Sulfate Reduction Research Articles

Genome-based approach to evaluate the metabolic potentials and exopolysaccharides production of Bacillus paralicheniformis CamBx3 isolated from a Chilean hot spring.

In the present study, a thermophilic strain designated CamBx3 was isolated from the Campanario hot spring, Chile. Based on 16S rRNA gene sequence, phylogenomic, and average nucleotide identity analysis the strain CamBx3 was identified as Bacillus paralicheniformis. Genome analysis of B. paralicheniformis CamBx3 revealed the presence of genes related to heat tolerance, exopolysaccharides (EPS), dissimilatory nitrate reduction, and assimilatory sulfate reduction. The pangenome analysis of strain CamBx3 with eight Bacillus spp. resulted in 26,562 gene clusters, 7,002 shell genes, and 19,484 cloud genes. The EPS produced by B. paralicheniformis CamBx3 was extracted, partially purified, and evaluated for its functional activities. B. paralicheniformis CamBx3 EPS with concentration 5 mg mL-1 showed an optimum 92 mM ferrous equivalent FRAP activity, while the same concentration showed a maximum 91% of Fe2+ chelating activity. B. paralicheniformis CamBx3 EPS (0.2 mg mL-1) demonstrated β-glucosidase inhibition. The EPS formed a viscoelastic gel at 45°C with a maximum instantaneous viscosity of 315 Pa.s at acidic pH 5. The present study suggests that B. paralicheniformis CamBx3 could be a valuable resource for biopolymers and bioactive molecules for industrial applications.

Integrating Tide‐Driven Wetland Soil Redox and Biogeochemical Interactions Into a Land Surface Model

AbstractRedox processes, aqueous and solid‐phase chemistry, and pH dynamics are key drivers of subsurface biogeochemical cycling and methanogenesis in terrestrial and wetland ecosystems but are typically not included in terrestrial carbon cycle models. These omissions may introduce errors when simulating systems where redox interactions and pH fluctuations are important, such as wetlands where saturation of soils can produce anoxic conditions and coastal systems where sulfate inputs from seawater can influence biogeochemistry. Integrating cycling of redox‐sensitive elements could therefore allow models to better represent key elements of carbon cycling and greenhouse gas production. We describe a model framework that couples the Energy Exascale Earth System Model (E3SM) Land Model (ELM) with PFLOTRAN biogeochemistry, allowing geochemical processes and redox interactions to be integrated with land surface model simulations. We implemented a reaction network including aerobic decomposition, fermentation, sulfate reduction, sulfide oxidation, methanogenesis, and methanotrophy as well as pH dynamics along with iron oxide and iron sulfide mineral precipitation and dissolution. We simulated biogeochemical cycling in tidal wetlands subject to either saltwater or freshwater inputs driven by tidal hydrological dynamics. In simulations with saltwater tidal inputs, sulfate reduction led to accumulation of sulfide, higher dissolved inorganic carbon concentrations, lower dissolved organic carbon concentrations, and lower methane emissions than simulations with freshwater tidal inputs. Model simulations compared well with measured porewater concentrations and surface gas emissions from coastal wetlands in the Northeastern United States. These results demonstrate how simulating geochemical reaction networks can improve land surface model simulations of subsurface biogeochemistry and carbon cycling.

Методы и применение интенсификации фиторемедиации сточных вод горнодобывающей промышленности

The article presents the latest results of research on the biological treatment of mining and metallurgical industrial wastewater using higher aquatic plants: Eichhornia (Eichhornia crassipes Solm) and Pistia (Pistia stratiotes L). The features of these plants detected during contaminated wastewater treatment have been identified. The primary results of experiments are based on single-stage treatment processes that ensure efficient wastewater treatment upon completion of plant adaptation to these waters. However, the duration of the process is long, i.e., 15–30 days; therefore, the process intensification experiments have been conducted. Experiments conducted within a week have achieved significant reductions in calcium, magnesium, sulfate, and chlorine ions. During the first days of the experiments, the plants continued to grow and develop, but due to high salt concentrations, some of the plants (approximately 50–60 %) died due to insufficient time for adaptation. The remaining plants were slowly recovering and continued vegetation. These plants have demonstrated high cumulative and treatment effects as they are considered most adapted to the chemical composition of wastewater. The use of such plants, however, will require longer periods for wastewater treatment, namely around a month, which does not comply with the production requirements. Therefore, a decision to experiment during 24 hours has been made. The results of the analysis have shown that the plants completely absorb calcium, magnesium, chlorine, nitrates, zinc, and cobalt already on the first day of planting; bicarbonates and sodium are absorbed on the second day; and iron on the third day. Potassium, manganese, arsenic, and thiocyanates are neutralized during 7–10 days. The average efficiency of wastewater treatment per day is 51% on the condition of frequent renewal of the plant biomass. Based on the results obtained, a biotechnology built on a multi-stage biological wastewater treatment system of industrial scale has been developed.

Metals pre–enrichment during the syn–sedimentary period of Mengxing Pb–Zn Deposit, western Yunnan, SW China: Evidence on LA–ICP–MS trace elements and S isotopes of lamellar sphalerite

The Mengxing Pb–Zn deposit, which contains up to 1.02 Mt of Pb + Zn metal with an average Pb + Zn grade of ca. 12.13 %, is a representative of sedimentary–reworked deposit in western Yunnan. The orebodies, which are strata–bound and veined, occur in the Silurian Shangrenheqiao formation. The mineralization process has been divided into sedimentary stage and hydrothermal stage. Previous research has primarily focused on the economic ores enriched during the hydrothermal stage. However, the formation of syn–sedimentary ore, responsible for metal pre–enrichment, has been largely ignored. To solve the issue above, the in–situ trace elements and mapping, as well as in–situ S isotopes analyses, were conducted on lamellar sphalerite ore, which retains the characteristics of the syn–sedimentary ore. Analysis of the trace elements revealed that the sphalerite at Mengxing are rich in Ge, Cd, As, Sb and poor in Fe, Mn, In, Sn and Co overall, suggesting a metallogenic environment of medium–low temperature. The LA–ICP–MS trace elemental mapping graph indicated that colloidal sphalerite exhibits the obvious oscillation belts. The dark zonal band of sphalerite is more enriched in Fe, Mn, Cu, Ge, As, Ag, Sb, and Pb, and depleted in Ga, Cd, and Sn, compared to the light zonal band, suggesting the various formation temperature. Based on the equation of the first principal component (PC1*) relating trace elements to mineral formation temperature, it is estimated that ore in the sedimentary stage occurred at relatively lower temperatures (174.74℃ – 203.18℃), while that of the hydrothermal stage occurred at higher temperatures (209.78℃ – 240.18℃). The S isotopic composition of sphalerite indicated a significant distinction between the sedimentary stage (δ34SVCDT = 13.29 ‰ – 37.06 ‰, with an average value of 27.97 ‰) and the hydrothermal stage (δ34SVCDT = −6.45 ‰ – 31.57 ‰, with an average of 9.01 ‰). It is hypothesized that sulfur during the early stage originated primarily from thermochemical sulfate reduction (TSR) of seawater sulfate, while sulfur during the hydrothermal stage was likely influenced by hydrothermal fluid from the deep. In conclusion, the early lamellar ores formed during the Silurian period exhibit characteristics consistent with SEDEX type mineralization, leading to initial metal pre–enrichment, followed by further enrichment of ore grade by superimposed fluid during the hydrothermal stage.

Bioremediation of Sulfate in Water Environment: An Overview of Removal Pathways and Influencing Factors

Sulfate-laden wastewater generated from various natural and industrial activities, including mining, metallurgy, electroplating, and battery manufacturing and recycling, has the potential to contaminate both ground and surface water bodies. It is harmful to all forms of life and the environment. Thus, developing an efficient treatment system to address sulfate pollution is necessary. Biological sulfate reduction (BSR) involving sulfate-reducing bacteria offers a better removal of sulfate than conventional physicochemical methods. BSR offers various advantageous such as lower sludge production, removal and recovery of metals, and production of elemental sulfur. However, the performance of bioreactors depends on wastewater sources, microbes involved, and operating conditions. Currently, limited studies are available encapsulating the current state of the art of biological sulfate remediation aimed at optimization of bioreactor design and operation. Therefore, this paper attempts to provide a comprehensive review of the sources of sulfate, its health and ecological effects, microbes involved in sulfate reduction, and its removal pathways that would be beneficial for future bioreactor design. In addition, theoretical and practical aspects of influencing factors have been discussed. Considering the results of the reviewed articles, operating, and set-up conditions are recommended to obtain the higher sulfate removal. It includes dissimilatory sulfate reduction by mixed bacterial culture using sodium lactate as an electron donor with pH near about neutral, mesophilic conditions, COD/SO2−4 ratio of 0.67-1.7, ORP less than −100 mV, and lesser sulfide concentration. This overview helps to develop an effective strategy for bioremediation of sulfate and decreasing the sulfate-rich industrial effluent footprint.

Integrated stable S isotope, microbial and hydrochemical analysis of hydrogen sulphide origin in groundwater from the Legnica-Głogów Copper District, Poland

Hydrogen sulphide (H2S) was first reported in 2010 in an underground mining area of the Legnica-Głogów Copper District (LGCD). However, during the deposit exploration and exploitation stage in 1970, H2S was not detected. Previous studies have not indicated the origin of H2S in LGCD mine waters. Indirect evidence has suggested that, most likely, H2S migrated with the groundwater from the Main Dolomite aquifer to the mine galleries through cracks in the separating anhydrite and halite layers resulting from long-term mining operations. Interdisciplinary studies have been conducted to confirm this hypothesis. Investigations of the δ34S in H2S of 12 groundwater samples taken from leakages from cracks in galleries and drilled boreholes showed high isotopic similarity to H2S in natural gas and S-organic compounds of oil from petroleum reservoirs in the Main Dolomite unit, where this gas was generated in high volumes mainly as a result of thermochemical sulphate reduction (TSR). Microbial investigations of mine water indicated the presence of Desulfitobacterales, Desulfobacterales, Desulfotomaculales, Desulfovibrionales, and Desulfuromonadia as possible indicators of contact between the analysed water and rocks inhabited by sulphur-reducing bacteria and Halothiobacillales, as an indicator of contact between water and salt. Hydrochemical analysis revealed that water flowing out of mine galleries and boreholes has a higher salinity than groundwater that is naturally associated with the horizon where mines operate; this phenomenon is associated with H2S occurrence. This investigation confirmed the hypothesis that the H2S in the LGCD mines originates mainly from the Main Dolomite aquifer. Furthermore, this study confirms that a multifaceted approach is necessary to answer complex geochemical questions in mining.

Biomarker signatures and depositional environment of ore-bearing black shale in the Luishia Cu–Co deposit, Democratic Republic of Congo: Implications for regional copper mineralization

The Central African Copperbelt is a globally important sediment-hosted stratiform copper cluster, with regional Cu–Co deposits controlled by Neoproterozoic rift basin. Ore formation in the Copperbelt involves multiple stages of mineralization during diagenesis, basin inversion, and collisional orogeny. Understanding the depositional environment of ore-hosting rocks is crucial for revealing the geological settings and pre-orogenic ore genesis. This paper presents a biomarker study focusing on the ore-bearing black shale in the Luishia Cu–Co deposit, Democratic Republic of Congo. The research investigates thermal maturity, source, and depositional environment of organic matter through rock organic carbon and pyrolysis analysis, chloroform bitumen “A” group component analysis, as well as saturated hydrocarbon gas chromatography-mass spectrometry (GC-MS) analysis. The results indicate significant thermal maturation of organic matter in Luishia black shale. Bacteria are identified as the primary source of organic matter followed by red algae and green algae. The sedimentary environment is characterized by a restricted rift basin under shallow marine conditions with a stratified water column. The processes of bacterial sulphate reduction (BSR) and thermochemical sulphate reduction (TSR) significantly influence the mineralization during diagenesis and basin inversion, respectively. Enhanced thermal maturity promotes methane generation which plays a role in reducing anhydrite and subsequently precipitating ore minerals. The findings have important implications for regional exploration strategies.

Distribution of mercury in modern bottom sediments of the Beaufort Sea in relation to the processes of early diagenesis: Microbiological aspect

This study investigated the contents of total mercury (THg), trace metals, and CH4 and determined the signature microbes involved in various biogeochemical processes in the sediment of the Canadian Beaufort Sea. The THg ranged between 32 and 63 μg/kg and the trace metals such as Fe, Al, Mn, and Zn were significant in distributions. The pH, SO42−, Fe2+, and redox proxy metals were crucial factors in the spatial and vertical heterogeneity of geochemical distributions. CH4 was detected only at the mud volcano site. Microbial analyses identified Clostridium, Desulfosporosinus, Desulfofustis, and Desulftiglans as the predominant Hg methylators and sulfate reducers; Nitrosopumilus and Hyphomicrobium as the major nitrifiers and denitrifiers; Methanosarcina and Methanosaeta as keystone methanogens; and Methyloceanibacter and Methyloprofundus as signature methanotrophs. Altogether, this study expands the current understanding of the microbiological and geochemical features and could be helpful in predicting ecosystem functions in the Canadian Beaufort Sea.

Sulfate-reducing bacteria unearthed: ecological functions of the diverse prokaryotic group in terrestrial environments.

Sulfate-reducing prokaryotes (SRPs) are essential microorganisms that play crucial roles in various ecological processes. Even though SRPs have been studied for over a century, there are still gaps in our understanding of their biology. In the past two decades, a significant amount of data on SRP ecology has been accumulated. This review aims to consolidate that information, focusing on SRPs in soils, their relation to the rare biosphere, uncultured sulfate reducers, and their interactions with other organisms in terrestrial ecosystems. SRPs in soils form part of the rare biosphere and contribute to various processes as a low-density population. The data reveal a diverse range of sulfate-reducing taxa intricately involved in terrestrial carbon and sulfur cycles. While some taxa like Desulfitobacterium and Desulfosporosinus are well studied, others are more enigmatic. For example, members of the Acidobacteriota phylum appear to hold significant importance for the terrestrial sulfur cycle. Many aspects of SRP ecology remain mysterious, including sulfate reduction in different bacterial phyla, interactions with bacteria and fungi in soils, and the existence of soil sulfate-reducing archaea. Utilizing metagenomic, metatranscriptomic, and culture-dependent approaches will help uncover the diversity, functional potential, and adaptations of SRPs in the global environment.

A Lewis Acid–Lewis Base Hybridized Electrocatalyst for Roundtrip Sulfur Conversion in Lithium–Sulfur Batteries

AbstractElectrocatalysts can optimize the sulfur/sulfide reaction kinetics in Li–S batteries to compete with the loss of lithium polysulfides (LiPSs) caused by the shuttling effect. However, the design rationale of electrocatalysts to drive roundtrip sulfur/sulfide conversion is lacking. Here, pairing Lewis acidic and Lewis basic active sites to reach collective adsorption of LiPSs and simultaneous activation of electrophiles and nucleophiles in LiPSs is proposed. This concept is validated by doping polyaniline with protonated metatungstate anions, which enables reduced activation energies for both sulfur reduction reaction and sulfide oxidation reaction and results in significantly improved kinetics. Such electrocatalysts enable a Li–S battery to reach a low capacity‐decay rate of 0.029% per cycle for 1000 cycles. This work would offer insights into battery technologies where sulfur electrocatalysis will play pivotal roles.

Design of Defect-Rich MgCo-Layered Double Hydroxide Microspheres as Highly Effective Sulfur Reduction Reaction Electrocatalyst for High-Performance Li-S Batteries

Design of Defect-Rich MgCo-Layered Double Hydroxide Microspheres as Highly Effective Sulfur Reduction Reaction Electrocatalyst for High-Performance Li-S Batteries

An integrated process incorporating pH-controlled biomineralization and sulfate bioreduction to facilitate recovery of schwertmannite and sulfated polysaccharides from acid mine drainage

Acid mine drainage (AMD) poses an environmental challenge to the global mining industry. However, it is also a potential source of iron and sulfate for recovery. In this work, we proposed an integrated process of pH-controlled biomineralization of iron and biological sulfate reduction to facilitate the concurrent purification of AMD and selective recovery of iron and sulfate as valuable products. Compared with the biomineralization controlling pH at 2.8, the modified biomineralization controlling pH at 3.2 improved the iron precipitation efficiency from 9.7 % to 95.3 %, leading to a 53–fold increase in pure-grade schwertmannite Fe8O8(OH)4.08(SO4)1.96 production in AMD. This improvement may be related to the relatively low Gibbs free energy value of the Fe3+ mineralization reaction at pH 3.2. The solution equilibrium calculation using Visual MINTEQ indicated that keeping the system pH at an appropriate level is crucial for the spontaneous and effective biomineralization of Fe to schwertmannite at room temperature. The specific pH required for Fe biomineralization is slightly affected by the content of metal cations (e.g., Al3+, Ca2+, Mg2+, Cu2+, and Mn2+) and oxoanion (AsO33−/AsO43−) in AMD but greatly affected by sulfate content (mM) (pH = 0.149 ln c(SO42−) + 2.551). For the effluent resulting from AMD biomineralization, sulfate reduction at pH 5.0 removed residual Zn2+ (99.9 %), Mn2+ (97 %), Cu2+ (100 %), and sulfate (87.1 %) while recovering sulfated polysaccharides with antiangiogenic bioactivity (as confirmed by the chorioallantoic membrane tests). The pilot-scale continuous flow operation experiments demonstrated that this integrated method has the potential to recover valuable iron/sulfate products from AMD.

Multi-approach assessment of groundwater biogeochemistry: Implications for the site characterization of prospective spent nuclear fuel repository sites

The disposal of spent nuclear fuel in deep subsurface repositories using multi-barrier systems is considered to be the most promising method for preventing radionuclide leakage. However, the stability of the barriers can be affected by the activities of diverse microbes in subsurface environments. Therefore, this study investigated groundwater geochemistry and microbial populations, activities, and community structures at three potential spent nuclear fuel repository construction sites. The microbial analysis involved a multi-approach including both culture-dependent, culture-independent, and sequence-based methods for a comprehensive understanding of groundwater biogeochemistry. The results from all three sites showed that geochemical properties were closely related to microbial population and activities. Total number of cells estimates were strongly correlated to high dissolved organic carbon; while the ratio of adenosine-triphosphate:total number of cells indicated substantial activities of sulfate reducing bacteria. The 16S rRNA gene sequencing revealed that the microbial communities differed across the three sites, with each featuring microbes performing distinctive functions. In addition, our multi-approach provided some intriguing findings: a site with a low relative abundance of sulfate reducing bacteria based on the 16S rRNA gene sequencing showed high populations during most probable number incubation, implying that despite their low abundance, sulfate reducing bacteria still played an important role in sulfate reduction within the groundwater. Moreover, a redundancy analysis indicated a significant correlation between uranium concentrations and microbial community compositions, which suggests a potential impact of uranium on microbial community. These findings together highlight the importance of multi-methodological assessments in better characterizing groundwater biogeochemical properties for the selection of potential spent nuclear fuel disposal sites.

Assessment of rapid initiators and long-lasting nutrients for developing biological permeable reactive barriers to treat mine-contaminated groundwater

ABSTRACT The formation of mine-contaminated groundwater as a result of acidic mine drainage from the oxidation of sulfur-containing minerals entering the groundwater. Biological permeable reactive barrier (Bio-PRB) technology is excellent for the remediation of mine-contaminated groundwater. Usually, the organic substrates utilized in Bio-PRB are a combination of rapid initiators, which are readily bioavailable, and long-lasting nutrients, which are more difficult to degrade. Herein, we investigated the effectiveness of three rapid initiators and three long-lasting nutrients to remove sulfate from simulated mine-contaminated groundwater via simulated column experiments. The rapid initiators comprised crude glycerol, sodium acetate, and industrial syrup (IS), and the long-lasting nutrients included biodiesel emulsified oil, soybean oil emulsified oil, and high-carbon alcohol emulsified oil (HO). Microorganisms were stimulated using IS to create a sulfate reduction system owing to its high total organic carbon content (24.30 g L−1), achieving optimal sulfate removal rate (1.69 mmol dm−3 d−1). The fastest (2.93 mmol dm−3 d−1) and highest (88%) sulfate removal rates were achieved using HO, which is probably associated with the ability of HO to provide the most suitable C/N ratio (111.75) and induce the growth of sulfate-reducing bacteria (SRB) for substrate degradation. Conversely, a high concentration of sulfate reduction products inhibited SRB growth in the HO column. The addition of organic materials promoted SRB growth and various organic substrate–degrading bacteria. Furthermore, the competitive growth of methanogens (86.6%) may be responsible for the decrease in the relative abundance of SRB during the later stages of the experiment in the HO column.

Cd–Pb isotopic characteristics within the Hehuashan carbonate-hosted Pb–Zn deposit, Middle-Lower Yangtze River Metallogenic Belt: Constraints for ore-forming metal sources and implications for exploration

The Hehuashan carbonate-hosted Pb–Zn deposit is a large-scale deposit situated in the Middle-Lower Yangtze-River Metallogenic Belt (MLYRMB) in China. It contains 0.99 million tons of Zn at an average grade of 1.5 % and 0.41 million tons of Pb at an average grade at 1.9 %, accompanied by critical metals of Cd and Ga. The ores are mainly composed of breccia-type and vein-type in the deposit. Though previous chemical compositions of sphalerite showed that Cd is enriched in both two types of mineralization and the sulfide sulfur isotopes research showed that the reduced sulfur is derived from the marine sulfate reduction, the source of ore-forming metals is still unclear. In this research, we studied the non-traditional stable isotope of Cd and the radioactive isotope Pb of the Hehuashan deposit to discuss the ore-forming metal sources and provide genesis constraints to the Hehuashan Pb–Zn deposit. The sphalerite Cd isotopic compositions are relatively concentrated but the Zn/Cd ratios are scattered in the Hehuashan deposit, of which the early-stage sphalerite δ114/110Cd values ranged from 0.21 ‰ to 0.30 ‰ with an outlier of 0.09 ‰, mean of 0.22 ‰ and a wide range of Zn/Cd ratios (78 to 430), and the late-stage sphalerite δ114/110Cd values ranged from 0.09 ‰ to 0.15 ‰ with two outliers of −0.05 ‰ and 0.52 ‰, mean of 0.17 ‰ with also a wide range of Zn/Cd ratios (50 to 286), both stages of Cd isotopic compositions are overlapped with the ranges of diorite and OIB & MORB, implying the Cd is might be derived from the dioritic intrusions of the Hehuashan deposit district, and the varied Zn/Cd ratios imply that the limestone also provided some of ore-forming metals to the both two ore-forming stages. Additionally, the Pb isotopic compositions of galena in the two mineralization stages exhibit a concentrated range (206Pb/204Pb = 18.2806 – 18.4190, 207Pb/204Pb = 15.6262 – 15.6484, and 208Pb/204Pb = 38.5710 – 38.6529) and all the Pb isotopic data points of the Hehuashan deposit are plotted in the right-hand side of the geochron and the overlapped field of marine sediments, Tongling dioritic intrusions, and Lower Triassic limestones in the Tongling area in the diagrams of (207Pb/204Pb)i vs. (206/204Pb)i and in the field (208Pb/204Pb)i vs. (206/204Pb)i, implying that the Pb is mainly derived from the magma of dioritic intrusions and marine sediments. Subsequently, the sulfide Cd–Pb isotopic compositions show that the ore-forming metals in the Hehuashan deposit are mainly originated from the dioritic intrusions and marine sediments. The plots of deposit genesis classification show that the Cd isotopic compositions in the Hehuashan deposit are unsuitable to the plots of δ114/110Cd vs. Zn/Cd ratios, but imply the metals were derived from multi sources. Finally, the Cd-Pb studies of the Hehaushan Pb–Zn deposit show that the earlier Lower Triassic carbonate formations and its contact with dioritic rocks should be ideal exploration targets for Pb–Zn and associated Cd sources in the Tongling mining area.

Groundwater Bioremediation through Reductive Dechlorination in a Permeable Bioelectrochemical Reactor

A new membrane-less bioelectrochemical reactor configuration was developed for contaminated groundwater remediation. The new bioelectrochemical reactor configuration was inspired by the utilisation of a permeable reactive barrier (PBR) configuration with no separation membrane. The corresponding reactive zones were created by using graphite granules and mixed metal oxide (MMO) electrodes to stimulate the reductive and oxidative biological degradation of chlorinated aliphatic hydrocarbons. In the present study, the PBR-like bioelectrochemical reactor has been preliminarily operated with synthetic contaminated groundwater, testing the reductive dechlorination activity on cis-dichloroethylene (cisDCE). Moreover, to assess the effects of competing anions presence for the electron donor (i.e., the cathode), the synthetic wastewater contained sulphate and nitrate anions. In the PBR-like reactor operation, nearly all cisDCE was removed in the initial sampling port, with only VC detected as the observable RD product. During the same biotic test of the PRB reactor, the presence of both the reductive dechlorination and anions reduction was confirmed by the complete nitrate reduction in the cathodic chamber of the PRB reactor. On the contrary, sulphate reduction showed a lower activity; indeed, only 25% of the influent sulphate was removed by the PRB reactor.

Dual corrosion promotion of pipeline steel in sea mud induced by sulfate reducing bacteria: Bacteria concentration cell and electronic conduction of the biofilms covered sand grains

The microbiologically influenced corrosion (MIC) of X80 carbon steel in sea mud by sulfate reducing bacteria (SRB) was investigated and two unique MIC promotion mechanisms in sea mud were identified. For carbon steel at the seawater-mud interface, difference in the concentrations of sessile cells enhanced galvanic effect between the regions in seawater and sea mud, with the carbon steel in sea mud serving as the anode. SRB in sea mud established significant biofilms on sand grains, enabling the SRB attached on sand grains to participate in the biocatalytic cathodic process of MIC by the contact between sand grains and metal.

Electrocatalytic Mechanism and Sabatier Principle in C2N-Supported Atomically Dispersed Catalysts for the Sulfur Reduction Reaction in Lithium-Sulfur Batteries.

The sluggish kinetics of the sulfur reduction reaction (SRR) impedes the practical application of lithium-sulfur batteries (LSBs). Electrocatalysts are necessary to expedite the conversion of polysulfides. Here, we systematically investigate the chemical mechanisms and size dependence of catalytic activities toward the SRR from Li2S4 to Li2S on single-, double-, and triple-atom catalysts supported on C2N (Mn@C2N, where M is a 3d transitional metal and n = 1-3) as model systems by using first-principles calculations and a comprehensive electrocatalytic model. Our results reveal that the adsorption strength of the LiS• intermediate is identified as an optimal descriptor for catalytic activity. M1@C2N exhibits superior stability and exceptional activity compared to those of the other two catalyst types. Cu1@C2N exhibits the lowest overpotential of 0.426 V. Li embedding or a prelithiation strategy verifies the therein Sabatier principle. This work emphasizes the precise control of the active site structure and microenvironment in catalytic SRR and offers guidance for the design of electrocatalysts for metal-sulfur batteries.

The effect of Ni- and Mo-based materials on thermochemical sulfate reduction by glycerol under hydrothermal process conditions

Catalytic hydrothermal gasification (cHTG) is a sustainable and promising route to convert wet biomass into renewable methane, but the catalyst is deactivated by small amounts of soluble sulfate stemming from the biomass feedstock. Under hydrothermal conditions, sulfate can be converted to the strong catalyst poisons thiols or sulfides by thermochemical sulfate reduction (TSR). In this work, we explored the extent to which TSR occurs under conditions relevant to cHTG operation, along with the impact of various materials on the reaction. Our results indicated that within 60 min, an aqueous solution of 20 wt% glycerol and 10 mM potassium sulfate at 25 MPa started to produce organosulfur compounds at ca. 420–440 °C, with yields for the volatile ones of 3% and 6% at 440 °C and 490 °C, respectively. The main products were non-volatile organosulfur compounds (NVOSC), which were tentatively identified as sulfate esters of glycerol or of glycerol decomposition products. A smaller fraction of products consisted of volatile organosulfur compounds (VOSC). The VOSC identified from the TSR with glycerol were mostly alkyl thiophenes, as well as methanethiol, disulfides and trisulfides with no evidence of H2S formed. Ni-, Mo-, or NiMox-based materials did not show any catalytic effect on sulfate reduction, independent of the sulfidation of the material. Glycerol was proven to be much more reactive towards TSR than acetone, as no TSR products could be observed when acetone was used as a reducing agent. A reaction pathway for the formation of thiophenes from H2S and glycerol is proposed that consists of the dehydration of glycerol, the formation of CO and H2 from glycerol decomposition, hydroformylation of acrolein, and the Paal-Knorr synthesis with succinaldehyde and H2S as intermediates.

Phosphorus release and realignment in anaerobic digestion of thermal hydrolysis pretreatment sludge – Masking effects from high ammonium

Waste activated sludge (WAS) is a significant phosphorus (P) repository, and there is a growing interest in P recovery from WAS. Typically, the commercial technology for treating WAS involves thermal hydrolysis pretreatment (THP) coupled with anaerobic digestion (AD). However, there is ongoing debate regarding the transformation and distribution of P throughout this process. To address this, a long-term THP-AD process was operated in this study to comprehensively investigate P transformation and distribution. The results revealed that a substantial biodegradation of dissolved organic nitrogen (DON) raised the pH of the digestate to 8.3 during the AD process. This increased pH facilitated the dissolution of Al, leading to a reduction of 6.92 mg/L of NaOH-P. Simultaneously, sulfate reduction contributed to a decrease of 11.04 mg/L of Bipy-P in the solid. However, the reduction of Bipy-P and NaOH-P in the solid did not result in an improved P release to the supernatant. Conversely, a decrease of 23.60 mg/L P in the aqueous phase was observed after anaerobic digestion. The disappeared P was primarily precipitated with Mg and Ca, driven by the increased pH, and it contributed to the increase of HCl-P in the solid from 107.80 to 144.52 mg/L. These findings were further confirmed by results obtained from scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and solid-state 31P nuclear magnetic resonance (NMR) spectroscopy. This study provides valuable insights into the mechanisms of P transformation during THP-AD process that is nearly opposite from conventional AD system.