attenuation (T 1), bioaugmentation (T2), biostimulation (T3), and bioaugmentation plus biostimulation (T4) for AM-contaminated groundwater remediation. Bioaugmentation and bio-stimulation showed the greatest sulfate reduction (75.3%) and metal removal (95–99%). Due to carbon supply scarcity, T1 and T2 demonstrated 15.7% and 27.8% sulfate reduction activities. Acetate concentrations in T3 and T4 increased bacterial activity by providing carbon sources. Metal bio-precipitation was substantially linked with sulfate reduction and cell growth. SEM-EDS study of precipitates in T3 and T4 microcosm spectra indicated peaks for S, Cd, Mn, Cu, Zn, and Fe, indicating metal-sulfide association for metal removal precipitates. The MOD provided a constant carbon source for indigenous bacteria, while Desulfovibrio vulgaris increased biogenic sulfide synthesis for heavy metal removal.

Self-stabilization of Zn, Pb, Cd, and As in smelter-impacted organic-rich soil: The effect of hydrous Fe oxides and ZnCd sulfide coprecipitation

Soil constitutes a direct sink for elements mobilized due to mining and smelting activities. One of the desired pathways for reducing the bioavailability and toxicity of the contaminants is their transformation into sparingly soluble solid phases. Here, we report the formation of secondary mineral phases in extremely contaminated (up to 210 g Zn kg−1,102 g Pb kg−1, 5.68 g Cd kg−1, and 6.42 g As kg−1, respectively) organic-rich soil. Combining mineralogical techniques (SEM, XRD), a nonspecific sequential extraction (CISED) with Mössbauer and X-ray photoelectron (XPS) spectroscopies evidenced two poorly crystalline goethite components differing in crystallite size and As, Zn, Pb, Ca, Al, P substitutions and minor magnetite associated with plant roots (mainly Deschampsia caespitosa, Equisetum palustre, and Carex rostrate) directly below a layer of smelter-derived particles deposited into the soil. SEM was the only method that unambiguously documented the occurrence of ZnCd sulfide microsize aggregates incrusting plant roots and located in between the (hydrous) Fe oxides. Sequential extraction confirmed a complete As immobilization by goethite, while Cd forms a solid solution with ZnS and is lacking in the Fe hydroxides. The partitioning of Zn and Pb between the goethite and sulfide phases depends on soil water saturation. It is proposed that the coexistence of hydrous Fe oxides and nonferrous metal sulfides in the soil subsurface is possible because of redox heterogeneity of the rhizosphere and the decoupling of sulfur and iron cycles. Low mobility of biogenic sulfide ions and the protecting role of organic matter limits goethite sulfidation. The system remains active, adapting to the seasonally changeable plant roots ecology and fluctuations in water saturation. The obtained results are of value in remediation and managing strategies for contaminated soils and in reconstructing processes related to the formation and/or transformation of low-temperature sulfide deposits.

Bacterial Sulfate Reduction Facilitates Iodine Mobilization in the Deep Confined Aquifer of the North China Plain.

Bacterial sulfate reduction plays a crucial role in the mobilization of toxic substances in aquifers. However, the role of bacterial sulfate reduction on iodine mobilization in geogenic high-iodine groundwater systems has been unexplored. In this study, the enrichment of groundwater δ34SSO4 (15.56 to 69.31‰) and its significantly positive correlation with iodide and total iodine concentrations in deep groundwater samples of the North China Plain suggested that bacterial sulfate reduction participates in the mobilization of groundwater iodine. Similar significantly positive correlations were further observed between the concentrations of iodide and total iodine and the relative abundance of the dsrB gene by qPCR, as well as the composition and abundance of sulfate-reducing bacteria (SRB) predicted from 16S rRNA gene high-throughput sequencing data. Subsequent batch culture experiments by the SRB Desulfovibrio sp. B304 demonstrated that SRB could facilitate iodine mobilization through the enzyme-driven biotic and sulfide-driven abiotic reduction of iodate to iodide. In addition, the dehalogenation of organoiodine compounds by SRB and the reductive dissolution of iodine-bearing iron minerals by biogenic sulfide could liberate bound or adsorbed iodine into groundwater. The role of bacterial sulfate reduction in iodine mobilization revealed in this study provides new insights into our understanding of iodide enrichment in iodine-rich aquifers worldwide.

Optimization of sulfate leaching from Phosphogypsum for efficient bioreduction in a batch bioreactor using a sulfate-reducing microbial consortium

Phosphogypsum (PG) is generated annually from phosphoric acid production. This by-product contains 50% of sulfate (SO42−), which can be recycled biologically. Biorecovery of elemental sulfur (S0) involves firstly converting SO42− into biogenic sulfide using sulfate-reducing bacteria under anaerobic conditions, then oxidizing the sulfide produced into S0 using sulfur-oxidizing bacteria. This study focused on selecting and evaluating natural microbial consortia from SO42− rich biotopes for their application in the initial first step of S0 biorecovery. The PG sample was first comprehensively characterized using ICP-MS/OES, XRD, FTIR, and TGA analyses. Subsequently, SO42− leaching optimization was performed through a design of experiments approach. The analysis revealed that CaSO4 was the major component of the PG (78%), and the optimal parameters for leaching of SO42− from PG were at a NaOH concentration of 7.4% and PG concentration of 158 g.L−1. Furthermore, the MYC-consortium isolated from a hydrothermal niche demonstrated the highest reduction capacity among the studied consortia. It also exhibited the highest performance under SO42− concentrations up to 3.5 g.L−1, salinity levels up to 30 g.L−1, and in the presence of 60 ppm of Zn(II), 3 ppm of Cd(II), and 6 ppm of Pb(II). Moreover, this consortium showed a high capacity for reducing SO42− in the bioreactor (90% after 6 weeks) when utilizing SO42− from the PG-leached solution, as attested by the chemical analyses of the precipitate formed in the bioreactor. This research offers a comprehensive insight into the potential of MYC-consortium to convert leached SO42− from PG into sulfide, which is the most critical step in the S0-biorecovery.

Impact of redox fluctuations on microbe-mediated elemental sulfur disproportionation and coupled redox cycling of iron

Elemental sulfur (S0) plays a vital role in the coupled cycling of sulfur and iron, which in turn affects the transformation of carbon and various pollutants. These processes have been well characterized under static anoxic or oxic conditions, however, how the natural redox fluctuations affect the bio-mediated sulfur cycling and coupled iron cycling remain enigmatic. The present work examined S0 disproportionation as driven by natural microbial communities under fluctuating redox conditions and the contribution of S0 disproportionation to ferrihydrite transformation. Samples were incubated at either neutral or alkaline pH values, applying sequential anaerobic, aerobic and anaerobic conditions over 60 days. Under anaerobic conditions, S0 was found to undergo disproportionation to sulfate and sulfide, which subsequently reduced ferrihydrite at both pH 7.4 and 9.5. Ferrihydrite promoted S0 disproportionation by scavenging biogenic sulfide and maintaining a suitable degree of sulfate formation. After an oxic period, during the subsequent anoxic incubation, bioreduction of sulfate occurred and the biogenic sulfide reduced iron (hydr)oxides at a rate approximately 25 % lower than that observed during the former anoxic period. A 16S rDNA-based microbial community analysis revealed changes in the microbial community in response to the redox fluctuations, implying an intimate association with the coupled cycling of sulfur and iron. Microscopic and spectroscopic analyses confirmed the S0-mediated transformation of ferrihydrite to crystalline iron (hydr)oxide minerals such as lepidocrocite and magnetite and the formation of iron sulfides precipitated under fluctuating redox conditions. Finally, a reaction mechanism based on mass balance was proposed, demonstrating that bio-mediated sulfur transformation maintained a sustainable redox reaction with iron (hydr)oxides under fluctuating anaerobic-aerobic-anaerobic conditions tested in this study. Altogether, the finding of our study is critical for obtaining a more complete understanding of the dynamics of iron redox reactions and pollutant transformation in sulfur-rich aquatic environments.

Elemental sulfur redox bioconversion for selective recovery of phosphorus from Fe/Al-bound phosphate-rich anaerobically digested sludge: Sulfur oxidation or sulfur reduction?

The biological oxidation of elemental sulfur (S0) to sulfate and the reduction of S0 to sulfide provide a potential route for extracting and reclaiming phosphorus (P) from anaerobically digested sludge (ADS). However, the treatment performance, stability, and cost-effectiveness of the two opposing bioprocesses based on S° for selective P recovery from ADS remain unclear. This study aimed to compare the roles of S0-oxidizing bacteria (S0OB) and S0-reducing bacteria (S0RB) in liberating insoluble P from ADS through single-batch and consecutive multibatch experiments. Changes in P speciation in the sludge during the biological extraction processes were analyzed by using complementary sequential extraction and P X-ray absorption near-edge spectroscopy. Results showed that S0OB treatment extracted more phosphate from the sludge compared with S0RB treatment, but it also released a considerable amount of metal cations (e.g., heavy metals, Mg2+, Al3+, Ca2+) and negatively affected sludge dewaterability due to intense sludge acidification and cell lysis. At pH 1.2, the S0OB treatment released 92.9% of P from the sludge, with the dissolution of HAP, Fe-PO4, Mg3(PO4)2, and P-fehrrihy contributing 26.8%, 22.1%, 12.8%, and 10.5%, respectively. The S0RB treatment released 63.6% of P from the sludge at pH 7.0, with negligible dissolution of metal cations, thereby avoiding costly purification of the extract and alkali neutralization for pH adjustment. This treatment involved the replacement of phosphates bounded with Fe-PO4 (FePO4 and P-fehrrihy) and Al–PO4 (P-Alumina and AlPO4) with biogenic sulfides, with contributions of 72.7%, and 20.9%, respectively. Consecutive bioprocesses for P extraction were achieved by recirculating the treated sludge. Both S0OB and S0RB treatments did not affect the extent of sludge dewatering but considerably weakened the dewatering rate. The S0OB-treated sludge exhibited prolonged filtration time (from 3010 s to 9150 s) and expressing time (from 795 s to 4690 s) during compression dewatering. After removing metal cations using cation exchange resin (CER) and neutralizing using NaOH, a vivianite product Fe3(PO4)2·8H2O (purity: 84%) was harvested from the S0OB-treated extract through precipitation with FeSO4·7H2O. By contrast, a vivianite product Fe3(PO4)2·8H2O (purity: 81%) was directly obtained from the S0RB-treated extract through precipitation with FeSO4·7H2O. Ultimately, 79.8 and 57.9wt% of P were recovered from ADS through S0OB extraction–CER purification–alkali neutralization–vivianite crystallization, and S0RB extraction–vivianite crystallization, respectively. Collectively, biological S0 reduction is more applicable than biological S0 oxidation for selectively reclaiming P from Fe/Al-associated phosphate-rich ADS due to better cost-effectiveness and process simplicity. These findings are of significance for developing sludge management strategies to improve P reclamation with minimal process inputs.

Assessment of chemo-mechanical degradation of concrete sewer pipes through an integrated experimental approach

The chemo-mechanical degradation of unreinforced concrete sewer pipes applied in domestic service locations is assessed through a systematic, integrated experimental approach, considering 18 new and 35 used sewer pipes. The characteristics and environmental conditions of the sewer pipes are reported, and data obtained from surface condition classification, residual alkalinity tests and XRD analyses are combined to identify the type and degree of chemical attack of the used sewer pipes. Concrete material properties are determined by material tests on sewer pipe samples, providing quantitative insight into the age dependency of the Young’s modulus, compressive strength, tensile strength and mode I toughness. All relatively old pipes (installed in the 1920s and 1950s) show substantial chemical attack by biogenic sulphide corrosion (at the inner side of the pipe) and carbonation (at the outer side of the pipe). The time development of the corresponding corrosion depths on average follows a linear trend, whereby the corrosion rate for biogenic sulphide corrosion is about a factor of 1.3 larger than for carbonation. Due to these chemical processes, the mechanical properties of concrete may significantly depend on the age of the sewer pipe. In particular, the average compressive strength and average tensile strength decrease approximately linearly with the age of the pipe, in correspondence with relative reductions of, respectively, a factor of 1.7 and 1.5 over a period of almost 100 years. The values and time-dependent trends found for the concrete properties and corrosion depths of sewer pipes can serve as input for practical analyses and advanced numerical simulations on their bearing capacity and time-dependent degradation. The experimental results also emphasize the importance of regularly assessing the amount of chemical degradation of (especially older) in-situ sewer pipes, by determining the (decrease in) effective wall thickness via core sampling and laser profiling.

S, Pb, and Fe isotope compositions of sulfides in middle and southern Okinawa Trough: Implying the complicated hydrothermal systems in back-arc spreading centers

Sulfur, lead, and iron isotopic systematics of sulfides from the Iheya North hydrothermal field in middle Okinawa Trough and the Yonaguni Knoll IV hydrothermal field in southern Okinawa Trough were investigated to understand the origin of ore-forming material and isotope fractionation during sulfide precipitation in back-arc spreading centers. The δ34S values (from 8.60‰ to 9.68‰) of sulfide minerals in Iheya North field suggest sulfur was derived from the leaching of basement rocks and the reduction of seawater sulfate. But an additional light sulfur source from the dissolution of biogenic sulfides in sediments is indispensable for the observed low δ34S values (between 4.78‰ and 4.97‰) of Yonaguni Knoll IV sulfides. Lead isotope compositions of all sulfides vary in a relatively wide range (206Pb/204Pb = 18.432 to 18.563, 207Pb/204Pb = 15.579 to 15.671, and 208Pb/204Pb = 38.539 to 38.979, respectively) which involves the mixing of mantle-derived and sediment-derived lead in varying proportions. Unusually high radiogenic lead isotope ratios of Yonaguni Knoll IV sulfides (207Pb/204Pb = 15.628 to 15.671, and 208Pb/204Pb = 38.854 to 38.979) imply the presence of old crustal fragments beneath southern OT. The hydrothermal fluids in OT are characterized by extremely low calculated δ56Fe values (−1.00‰ to −1.32‰) which is attributed to reducing sediments. The paired Fe-isotope compositions of pyrite and chalcopyrite revealed significantly different iron isotope compositions of hydrothermal fluids in study areas and extremely complicated ore-forming processes. Rapid precipitation of pyrite from FeS precursors accompanying iron isotopic disequilibrium moves from FeS-fluid equilibrium to pyrite-fluid equilibrium during pyrite recrystallization. The combination of sulfur, lead, and iron isotopic data suggests that hydrothermal systems in back-arc spreading centers related to plate subduction are generally affected by mantle, overlying sediments as well as potential old continental crust fragments, which results in various hydrothermal fluids and complicated mineralization processes.

Effect of Varying Zinc Concentrations on the Biomethane Potential of Sewage Sludge

The anaerobic digestion of sewage sludge is highly sensitive to high zinc concentrations. Although sulfate-reducing bacteria (SRB) activity can negatively affect methanogenesis, SRB-mediated metal sulfide precipitation can alleviate zinc toxicity. A series of mesophilic anaerobic batch experiments was performed for the biomethane potential of three different sewage sludge samples for 74 days using the background sludge zinc content, alone or in combination with the external addition of 200, 300 and 400 mg Zn/L. The highest biomethane production was 165 ± 1 mL CH4/g VS using activated sludge (AS) with a background concentration of 93 mg Zn/L. A slight decrease in the biomethane yield (i.e., 157 ± 1, 158 ± 1 and 159 ± 1 mL CH4/g VS) was obtained in the presence of 293, 393 and 493 mg Zn/L, respectively. The potential reason for the high methanogenic activity at high inlet Zn concentrations could be that the AS used in this study was already acclimated to those conditions. Zinc was likely removed from the system by sulfide precipitation, and a removal efficiency above 99% was achieved under all zinc concentrations. A sulfate reduction efficiency of 99% was also obtained. Overall, this study details the potential utilization of biogenic sulfide as a metal detoxifying agent without detrimental effects on methane production from sewage sludge.

Crystal lattice defects in nanocrystalline metacinnabar in contaminated streambank soils suggest a role for biogenic sulfides in the formation of mercury sulfide phases.

At mercury (Hg)-contaminated sites, streambank erosion can act as a main mobilizer of Hg into nearby waterbodies. Once deposited into the waters, mercury from these soils can be transformed to MeHg by microorganisms. It is therefore important to understand the solid-phase speciation of Hg in streambanks as differences in Hg speciation will have implications for Hg transport and bioavailability. In this study, we characterized Hg solid phases in Hg-contaminated soils (100-1100 mg per kg Hg) collected from the incised bank of the East Fork Poplar Creek (EFPC) in Oak Ridge, TN (USA). The analysis of the soil samples by scanning electron microscopy-energy dispersive spectroscopy indicated numerous microenvironments where Hg and sulfur (S) are co-located. According to bulk soil analyses by extended X-ray absorption fine structure spectroscopy (EXAFS), the near-neighbor Hg molecular coordination in the soils closely resembled freshly precipitated Hg sulfide (metacinnabar, HgS); however, EXAFS fits indicated the Hg in the HgS structure was undercoordinated with respect to crystalline metacinnabar. This undercoordination of Hg-S observed by spectroscopy is consistent with transmission electron microspy images showing the presence of nanocrystallites with structural defects (twinning, stacking faults, dislocations) in individual HgS-bearing particles. Although the soils were collected from exposed parts of the stream bank (i.e., open to the atmosphere), the presence of reduced forms of S and sulfate-reducing microbes suggests that biogenic sulfides promote the formation of HgS nanoparticles in these soils. Altogether, these data demonstrate the predominance of nanoparticulate HgS with crystal lattice defects in the bank soils of an industrially impacted stream. Efforts to predict the mobilization and bioavailability of Hg associated with nano-HgS forms should consider the impact of nanocrystalline lattice defects on particle surface reactivity, including Hg dissolution rates and bioavailability on Hg fate and transformations.

Guar Gum Stimulates Biogenic Sulfide Production in Microbial Communities Derived from UK Fractured Shale Production Fluids.

Shale gas production fluids offer a window into the engineered deep biosphere. Here, for the first time, we report on the geochemistry and microbiology of production fluids from a UK shale gas well in the Bowland shale formation. The composition of input fluids used to fracture this well were comparatively lean, consisting only of water, sand, and polyacrylamide. This formation therefore represents an interesting comparison to previously explored fractured shales in which more additives were used in the input fluids. Here, we combine cultivation and molecular ecology techniques to explore the microbial community composition of hydraulic fracturing production fluids, with a focus on the potential for common viscosity modifiers to stimulate microbial growth and biogenic sulfide production. Production fluids from a Bowland Shale exploratory well were used as inocula in substrate utilization experiments to test the potential for polyacrylamide and guar gum to stimulate microbial metabolism. We identified a consortium of thiosulfate-reducing bacteria capable of utilizing guar gum (but not polyacrylamide), resulting in the production of corrosive and toxic hydrogen sulfide. Results from this study indicate polyacrylamide is less likely than guar gum to stimulate biogenic sulfide production during shale gas extraction and may guide planning of future hydraulic fracturing operations. IMPORTANCE Shale gas exploitation relies on hydraulic fracturing, which often involves a range of chemical additives in the injection fluid. However, relatively little is known about how these additives influence fractured shale microbial communities. This work offers a first look into the microbial community composition of shale gas production fluids obtained from an exploratory well in the Bowland Shale, United Kingdom. It also seeks to establish the impact of two commonly used viscosity modifiers, polyacrylamide and guar gum, on microbial community dynamics and the potential for microbial sulfide production. Not only does this work offer fascinating insights into the engineered deep biosphere, it could also help guide future hydraulic fracturing operations that seek to minimize the risk of biogenic sulfide production, which could reduce efficiency and increase environmental impacts of shale gas extraction.

Selective removal and recovery of gallium and germanium from synthetic zinc refinery residues using biosorption and bioprecipitation.

The depletion of primary ores, the environmental concerns related to mining activities, and the need to promote circular economy has drawn attention to the recycling of metallic compounds. Bio-based technologies are suitable for metal recovery, as they operate under mild conditions (ambient temperature and pressure) and are ideal for treating low-concentration waters. This study compared the effectiveness of adsorption and precipitation for the removal and recovery of gallium, germanium and zinc. Adsorption of the metallic ions on elemental forms of sulfur (S0), selenium (Se0) and tellurium (Te0), both of chemical and biological sources, was tested. Biosorption onto elemental forms of S0bio, Se0bio and Te0bio effectively removed Ga and Zn. The highest removal efficiency (ղ) was obtained for Ga onto the adsorbent Te0bio (69±0.4%), with an adsorption capacity (q) of 74mgGa (g Te0bio)-1, followed by Zn (ղ=40±0.7%) with 43mg Zn (g Te0bio)-1. Precipitation with chemical and biogenic sulfide at different metal to sulfide (Me/S) ratios was also assessed. Biologically produced sulfide was more efficient for Ga and Zn compared to chemical sulfide. Precipitation with biogenic sulfide was efficient for the removal of Ga (ղ=59.9±2.6%) and Zn (ղ=44.2±3.0%). The lowest ratio between metal to sulfide (Me/S=0.2) achieved higher zinc removal efficiencies, whereas gallium removal was more efficient at Me/S=1.5. None of the tested methods allowed for recovery of Ge. Biosorption and bioprecipitation gave nevertheless high removal and recovery of Ga and Zn.

Effect of biochemical attack on the mechanical performance of used concrete sewer pipes

The structural response and failure mechanisms of 35 used concrete sewer pipes are investigated by means of a combined experimental–numerical approach, whereby specific attention focuses on determining the effect by biochemical attack. Accordingly, the degree of degradation of the inner and outer surfaces of the pipes is carefully analysed by visual inspection, and subsequently categorized in 6 different surface condition classes. The type and degree of biochemical attack are determined by respectively performing X-ray diffraction analyses and phenolphthalein tests. The sewer pipes, which vary in age, size and geometry, are subjected to biaxial loading conditions in a full-scale test set-up. The experiments show that the material degradation of relatively old sewer pipes can be considerable, and for a large part may be attributed to the process of biogenic sulphide corrosion. This process typically induces a weak, corroded layer at the inside of the pipe, which is characterized by the appearance of exposed granulates and porous mortar between the granulates. The experimental failure responses of the used sewer pipes are compared against numerical results obtained from detailed Finite Element Method (FEM) simulations. The failure response of each sewer pipe type is well predicted by the FEM model if the negligible mechanical properties of the biogenic sulphide corrosion layer at the inside of the pipe are accounted for in the simulations. The relatively low concrete tensile strength of old sewer pipes and the reduced effective wall thickness due to biogenic sulphide corrosion cause that the ultimate bearing strength and structural stiffness of these pipes may be more than a factor of two lower than those of completely new sewer pipes. The results of the present work provide a scientific basis for the decision-making process on sewer rehabilitation and replacement, in particular by revealing and quantifying the influence on the structural bearing strength by biogenic sulphide corrosion. • Structural response and failure mechanisms of 35 used concrete sewer pipes are investigated via a combined experimental–numerical approach. • Effect of biochemical attack on bearing strength is quantified. • Mechanical collapse of sewer pipes is characterized by the development of 4 failure cracks. • Results provide a scientific basis for decision-making process on sewer rehabilitation and replacement.

A chemo-mechanical model for biogenic sulphide corrosion of concrete

A chemo-mechanical model is presented for the simulation of biogenic sulphide corrosion in concrete sewer pipes. The chemical model is formulated in terms of a system of coupled diffusion-reaction equations, which describe the processes of calcium hydroxide dissolution, calcium silicate hydrate dissolution and gypsum formation. The chemical problem is two-way coupled with a mechanical model that captures the damage processes caused by mechanical deformations, calcium silicate hydrate dissolution and gypsum formation. A set of numerical analyses illustrates that the model realistically simulates the growth of a gypsum corrosion layer and the consequent damage development in the concrete material. A validation experiment is performed that mimics the chemical process of biogenic sulphide corrosion, from which it is confirmed that the chemo-mechanical model adequately simulates both the shape of the experimental corrosion profile and the square root time development of the corrosion depth.