Rate Of Sulfide Oxidation Research Articles

Electrochemical and bioelectrochemical sulphide removal: A review

AbstractThe increased demand for energy worldwide and the focus on the green shift have raised interest in renewable energy sources such as biogas. During biogas production, sulphide (H2S, HS− and S2−) is generated as a byproduct. Due to its corrosive, toxic, odorous, and inhibitory nature, sulphide is problematic in various industrial processes. Therefore, several techniques have been developed to remove sulphide from liquid and gaseous streams, including chemical absorption, chemical dosing, bioscrubbers, and biological oxidation. This review aims to elucidate electrochemical and bioelectrochemical sulphide removal methods, which are gaining increasing interest as possible supplements to existing technologies. In these systems, the sulphide oxidation rate is affected by the reactor design and operational parameters, including electrode materials, anodic potential, pH, temperature and conductivity. Anodic and bioanodic materials are highlighted here, focusing on recent material developments and surface modification techniques. Moreover, the review focuses on sulphide generation and inhibition in biogas production processes and introduces the prospect of removing sulphide and producing methane in one single bioelectrochemical reactor. This could introduce BESs for combined biogas upgrading and cleaning, thereby increasing the methane content and removing pollutants such as sulphide and ammonia in one unit.

Temperature sensitivity of the mineral permafrost feedback at the continental scale.

Oxidative weathering of sulfide minerals in sedimentary rocks releases carbon dioxide (CO2) into the atmosphere. In permafrost zones, this could be a positive feedback on climate change if it increases with warming, yet sulfide oxidation rates and their temperature response remain unknown over large spatial and temporal scales. We analyze a 60-year sulfate concentration dataset from catchments across the Mackenzie River Basin. Sulfate fluxes increased by 45% in the mainstem with 2.3°C of warming, and the temperature sensitivity suggests that continental-scale CO2 fluxes could double by 2100. The largest increases occur in catchments with geomorphic settings which act to rapidly expose rocks through physical weathering and thermokarst processes. Comparisons with a weathering model suggest that warming can increase reaction rates, and changes in the exposure of minerals with warming are also required. Future warming across vast Arctic landscapes could further increase sulfide oxidation rates and affect regional carbon cycle budgets.

Coupled sulfur and nitrogen cycling at a catchment scale: insights from isotopic and molecular techniques

The biogeochemical cycles of nitrogen (N) and sulfur (S) play important roles in sustaining the Earth's ecosystem. However, their potential coupling process and underlying mechanisms in the nature remain unclear. Through joint applications of river water's isotopic compositions, isotope-pairing experiments, and molecular techniques, this study revealed the coupled N-S cycling processes at a catchment scale from both geochemical and biological perspectives. The river water's natural abundance isotopic compositions indicated that sulfide oxidation was an important source (67.0 ± 5.5 % in summer and 72.0 ± 5.5 % in winter) of riverine sulfate (SO42−). In addition, sulfide oxidation and NOx reduction (especially denitrification) were tightly coupled in summer but less significantly so in winter. However, the coupling of sulfide oxidation and dissimilatory nitrate reduction to ammonium (DNRA) could not be overlooked in winter. The 15N pairing experiments quantitatively showed that the high sulfide oxidation rates in summer (4.7 ± 2.3 mol/km2/h) were significantly associated with the denitrification. Metagenomics and qPCR analyses of the soils supported the isotopic interpretations, substantiating the metabolic potential and coexistence of bacterial denitrification, DNRA, and sulfide oxidation, which was more prevalent in summer. This study reveals comprehensive evidence that sulfide oxidation and NOx reduction are tightly coupled at the catchment scale, which provides a new perspective towards a better understanding of N-S cycling.

Rational modulation of covalent organic frameworks heterogeneous catalyst: Structural cationization effect on accelerating photocatalytic oxidation process

Photocatalytic technology has been playing a key role in energy conversion and environmental remediation. It is critical and challenging that understanding and modulating the local structure effect on accelerating each rate-dependent step during the photocatalytic process. Herein, we utilize the highly ordered and structurally tunable COFs as a favorable platform for integrating multiple modulations of photochemical properties, including light capture, exciton dissociation, charge separation, and mass transfer by structural cationization strategy. Moreover, it is found that the cationized COF has a strong enrichment ability on the sulfide substrates, exhibiting an extremely fast selective oxidation rate of sulfides even in air. The calculation results indicate that the structural cationization successfully aggregates reaction substrates and increases the molecular collision probability, generating a reaction environment to promote the photocatalytic performances. This study will be expected to facilitate the new insights for the exploration of highly active COFs heterogeneous photocatalysts.

Sulfide oxidation by members of the Sulfolobales.

The oxidation of sulfur compounds drives the acidification of geothermal waters. At high temperatures (>80°C) and in acidic conditions (pH <6.0), oxidation of sulfide has historically been considered an abiotic process that generates elemental sulfur (S0) that, in turn, is oxidized by thermoacidophiles of the model archaeal order Sulfolobales to generate sulfuric acid (i.e. sulfate and protons). Here, we describe five new aerobic and autotrophic strains of Sulfolobales comprising two species that were isolated from acidic hot springs in Yellowstone National Park (YNP) and that can use sulfide as an electron donor. These strains significantly accelerated the rate and extent of sulfide oxidation to sulfate relative to abiotic controls, concomitant with production of cells. Yields of sulfide-grown cultures were ∼2-fold greater than those of S0-grown cultures, consistent with thermodynamic calculations indicating more available energy in the former condition than the latter. Homologs of sulfide:quinone oxidoreductase (Sqr) were identified in nearly all Sulfolobales genomes from YNP metagenomes as well as those from other reference Sulfolobales, suggesting a widespread ability to accelerate sulfide oxidation. These observations expand the role of Sulfolobales in the oxidative sulfur cycle, the geobiological feedbacks that drive the formation of acidic hot springs, and landscape evolution.

Reactive transport modelling of tailings hydrogeochemistry under a composite cover

Quantitative forecasts of acid mine drainage (AMD) production are important for remediation planning. Reactive transport simulations corresponding to a detailed sampling location at a covered legacy tailings impoundment in northern Ontario, Canada, were conducted to quantitatively assess the predominant hydrogeochemical reactions. The simulations span the period from the end of tailings deposition (circa 1970) to early 2020, 12 years after remediation by a five-layer composite cover. The conceptual model of uncovered tailings weathering and subsequent geochemistry of the covered tailings system was implemented in 1D using the multi-component reactive transport code MIN3P. Transient monthly infiltration, post-cover boundary condition changes, and a dynamic temperature regime were incorporated. The shrinking core model, including parallel O2(aq) and Fe3+ oxidation reactions for the waste rock in the cover and the underlying tailings, was implemented to simulate the oxidation of As-bearing pyrite, chalcopyrite, and sphalerite. Primary carbonate and aluminosilicate host minerals promoted acid-neutralization reactions. Precipitation of secondary phases and sorption/desorption of Cu, Zn, and arsenite were incorporated into the model. The overall agreement between key simulated and field-measured post-cover aqueous geochemical parameters suggests that the conceptual model captured the primary hydrogeochemical processes in the covered tailings. A lack of reliable data on initial tailings mineralogy and pre-cover hydrogeochemistry increased simulation uncertainty. Simulated reaction rates indicate that where intact, the cover decreased sulfide oxidation rates by both O2(aq) and Fe3+ and improved pore-water quality over time. Simulation results indicate that elevated concentrations of Zn and As are likely to persist in the tailings regardless of cover performance, whereas concentrations of Cu and Al are the parameters most sensitive to cover effectiveness.

Geochemistry and mineralogy of legacy tailings under a composite cover

Remediation by a composite cover was implemented on partly oxidized sulfide-rich tailings in northern Ontario, Canada to reduce the production and release of acid mine drainage (AMD). The impact of the cover on sulfide oxidation rates and trace element mobility was initiated a decade after cover installation via multi-year measurements of pore-gas concentrations, pore-water and groundwater sampling and analysis, mineralogical studies of the tailings, selective chemical extractions, and synchrotron-based X-ray absorption experiments. Depleted pore-gas O2 concentrations, circumneutral pH, and improvement in water quality were observed at one detailed sampling location, suggesting that the cover decreased AMD generation and transport. Carbon and sulfur isotope ratios indicate sulfate reduction occurred at the base of the tailings. In contrast, near-atmospheric pore-gas O2 concentrations, low pH, and elevated aqueous concentrations of Fe, sulfate, Zn, Cu, As, and Pb were observed at another location, suggesting localized sulfide oxidation. Trace elements in the tailings are associated with secondary crystalline and amorphous Fe(III) oxyhydroxides, covellite, and Fe(III) hydroxysulfate phases, formed prior to cover installation. Substantial reductive dissolution of Fe(III) oxyhydroxides due to the isolation of the tailings from the atmosphere by the cover was not observed. Concentrations of Zn and Mn remained elevated due to limited sequestration under the current acidic to circumneutral pH. Although secondary Fe(III) oxyhydroxides contain As(V) and As(III), which were released by arsenopyrite oxidation, dissolved As persists. Due to localized sulfide oxidation, element remobilization, and limited capacity for sulfate reduction, diminished water quality, with elevated aqueous concentrations of sulfate, Zn, As, and Mn, may endure.

Recovery of bio‑sulfur and metal resources from mine wastewater by sulfide biological oxidation-alkali flocculation: A pilot-scale study

Mine wastewater treatment using bio-sulfate reduction technology forms sulfur-containing wastewater that comprises sulfides (HS− and S2−) and metal ions. Bio‑sulfur generated by sulfur-oxidizing bacteria in such wastewater is usually negatively charged hydrocolloidal particles. However, bio‑sulfur and metal resource recovery are difficult using traditional methods. In this study, the sulfide biological oxidation-alkali flocculation (SBO-AF) method was investigated to recover the above resources, and to provide a technical reference for mine wastewater resource recovery and heavy metal pollution control. Specifically, the performance of SBO in forming bio‑sulfur and the key parameters of SBO-AF were explored and then applied in a pilot-scale process to recover resources from wastewater. Results show that partial sulfide oxidation was achieved under a sulfide loading rate of 5.08 ± 0.39 kg/m3·d, dissolved oxygen of 2.9–3.5 mg/L and temperature of 27–30 °C. The average sulfide oxidation rate and sulfur selectivity ratio were 92.86 % and 90.22 %, respectively. At pH 10, metal hydroxide and bio‑sulfur colloids co-precipitated through the precipitation catching and adsorption charge neutralization effect. The average manganese, magnesium and aluminum concentrations and turbidity in the wastewater were 53.93 mg/L, 522.97 mg/L, 34.20 mg/L and 505 NTU, respectively, and decreased to 0.49 mg/L, 80.65 mg/L, 1.00 mg/L and 23.33 NTU, respectively, after treatment. The recovered precipitate mainly contained sulfur, along with metal hydroxides. The average sulfur, manganese, magnesium and aluminum contents were 45.6 %, 29.5 %, 15.1 % and 6.5 %, respectively. Economic feasibility analysis and the above results show that SBO-AF has obvious technical and economic advantages in the recovery resources from mine wastewater.

Effect of Stoichiometry on Nanomagnetite Sulfidation.

Magnetite (Mt) has long been regarded as a stable phase with a low reactivity toward dissolved sulfide, but natural Mt with varying stoichiometries (the structural Fe(II)/Fe(III) ratio, xstru) might exhibit distinct reactivities in sulfidation. How Mt stoichiometry affects its sulfidation processes and products remains unknown. Here, we demonstrate that xstru is a master variable controlling the rates and extents of sulfide oxidation by magnetite nanoparticles (11 ± 2 nm). At pH = 7.0-8.0 and the initial Fe/S molar ratio of 10-50, the partially oxidized magnetite (xstru = 0.19-0.43) can oxidize dissolved sulfide to elemental sulfur (S0), but only surface adsorption of sulfide, without interfacial electron transfer (IET), occurs on the nearly stoichiometric magnetite (xstru = 0.47). The higher initial rate and extent of sulfide oxidation and S0 production are observed with the more oxidized magnetite that has the higher electron-accepting capability from surface-complexed sulfide (S(-II)(s)). The FeS clusters formed from magnetite sulfidation can be oxidized by the most oxidized magnetite with xstru = 0.19 but not by other magnetite particles. A linear relationship between the Gibbs free energy of reaction and the surface area-normalized initial rate of sulfide oxidation is observed in all experiments under the different conditions, suggesting the S(-II)(s)-magnetite IET dominates magnetite sulfidation at high Fe/S molar ratios and near-neutral pH.

Lithological and glacial controls on sulfide weathering and the associated CO2 budgets in the Tibetan Plateau: New constraints from small catchments

The Tibetan Plateau, a region that hosts low to middle-latitude glaciers and a high density of metasedimentary rocks, is a hotspot of continental weathering and carbon cycling. However, quantitative estimations of sulfide oxidation and how it affects CO2 budgets from the plateau weathering are lacking. Here we use chemical and isotopic datasets from the studied small catchments in the Tibetan Plateau to estimate that 69.1% to 77.0% of stream SO42– originates from sulfide oxidation. Thus, more than 80% of the CO2 consumed by silicate weathering is counterbalanced by transient CO2 release from H2SO4-driven carbonate dissolution in the study area. In addition, the sulfide oxidation rate for glacial catchments is 5 times that of nonglacial catchments. The CO2 release rate from acid generated by sulfide oxidation in metasedimentary catchments is approximately 3 times that of granitic catchments. We propose that sulfide oxidation has greatly modified the CO2 budget of chemical weathering of the Tibetan Plateau. This study reveals new constraints on the CO2 budget in the Tibetan Plateau weathering, and will provide important insights into the carbon cycle during the plateau uplifting in Cenozoic.

Enhanced sulfide oxidation by monsoon rainfall in a small typical karstic catchment of Southwest China

CO2 is released to the atmosphere via sulfuric acid weathering of carbonate rocks, affecting the flux of CO2 drawdown via silicate weathering. Precisely quantifying the proportion of oxidative weathering of sulfide minerals to riverine sulfate is critical to improving the estimation of the global carbon budge. Sulfur and oxygen isotopic compositions of sulfate and major ion concentrations in river water samples collected monthly at 12 sampling sites from a small typical karstic catchment of Southwest China were analyzed, in order to quantify the relative contribution of sulfide oxidation to riverine sulfate and elucidate the factors affecting its changes. Results show that the sulfate concentration and δ34Ssulfate and δ18Osulfate values at most sampling sites have obvious seasonal changes, with low values in the monsoon season and high values in the non-monsoon season, suggesting that the relative contributions of different sulfur sources to riverine sulfate are seasonally variable throughout of the year. Results from the Beyesian isotope mixing model show that overall, the fraction of sulfide-derived sulfate to riverine sulfate ranges from 44.3 ± 13.7% to 53.3 ± 10.5%, although it has a wide range for different sampling sites. In addition, the relative contribution of sulfide weathering displays a seasonal variation and is higher in the monsoon season, which is mainly attributed to the influence of high rainfall in wet season. This study indicates that an increase in rainfall intensity under climate change may lead to a raised sulfide oxidation rate in the karstic catchment, which is important for assessment of global carbonate and silicate weathering in future.

Systems analysis of the effect of hydrogen sulfide on the growth of Methylococcus capsulatus Bath.

Methanotrophs are bacteria capable on growing on methane as their sole carbon source. They may provide a promising route for upgrading natural gas into more valuable fuels and chemicals. However, natural gas may contain significant quantities of hydrogen sulfide. Little is known about how hydrogen sulfide affects the growth and physiology of methanotrophs aside from a few studies showing that it is inhibitory. This study investigated how hydrogen sulfide affects the growth and physiology of the model methanotroph, Methylococcus capsulatus Bath. Growth studies demonstrated that hydrogen sulfide inhibits the growth of M. capsulatus Bath when the concentration exceeds 0.5% (v/v). To better understand how hydrogen sulfide is inhibiting the growth of M. capsulatus Bath, transcription and metabolite concentrations were profiled using RNA sequencing and gas chromatography-mass spectrometry, respectively. Our analysis of the differentially expressed genes and changes in metabolite concentrations suggests that hydrogen sulfide inhibits cellular respiration. The cells respond to sulfide stress in part by increasing the rate of sulfide oxidation and by increasing the expression of sulfide quinone reductase and a putative persulfide dioxygenase. In addition, they reduce the expression of the native calcium-dependent methanol dehydrogenase and increase the expression of XoxF, a lanthanide-dependent methanol dehydrogenase. While the reason of this switch in unknown, XoxF has previously been shown to be induced by lanthanides or nitric oxide in methanotrophs. Collectively, these results further our understanding of how methanotrophs respond to sulfide stress and may aid in the engineering of strains resistant to hydrogen sulfide. KEY POINTS: • Hydrogen sulfide inhibits growth of Methylococcus capsulatus Bath • Sulfide stress inhibits cellular respiration • Sulfide stress induces XoxF, a lanthanide-dependent methanol dehydrogenase.

The Optimization of Sulphide Oxidizing Bacteria (SOB) for Oil Corrosivity Reduction at Indramayu Coast, The Northern Coastal Area of West Java

Highlight Research First NR-SOB from Indramayu coast was successfully isolated and identified. Bactrerial characterization morphologically and biochemically, foster with in situ hybridization confirm the isolate was Thiobacillus denitrificans, and Arcobacter sp. Both isolate, Thiobacillus denitrificans and Arcobacter sp., were able to grow in sulphide rich environment in the presence of essential nutrient Thiobacillus denitrificans and Arcobacter sp. exhibit an outstanding sulphide oxidation ability up to 100% in the presence of nitrate. Abstract Crude oil production triggers the formation of hydrogen sulphide, also known as souring, which is extremely toxic and corrosive to the environment. It additionally give an adverse consequence to aquatic, terrestrial, and human existence. Studies of hydrogen sulphide reduction in sediments polluted by crude oil have been carried out recently to investigate the capability of indigenous Nitrate-Reducing Sulphide Oxidising Bacteria, hereinafter referred to as NR-SOB, as bioremediation agents. The experiments utilised hydrogen sulphide with 200 µM concentration combined with NO3 with different concentrations of 100 µM, 200 µM, and 300 µM. Measurements of the hydrogen sulfide concentrations were observed up to 48 hours within the experimental period. The SOB used in this study were taken from Balongan Bay at Indramayu coast using Nansen bottle to carry out water sample. The sulphide-oxidising ability of SOB was then evaluated at room temperature in control environment. Methylene blue method was applied to monitor the sulphide concentration. The results showed a complete removal of hydrogen sulphide concentrations in 48 hours accompanied with gradual drops of nitrate in all experiment series. Sulphide oxidation rate was detected to appear between 6.8 and 10.2 fmol/cell/hour. Measurements of cell abundance after 48 hours showed 6.2 x 105, 7.5 X 105, and 8.2 X 105 cell/ml from Experiments I, II, and III respectively. Using MSS selective medium, the bacteria were identified as Thiobacillus denitrificans and Arcobacter sp. Overall, the isolated NR-SOB from the coast of Balongan Bay, Indramayu proves to be a promising candidate for sulphide controls and mitigation.

Sulfur isotope fractionation derived from reaction-transport modelling in the Eastern Equatorial Pacific

Microbial sulfate reduction in subseafloor sediments regulates a significant portion of the marine organic matter burial flux. Over secular timescales, sulfate reduction is the fundamental process connecting the biogeochemical cycles of sulfur, carbon, oxygen and phosphorus. Similar to carbon reduction, sulfate reduction is associated with a strong isotope fractionation process that allows us to track this process through time. It depends on a variety of factors and it has been argued previously that systematic differences between shallow and deep-sea environments might explain secular changes in the marine S-isotope ratio. However, observational data of in situ fractionation from deep-sea areas are scarce. Here we use a reaction-transport model to analyse the S-isotope fractionation during microbial sulfate reduction in the interstitial water of Ocean Drilling Program (ODP) Site 1226 (Leg 201). We find that the upper 100 m below seafloor are best explained with fractionation around −76‰, whereas below this depth the degree of fractionation drops to around −42‰. We propose that this shift is caused by changes in the ratio of the rate of microbial sulfate reduction relative to the rate of abiotic sulfide oxidation. Because large parts of deep oceans are characterized by exceedingly low sulfate reduction rates, this process may be widespread and possibly explain why pyrite S-isotope data suggest that the average S-isotope fractionation is around −50‰, rather than the theoretically predicted value below −70‰. Supplementary material: Supplementary figures and model results are available at https://doi.org/10.6084/m9.figshare.c.5976772 Thematic collection: This article is part of the Sulfur in the Earth system collection available at: https://www.lyellcollection.org/cc/sulfur-in-the-earth-system

Effect of relative humidity on oxidation products of arsenopyrite and löllingite

Arsenopyrite (FeAsS) and löllingite (FeAs2) are among the most common primary As minerals in the wastes produced by mining and associated ore processing activities. This study explores the oxidation of these minerals at high relative humidity that frequently occur in underground mines and unsaturated waste piles and tailings. Our objectives were to examine the effect of relative humidity on the mineralogy of secondary phases that formed after 40 months of exposure of arsenopyrite-rich (Apy) and löllingite-rich (Lö) concentrates to six constant relative humidity (RH) levels between 75% and 100%. X-ray diffraction, electron microprobe, Raman microspectrometry, and sequential extraction results showed that the dominant oxidation product in Apy concentrates at any controlled RH level was poorly crystalline ferric arsenate (PCFA). This phase revealed increasing dehydration, and release of sulfate with increasing RH ≥ 94%; indicating that high humidity accelerates the transformation process of PCFA to scorodite. Newly formed elemental sulfur, parascorodite, hydroniumjarosite, and ferric (hydr)oxides were minor (to trace) phases in Apy concentrates; and the latter two phases only formed on the surface of pyrite as a result of the limited transport of solutes between individual grains of sulfides at RH ≤ 81%. In comparison, well crystallized scorodite and arsenolite were the dominant oxidation products in Lö concentrates at every RH. Increasing RH significantly increased the oxidation rate of sulfide and arsenide minerals in the concentrates. The highest sulfide and arsenide oxidation rates in the Lö concentrate occurred at RH 100%, and was approximately 40 times faster than at RH 81%. In comparison, the highest oxidation rate of sulfides in the Apy concentrate occurred at RH 94%, and was 6 to 7 times faster that than at RH 81%. Differences in the mineralogical compositions of oxidation products in the Apy and Lö concentrate reflect the high levels of sulfate in the Apy concentrate. This triggered formation of PCFA and retarded its transformation to scorodite. The substantial role of sulfate in the oxidation process is reinforced by the finding that stagnation of the sulfide oxidation rate in the Apy concentrate at high RH (> 94%) was probably due to the formation of ferric ion complexes in the presence of high levels of sulfate ions.

Aqueous system-level processes and prokaryote assemblages in the ferruginous and sulfate-rich bottom waters of a post-mining lake

Abstract. In the low-nutrient, redox-stratified Lake Medard (Czechia), reductive Fe(III) dissolution outpaces sulfide generation from microbial sulfate reduction (MSR) and ferruginous conditions occur without quantitative sulfate depletion. The lake currently has marked overlapping C, N, S, Mn and Fe cycles occurring in the anoxic portion of the water column. This feature is unusual in stable, natural, redox-stratified lacustrine systems where at least one of these biogeochemical cycles is functionally diminished or undergoes minimal transformations because of the dominance of another component or other components. Therefore, this post-mining lake has scientific value for (i) testing emerging hypotheses on how such interlinked biogeochemical cycles operate during transitional redox states and (ii) acquiring insight into redox proxy signals of ferruginous sediments underlying a sulfatic and ferruginous water column. An isotopically constrained estimate of the rates of sulfate reduction (SRRs) suggests that despite high genetic potential, this respiration pathway may be limited by the rather low amounts of metabolizable organic carbon. This points to substrate competition exerted by iron- and nitrogen-respiring prokaryotes. Yet, the planktonic microbial succession across the nitrogenous and ferruginous zones also indicates genetic potential for chemolithotrophic sulfur oxidation. Therefore, our SRR estimates could rather be portraying high rates of anoxic sulfide oxidation to sulfate, probably accompanied by microbially induced disproportionation of S intermediates. Near and at the anoxic sediment–water interface, vigorous sulfur cycling can be fuelled by ferric and manganic particulate matter and redeposited siderite stocks. Sulfur oxidation and disproportionation then appear to prevent substantial stabilization of iron monosulfides as pyrite but enable the interstitial precipitation of microcrystalline equant gypsum. This latter mineral isotopically recorded sulfur oxidation proceeding at near equilibrium with the ambient anoxic waters, whilst authigenic pyrite sulfur displays a 38 ‰ to 27 ‰ isotopic offset from ambient sulfate, suggestive of incomplete MSR and open sulfur cycling. Pyrite-sulfur fractionation decreases with increased reducible reactive iron in the sediment. In the absence of ferruginous coastal zones today affected by post-depositional sulfate fluxes, the current water column redox stratification in the post-mining Lake Medard is thought relevant for refining interpretations pertaining to the onset of widespread redox-stratified states across ancient nearshore depositional systems.

Biological manganese-dependent sulfide oxidation impacts elemental gradients in redox-stratified systems: indications from the Black Sea water column

The reduction of manganese oxide with sulfide in aquatic redox-stratified systems was previously considered to be mainly chemical, but recent isolation of the Black Sea isolate Candidatus Sulfurimonas marisnigri strain SoZ1 suggests an important role for biological catalyzation. Here we provide evidence from laboratory experiments, field data, and modeling that the latter process has a strong impact on redox zonation in the Black Sea. High relative abundances of Sulfurimonas spp. across the redoxcline in the central western gyre of the Black Sea coincided with the high-level expression of both the sulfide:quinone oxidoreductase gene (sqr, up to 93% expressed by Sulfurimonas spp.) and other sulfur oxidation genes. The cell-specific rate of manganese-coupled sulfide oxidation by Ca. S. marisnigri SoZ1 determined experimentally was combined with the in situ abundance of Sulfurimonas spp. in a one-dimensional numerical model to calculate the vertical sulfide distribution. Abiotic sulfide oxidation was too slow to counterbalance the sulfide flux from euxinic water. We conclude that microbially catalyzed Mn-dependent sulfide oxidation influences the element cycles of Mn, S, C, and N and therefore the prevalence of other functional groups of prokaryotes (e.g., anammox bacteria) in a sulfide-free, anoxic redox zone.

Response difference of simultaneous sulfide and nitrite removal process to different cooling modes

The effects of various cooling modes (sudden cooling (25℃→10℃) and step cooling (25℃→20℃→15℃→10℃)) on the performance of simultaneous sulfide and nitrite removal process were reported. Regardless of cooling mode adopted, the process maintained good sulfide removal performance, and removal percentage was 100.00%. Considering nitrite removal percentage, the process was more sensitive to step cooling mode (k = 0.06707) in comparison to sudden cooling mode (k = 0.02760). Lowering temperature promoted the transformation from sulfate to elemental sulfur, and it was easier to increase the proportion of elemental sulfur (79.90%) by means of step cooling. The sulfide oxidation rate and nitrite reduction rate were 0.01540 mg /(L∙min) and 0.00354 mg /(L∙min), respectively, in the sudden cooling mode, and 0.01168 mg /(L∙min) and 0.00138 mg /(L∙min), respectively, in the step cooling mode. Low temperature reduced the diversity of microbial community, and Sulfurovum was still a dominant bacterial member in both cooling modes.

Microbiology of a multi-layer biosolid/desulfurized tailings cover on a mill tailings impoundment

The Strathcona Waste Water Treatment System (SWWTS; Sudbury, ON, Canada) has received mill tailings from Ni/Cu ore processing from 1970 to present. Demonstration-scale, multi-layer cover systems were installed on selected tailings deposition cells at the SWWTS. The cover systems are comprised of an upper layer of organic carbon-rich material, composed of a layer biosolids fertilizer along with composted municipal food and yard waste, then a layer of desulfurized, fine-grained tailings. Organic carbon components used in these covers promote microbial communities that consume O2, thus decreasing sulfide oxidation rates in the underlying tailings. The aim of this study was to investigate the microbiology of the cover systems and the underlying tailings, using a combination of culture-dependent (most probable number) and culture-independent (16S rRNA gene amplicon sequencing) techniques, and assess the impact of the organic component of the cover system four to six years after implementation. Most tailings samples were characterized by circumneutral bulk pH and low concentrations of dissolved metals. The presence of the organic cover resulted in elevated counts of sulfate-reducers (by two orders of magnitude, compared to control samples) immediately below the organic cover, as well as an increased abundance of heterotrophic species (∼108 cells g−1) at greater depth (∼4 m) in the tailings profile. Mineral-oxidizing microorganisms were also present in the tailings, with neutrophilic sulfur-oxidizers dominating the samples (mean ∼106 cells g−1). Relative abundances of sulfur- and/or iron-oxidizers determined by sequencing ranged from 0.5 to 18.3% of total reads (mean ∼5.6% in amended tailings) and indicated the presence of local microenvironments with ongoing sulfide oxidation. This work provides a detailed characterization of the microbiology of a tailings impoundment with an organic cover, highlighting the opportunities associated with monitoring microbial processes in such remediation systems.

Geochemistry of natural acid rock drainage in the Mt Evans area, Anaconda–Pintler Range, Montana, USA

This paper investigates natural acid rock drainage in two streams draining either side of Mt Evans, Montana. Bedrock consists of pyrrhotite-bearing schist intruded by granitic dykes and plutons of Late Cretaceous to Tertiary age. The headwaters of both streams are moderately acidic (pH &lt; 5.0) and carry elevated loads of dissolved sulfate, aluminum and other trace metals (Cd, Co, Cu, Mn, Zn) as well as rare earth elements (REEs). Copious aluminum precipitates inferred to be hydrobasaluminite coat boulders of both streams as pH rises &gt; 5, with adsorption of copper and REEs. Concentrations and loads of dissolved sulfate and trace elements are anomalously high in a small tributary that is sourced by meltwater from a rock glacier. The S-isotope composition of dissolved sulfate in both watersheds is similar to that of pyrrhotite in the meta-sediments, but not molybdenite in late porphyry dykes. Calculations of sulfate flux (i.e. sulfate load divided by surface area) indicate a relatively fast rate of sulfide oxidation in the study area, possibly due to exposure of fresh bedrock in the steep and recently glaciated field area. Overall, the geochemistry of the site suggests the possible presence of a metamorphosed sedimentary–exhalative deposit, a possibility that is unlikely to be tested by drilling given the proximity of the site to a federal wilderness area. Supplementary material: All analytical data related to this project, additional maps and photographs, and selected results from geochemical modelling are available at https://doi.org/10.6084/m9.figshare.c.5649850 Thematic collection: This article is part of the Hydrochemistry related to exploration and environmental issues collection available at: https://www.lyellcollection.org/cc/hydrochemistry-related-to-exploration-and-environmental-issues