Rate Of Sulfide Oxidation Research Articles

Development of whole-cell catalyst system for sulfide biotreatment based on the engineered haloalkaliphilic bacterium

Microorganisms play an essential role in sulfide removal. Alkaline absorption solution facilitates the sulfide’s dissolution and oxidative degradation, so haloalkaliphile is a prospective source for environmental-friendly and cost-effective biodesulfurization. In this research, 484 sulfide oxidation genes were identified from the metagenomes of the soda-saline lakes and a haloalkaliphilic heterotrophic bacterium Halomonas salifodinae IM328 (=CGMCC 22183) was isolated from the same habitat as the host for expression of a representative sequence. The genetic manipulation was successfully achieved through the conjugation transformation method, and sulfide: quinone oxidoreductase gene (sqr) was expressed via pBBR1MCS derivative plasmid. Furthermore, a whole-cell catalyst system was developed by using the engineered strain that exhibited a higher rate of sulfide oxidation under the optimal alkaline pH of 9.0. The whole-cell catalyst could be recycled six times to maintain the sulfide oxidation rates from 41.451 to 80.216 µmol·min−1·g−1 dry cell mass. To summarize, a whole-cell catalyst system based on the engineered haloalkaliphilic bacterium is potentiated to be applied in the sulfide treatment at a reduced cost.

Rapid sulfur cycling in sediments from the Peruvian oxygen minimum zone featuring simultaneous sulfate reduction and sulfide oxidation

AbstractBacterial sulfate reduction (SR) is often determined by radiotracer techniques using 35S‐labeled sulfate. In environments featuring simultaneous sulfide oxidation, SR can be underestimated due to re‐oxidation of 35S‐sulfide. Recycling of 35S‐tracer is expected to be high in sediment with low concentrations of pore‐water sulfide and high abundance of giant filamentous sulfur‐oxidizing bacteria (GFSOB). Here, we applied a sulfide‐spiking method, originally developed for water samples, to sediments along a shelf‐slope transect (72, 128, 243, 752 m water depth) traversing the Peruvian oxygen minimum zone. Sediment spiked with unlabeled sulfide prior to 35S‐sulfate injection to prevent radiotracer recycling was compared to unspiked sediment. At stations characterized by low natural sulfide and abundant GFSOB (128 and 243 m), the method revealed 1–3 times higher SR rates in spiked sediment. Spiking had no effect on SR in sediment with high natural sulfide despite presence of GFSOB (72 m). Bioturbated sediment devoid of GFSOB (752 m) showed elevated SR in spiked samples, likely from artificial introduction of sulfidic conditions. Sulfide oxidation rates at the 128 and 243 m station, derived from the difference in SR between spiked and unspiked sediment, approximated rates of dissimilatory nitrate reduction to ammonium by GFSOB. Gross SR contributed considerably to benthic dissolved inorganic carbon fluxes at the three shallowest station, confirming that SR is an important process for benthic carbon respirations within the oxygen minimum zone. We recommend to further explore the spiking method to capture SR in sediment featuring low sulfide concentrations and high sulfur cycling by GFSOB.

The waste rock of the Touro copper deposit in Galicia, Spain: challenges for its environmental characterization

Characterization of metamorphic rocks to evaluate waste material acid rock drainage potential is particularly challenging as commonly used laboratory methods can result in its significant underprediction. Static tests were conducted for over 300 samples from the Touro copper project and indicate that carbon-based methods frequently overestimate acid neutralization potential due to the presence of both graphite and manganese–iron carbonates. The Modified Sobek method more accurately accounts for the buffering capacity of carbonates and does not account for graphite, although aluminosilicate dissolution kinetics need to be evaluated in the context of sulfide oxidation rates. Historic sulfur assays for the project relied on methods insufficient to fully digest metamorphosed sulfides and required correction. The more aggressive Leco method provides accurate sulfur estimates and has now been adopted for the project. Static test metrics such as the net neutralization potential or neutralization potential ratio, therefore, can give misleading results when incorrect characterization methods are employed. Such metrics should be considered as screening level, used with caution, and complemented with careful field and laboratory kinetic tests. Preliminary humidity cell testing of five Touro samples suggests that terminal pH values for cells that have become acidic closely match predicted net acid generation (NAG) pH values. The NAG pH test avoids some of the challenges associated with sulfur and carbon predictions in metamorphic rocks as it directly buffers sulfide oxidation acidity with available material neutralization potential. As such, NAG pH has been adopted as the accepted project metric for segregating acid-generating from non-acid-generating waste. Supplementary material: All Touro project static and kinetic test data are available at https://doi.org/10.6084/m9.figshare.c.5389948 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

Study on detoxification property of alkaline-modified MoO42--H2O2 decontaminants against PhSMe under subzero environment

The decontaminant activated by MoO42- (MoO42--H2O2) suitable for subzero environment shows strong oxidizing ability and weak nucleophilicity due to its acid. In this paper, in order to improve nucleophilicity and retain oxidation of MoO42--H2O2 as far as possible, NH3 and NaOH were used as alkaline modifiers, and PhSMe was used as a simulant of HD to study the oxidation rate and products of sulfides by alkaline-modified MoO42--H2O2 below zero. Results showed that the reaction rate constants decreased with the increase of pH in both NH3 and NaOH modified MoO42--H2O2 at -20°C, and the relative ratio of sulfone to sulfoxide increased especially at pH>9. The reaction activation energy Ea of PhSMe oxidation in the alkaline-modified MoO42--H2O2 decontaminants was lower than that in the MoO42--H2O2 decontaminant, which indicated that the sensitivity of the oxidation reaction rate to temperature in MoO42--H2O2 was reduced after modification.

Degradation of odorous sulfide compounds by different oxidation processes in drinking water: Performance, reaction kinetics and mechanism

Swampy/septic odor caused by various sulfides is one of the most frequently encountered odor problems in drinking water. However, even though it is much more offensive, few studies have specifically focused on swampy/septic odor compared to the extensively studied musty/earthy problems. In this work, four sulfide odorants, diamyl sulfide (DAS), dipropyl sulfide (DPS), dimethyl disulfide (DMDS) and diethyl disulfide (DEDS), were selected to evaluate the treatment performance of different oxidation processes in drinking water. The results demonstrated that DMDS, DEDS, DPS and DAS could be oxidized effectively by KMnO4, NaClO and ClO2. The oxidation processes could be well described by the second-order kinetic model, in which k values of selected sulfides followed the order DMDS≈DEDS ≪ DPS≈DAS. As for the three oxidants, the order of reactivity was KMnO4 ≪ ClO2 < NaClO, which was also verified in raw water. The results of oxidation treatability, reaction kinetics and mechanisms confirmed that the characteristics of the central sulfur atom rather than the side chain is the decisive factor in controlling the oxidation rate and transformation pathway of sulfides. The transformation products and pathways were significantly different for the three oxidants. Sulfones (DPSO, DASO) were always formed by cycloaddition reactions during KMnO4 oxidation, yet recombination reactions proceeded during ClO2 oxidation and formed more products, such as MADS, DADS and EADS. Density functional theory (DFT) calculations confirmed that the differences in transformation pathways were caused by the variations in the activity of the oxidants and sulfides. Finally, NaClO was certified as the most effective oxidant for controlling sulfide odorants in drinking water treatment.

The Heterotrophic Bacterium Cupriavidus pinatubonensis JMP134 Oxidizes Sulfide to Sulfate with Thiosulfate as a Key Intermediate.

Heterotrophic bacteria actively participate in the biogeochemical cycle of sulfur on Earth. The heterotrophic bacterium Cupriavidus pinatubonensis JMP134 contains several enzymes involved in sulfur oxidation, but how these enzymes work together to oxidize sulfide in the bacterium has not been studied. Using gene-deletion and whole-cell assays, we determined that the bacterium uses sulfide:quinone oxidoreductase to oxidize sulfide to polysulfide, which is further oxidized to sulfite by persulfide dioxygenase. Sulfite spontaneously reacts with polysulfide to produce thiosulfate. The sulfur-oxidizing (Sox) system oxidizes thiosulfate to sulfate. Flavocytochrome c sulfide dehydrogenase enhances thiosulfate oxidation by the Sox system but couples with the Sox system for sulfide oxidation to sulfate in the absence of sulfide:quinone oxidoreductase. Thus, C. pinatubonensis JMP134 contains a main pathway and a contingent pathway for sulfide oxidation.IMPORTANCE We establish a new pathway of sulfide oxidation with thiosulfate as a key intermediate in Cupriavidus pinatubonensis JMP134. The bacterium mainly oxidizes sulfide by using sulfide:quinone oxidoreductase, persulfide dioxygenase, and the Sox system with thiosulfate as a key intermediate. Although the purified and reconstituted Sox system oxidizes sulfide, its rate of sulfide oxidation in C. pinatubonensis JMP134 is too low to be physiologically relevant. The findings reveal how these sulfur-oxidizing enzymes participate in sulfide oxidation in a single bacterium.

Liquid-Phase Oxidation of Hydrogen Sulfide in Oil with Molecular Oxygen in the Presence of an Ammonia Solution of Cobalt Phthalocyanine

The results of studying the dependence of the reaction rate of the hydrogen sulfide oxidation in oil with molecular oxygen in the presence of an ammonia solution of cobalt phthalocyanine on the process temperature, the consumption of the catalyst complex, and the concentration of cobalt phthalocyanine in the catalyst complex are reported. It was shown that the rate of the hydrogen sulfide oxidation strongly depends on the consumption of the catalyst complex and the concentration of cobalt phthalocyanine in the catalyst complex. Based on experimental data, a mathematical model was derived that describes the hydrogen sulfide oxidation with satisfactory accuracy. The calculated values obtained using this mathematical model are in good agreement with the experimental data.

Scale dependence of effective geochemical rates in weathering mine waste rock

Hydrogeochemical models for the prediction of drainage quality from full-scale mine waste-rock piles are often parameterized using data from small-scale laboratory or field experiments of short duration. Yet, many model parameters and processes (e.g., sulfide-oxidation rates) vary strongly with the spatiotemporal dimensions of the experiment: the “upscaling” of prediction models remains a critical challenge for mine-waste management worldwide. Here, we investigate scale dependence in laboratory and field experiments that spanned orders-of-magnitude in size (i.e. 2 kg to 100,000 kg) at the Antamina mine in Peru. Normalized drainage mass loading rates systematically decreased with increasing scale, irrespective of waste-rock type. A process-based reactive-transport model was used to simulate observed rates and reproduce the geochemical composition of drainage across scales. Long-term trends in drainage quality could be quantitatively reproduced when the model was parameterized with mostly scale- and experiment-specific measured bulk properties or literature values, leaving geochemical rate coefficients the sole calibrated model parameters. Analysis of these fitted parameters revealed that the scale dependence of geochemical rates was largely explained by reactive mineral surface area. This work demonstrates that practical drainage quality predictions for full-scale waste-rock piles can be established from readily available bulk parameters determined at multiple scales.

The stimulating metabolic mechanisms response to sulfide and oxygen in typical heterotrophic sulfide-oxidizing nitrate-reducing bacteria Pseudomonas C27

Micro-aeration is an effective tool that helps integrated autotrophic and heterotrophic denitrification process to withstand high sulfide concentration by making heterotrophic sulfide-oxidizing nitrate-reducing bacteria (h-soNRB) prevail. For further understanding of the dominance of h-soNRB, Pseudomonas C27 was selected as the typical bacterium and its metabolic characteristics responding to sulfide and oxygen stimulation were studied. Under high sulfide concentration condition, addition of trace oxygen led to a two-stage sulfide oxidation process, and sulfide oxidation rate in the first stage was 1.4 times more than that under anaerobic condition. According to transcriptome analysis, the pdo gene significantly up-regulated 2.36 and 2.57 times with and without oxygen under stimulation of high sulfide concentration. Additionally, two possible enhanced sulfide removal pathways coping with high sulfide concentration, namely sqr-cysI-gpx-gor-glpE and cysK-gshA-gshB-pdo-glpE, caused by oxygen were proposed in Pseudomonas C27. These findings provide a theoretical basis for locating high-efficiency sulfur oxidase in h-soNRB.

Quantification of sulphide oxidation rates in marine sediment

The marine sulphur cycle is driven by the reduction of sulphate to sulphide coupled to microbial decomposition of organic matter. The sulphide produced by sulphate reduction may either react with Fe or organic matter to be buried as pyrite or organic sulphur, respectively; or may be oxidised through different pathways and intermediates. The amount of sulphide that is oxidised in marine sediments is not well constrained, yet oxidative sulphur cycling has critical implications for hypoxic coastal waters and oxygen minimum zones, carbon mineralisation, microbial metabolism and the interpretation of ancient and modern stable isotope signatures. Here, we present an experimental method to directly determine sulphide oxidation rates in undiluted marine sediment incubations. We find that sulphide oxidation rates in the top two centimetres of organic-rich coastal sediments were greater than rates of sulphide production through sulphate reduction and calculate that in the top 6 centimetres, up to 92 % of sulphide produced during sulphate reduction was reoxidised. The rates decreased steeply with depth, however, and sulphide oxidation to sulphate could no longer be quantified 10 cm below the seafloor. Fe oxides were the primary oxidant for sulphide and the sulphide oxidation rate was related to the amount and reactivity of the Fe minerals. These results provide important insights into the magnitude and processes of the sulphur cycle in marine sediments.

Dissolved Inorganic Carbon Pump in Methane-Charged Shallow Marine Sediments: State of the Art and New Model Perspectives

Methane transport from subsurface reservoirs to shallow marine sediment is characterized by unique biogeochemical interactions significant for ocean chemistry. Sulfate-Methane Transition Zone (SMTZ) is an important diagenetic front in the sediment column that quantitatively consumes the diffusive methane fluxes from deep methanogenic sources toward shallow marine sediments via sulfate-driven anaerobic oxidation of methane (AOM). Recent global compilation from diffusion-controlled marine settings suggests methane from below and sulfate from above fluxing into the SMTZ at an estimated rate of 3.8 Tmol yr-1 and 5.3 Tmol yr-1 respectively, and wider estimate for methane flux ranges from 1—19 Tmol yr-1. AOM converts the methane carbon to dissolved inorganic carbon (DIC) at the SMTZ. Organoclastic sulfate reduction (OSR) and deep-DIC fluxes from methanogenic zones contribute additional DIC to the shallow sediments. Here, we provide a quantification of 8.7 Tmol yr-1 DIC entering the methane-charged shallow sediments due to AOM, OSR, and the deep-DIC flux (range 6.4–10.2 Tmol yr-1). Of this total DIC pool, an estimated 6.5 Tmol yr-1 flows toward the water column (range: 3.2–9.2 Tmol yr-1), and 1.7 Tmol yr-1 enters the authigenic carbonate phases (range: 0.6–3.6 Tmol yr-1). This summary highlights that carbonate authigenesis in settings dominated by diffusive methane fluxes is a significant component of marine carbon burial, comparable to ~15% of carbonate accumulation on continental shelves and in the abyssal ocean, respectively. Further, the DIC outflux through the SMTZ is comparable to ~20% of global riverine DIC flux to oceans. This DIC outflux will contribute alkalinity or CO2 in different proportions to the water column, depending on the rates of authigenic carbonate precipitation and sulfide oxidation and will significantly impact ocean chemistry and potentially atmospheric CO2. Settings with substantial carbonate precipitation and sulfide oxidation at present are contributing CO2 and thus to ocean acidification. Our synthesis emphasizes the importance of SMTZ as not only a methane sink but also an important diagenetic front for global DIC cycling. We further underscore the need to incorporate a DIC pump in methane-charged shallow marine sediments to models for coastal and geologic carbon cycling.

Manganese oxide-based porous electrodes for rapid and selective (electro)catalytic removal and recovery of sulfide from wastewater

Sulfide and its removal is a major concern in wastewater treatment as it represents a threat to human health and the structural integrity of the water distribution system. In this study, we demonstrated for the first time an exceptional performance of manganese oxide-coated graphite felt (GF-MnxOy) electrodes for selective sulfide oxidation to sulfur. Oxidation state, loading, morphology and crystallinity of MnxOy coating was tuned using electrodeposition synthesis method to enable an efficient and selective sulfide oxidation to sulfur. Excellent (electro)catalytic activity of GF-MnxOy yielded up to 25-fold increase in sulfide removal rates compared to pristine GF, both in the open circuit (OC, no applied potential) and under anodic polarization at 0.4 V vs Standard Hydrogen Electrode (SHE). Although anodic polarization did not further enhance sulfide oxidation rate compared to OC, it enabled a continuous re-oxidation of the reduced MnxOy coating after its reaction with sulfide. Thus, restoring of the catalytic properties of MnxOy coating enabled higher sulfide removal rates compared with the OC experiment. The formed elemental sulfur remained at the surface of GF-MnxOy leading to a gradual electrode passivation. The deposited sulfur was successfully dissolved by reversing the polarity of the GF-MnxOy electrode to -0.8 V vs SHE. However, full electrode recovery and restoring of the initial sulfide removal rates could not be achieved as cathodic polarization at -0.8 V vs SHE during longer time (>3 hours) required to remove S0 also caused a partial dissolution of the MnxOy coating. (Electro)catalytic sulfide removal was somewhat decreased in real sewage (2.42 ± 0.02 h-1 vs 0.93 ± 0.15 h-1 in NaNO3 supporting electrolyte and real sewage, respectively). The selectivity of the process towards deposition of elemental sulfur was decreased in real sewage due to partial production of colloidal sulfur, which was presumably caused by diffusion limitation imposed by presence of other ions. Due to lesser extend of GF-Mn2O3 electrode passivation in real sewage, sulfide removal rates remained stable over six subsequent application cycles. In summary, MnxOy-based electrodes demonstrated exceptional (electro)catalytic activity and selectivity for sulfide oxidation to sulfur and thus its complete separation from water. Upscaling of the proposed electrochemical system and its application for the treatment of complex wastewater streams requires further efforts to maintain the selectivity towards deposited sulfur as a final product and allow its complete recovery.

Glacial influence on the iron and sulfur cycles in Arctic fjord sediments (Svalbard)

Arctic fjord sediments of Svalbard receive terrestrial material from glacial runoff and organic matter from marine primary productivity. Organic carbon mineralization proceeds primarily through sulfate and iron reduction in the fjord sediment. The ongoing retreat of glaciers in the high Arctic is altering the input of glacial material to the fjords, with unknown consequences for the iron and sulfur cycles in the fjord sediments. We measured sulfate reduction rates in sediment cores and analyzed porewater geochemistry, then compared these results to long-term sediment incubations to determine the rates of iron reduction and sulfide oxidation in three glacially influenced fjords on the west coast of Spitsbergen, Svalbard. Despite an abundance of glacially-sourced Fe(III)-oxide minerals, active sulfate reduction took place throughout the sediment. Analyses of the sulfur and oxygen isotopic composition of porewater sulfate and sulfate concentrations suggest that sulfide produced from biological sulfate reduction is reoxidized to sulfate. Long-term sediment incubations indicated sulfide oxidation at all three stations. The rate of sulfide oxidation was controlled by both the rate of sulfate reduction and the quantity and reactivity of Fe(III)-oxides. In our experimental incubations, we detected a decrease in Fe(III) content of the 0.5 M HCl and ascorbate-extractable fractions, but not in the 6 M HCl fraction, indicating that the highly reactive Fe(III) fraction is utilized by microorganisms and serves as the oxidant for sulfide oxidation. Our results show that sulfide oxidation in glacially-influenced fjord sediments is a wide-spread geochemical process. Further warming will drive glacial retreat onto land, where sediment-laden glacial meltwater will be altered during flow through proglacial streams and lakes before entering the marine environment. Fjord sediments will likely become more sulfidic, as glaciers deliver less particulate, highly-reactive metal oxides to the marine environment.

The Effect of Particle Size on Mine Waste Sulfide Oxidation Rates and Conceptual Treatment Costs

Acid and metalliferous drainage (AMD) oxidation reaction rates were determined using oxygen consumption rates in a high sulfur overburden rock from the Australian Latrobe Valley coal provinces, and a mid to low range sulfur waste rock from a porphyry copper deposit in Papua, New Guinea. Nine grain sizes were tested, ranging from material retained by a 0.038 mm sieve through to a 40 mm sieve. Oxygen consumption rates in sealed cells were measured to establish pyrite oxidation rates (POR) in each sample. The oxygen consumption rates displayed a strong exponential reaction correlation with particle size for the material. The POR was found to range from 0.28 to 10.90 wt%/year FeS2 for the materials tested. A relationship between particle size and POR was established for comparative purposes. The smaller grind sizes included in this study extend the AMD/POR particle size data set available in the literature and will assist with geochemical engineering for designing tailings storage facilities. The potential economic and mine design ramifications of additional reactivity of fine mine materials is assessed and discussed using a unit cost framework for applying neutralizing materials.

Vertical stratification and stability of biogeochemical processes in the deep saline waters of Lake Vanda, Antarctica

AbstractLake Vanda is a permanently ice‐covered lake in the McMurdo Dry Valleys of Antarctica. Its bottom waters remain stratified year‐round because of a strong salinity‐driven density gradient. We have assessed spatial patterns in and relationships between major biogeochemical processes in the water column of Lake Vanda. Samples were collected in the austral summers of 2008 and 2011 to measure concentrations of metabolites associated with a suite of biogeochemical processes across the deep salinity gradient. The shapes of the resulting geochemical profiles were consistent between 2008 and 2011. Metabolite production and consumption rates were estimated using a reactive transport model based on the assumption that vertical diffusion was the only active physical transport process. We validated this model for nitrification by using stable isotope incubations to show that this process was only active at depths predicted by the model. No nitrification activity was observed at 68 m depth in spite of overlapping oxygen and ammonium gradients. We attribute this lack of activity to the competitive inhibition of ammonia monooxygenase by methane. Net nitrous oxide and nitrate consumption were observed in the oxic water column, providing evidence of aerobic denitrification. The depth of maximum net oxygen production did not coincide with the deep chlorophyll maxima (at 59.3, 63, and 68.2 m) measured in the same profile. Finally, the integrated sulfide oxidation rate was high compared with other oxidation processes, indicating that sulfide was an important electron donor for the water column microbial community.

Prevention of sulfide oxidation in waste rock by the addition of lime kiln dust

During the operation of a mine, waste rock is often deposited in heaps and usually left under ambient conditions allowing sulfides to oxidize. To focus on waste rock management for preventing acid rock drainage (ARD) formation rather than ARD treatment could avoid its generation and reduce lime consumption, costs, and sludge treatment. Leachates from 10 L laboratory test cells containing sulfide-rich (> 60% pyrite) waste rock with and without the addition of lime kiln dust (LKD) (5 wt.%) were compared to each other to evaluate the LKD’s ability to maintain near neutral pH and reduce the sulfide oxidation. Leaching of solely waste rock generated an acidic leachate (pH < 1.3) with high concentrations of As (21 mg/L), Cu (20 mg/L), Fe (18 g/L), Mn (45 mg/L), Pb (856 μg/L), Sb (967 μg/L), S (17 g/L), and Zn (23 mg/L). Conversely, the addition of 5 wt.% LKD generated and maintained a near neutral pH along with decreasing of metal and metalloid concentrations by more than 99.9%. Decreased concentrations were most pronounced for As, Cu, Pb, and Zn while S was relatively high (100 mg/L) but decreasing throughout the time of leaching. The results from sequential extraction combined with element release, geochemical calculations, and Raman analysis suggest that S concentrations decreased due to decreasing sulfide oxidation rate, which led to gypsum dissolution. The result from this study shows that a limited amount of LKD, corresponding to 4% of the net neutralizing potential of the waste rock, can prevent the acceleration of sulfide oxidation and subsequent release of sulfate, metals, and metalloids but the quantity and long-term stability of secondary minerals formed needs to be evaluated and understood before this method can be applied at a larger scale.

Development and validation of a physiologically based kinetic model for starting up and operation of the biological gas desulfurization process under haloalkaline conditions

Hydrogen sulfide is a toxic and corrosive gas that must be removed from gaseous hydrocarbon streams prior to combustion. This paper describes a gas biodesulfurization process where sulfur-oxidizing bacteria (SOB) facilitate sulfide conversion to both sulfur and sulfate. In order to optimize the formation of sulfur, it is crucial to understand the relations between the SOB microbial composition, kinetics of biological and abiotic sulfide oxidation and the effects on the biodesulfurization process efficiency. Hence, a physiologically based kinetic model was developed for four different inocula. The resulting model can be used as a tool to evaluate biodesulfurization process performance. The model relies on a ratio of two key enzymes involved in the sulfide oxidation process, i.e., flavocytochrome c and sulfide-quinone oxidoreductase (FCC and SQR). The model was calibrated by measuring biological sulfide oxidation rates for different inocula obtained from four full-scale biodesulfurization installations fed with gases from various industries. Experimentally obtained biological sulfide oxidation rates showed dissimilarities between the tested biomasses which could be explained by assuming distinctions in the key-enzyme ratios. Hence, we introduce a new model parameter α to whereby α describes the ratio between the relative expression levels of FCC and SQR enzymes. Our experiments show that sulfur production is the highest at low α values.

Experimental determination of pyrite and molybdenite oxidation kinetics at nanomolar oxygen concentrations

Constraining the rate at which sulfide minerals undergo oxidative weathering at low atmospheric O2 is crucial for understanding the evolution of the Archean and Proterozoic biosphere when O2 was a trace atmospheric gas. However, recent studies attempting to constrain sulfide oxidation rates, atmospheric O2 sinks, and trace metal delivery to seawater under Archean conditions are limited by the need to extrapolate from experimental pyrite oxidation kinetics determined at much higher O2 levels. Extrapolation of those data sets to Archean levels of O2 (<10−5 present atmospheric level or PAL prior to 2.4 Ga) leads to more than an order of magnitude uncertainty in sulfide mineral oxidation rates, hampering efforts to quantify oxidative weathering under early Earth conditions. To quantify sulfide oxidation kinetics at low pO2, we conducted aqueous pyrite and molybdenite oxidation experiments at ∼2–1200 nM dissolved O2 and pH values 1.83, 5.08, and 8.58. Our experimental approach used LUMOS O2 sensors to extend the pO2 range explored by oxidation experiments down to 10−5 PAL pO2, the limit of the sensors, which is up to three orders of magnitude lower than the pO2 range explored in previous work. From these experiments, we use 28 independent rate measurements to derive a new rate law for the oxidation of pyrite as a function of pO2: rpyrite=10-8.83(±0.27)O20.50±0.04H+-0.25±0.02, Where rpyrite is the rate of oxidation in mol/m2 sec, and the activities of dissolved [O2] and [H+] are in (mol/L). Our results most closely match the previous rate law presented by Williamson and Rimstidt (1994), but indicate a stronger pH dependence than previous studies. We also present the first kinetic rate law for molybdenite oxidation at low O2, based on 13 independent rate measurements: rmolybdenite=10-8.3(±2.3)O20.5±0.3, Where rmolybdenite is the rate of oxidation in mol/m2 sec, and the activity of dissolved [O2] is in (mol/L). We find molybdenite oxidation to be nearly as rapid as pyrite oxidation even at low concentrations of dissolved O2 (equivalent to <10−5 PAL pO2), in contrast to previous work which argued for a threshold effect for molybdenite oxidation. Both pyrite and molybdenite oxidation kinetics exhibit a constant half-order dependence on dissolved O2 down to nanomolar levels of O2. We show that this behavior is best explained by a reaction mechanism in which O2 undergoes dissociative adsorption to the sulfide mineral surface. This mechanism helps to resolve major uncertainties regarding the reaction mechanism of O2 with pyrite and molybdenite mineral surfaces and provides a strong theoretical basis for the robust extrapolation of present results to higher and lower O2 concentrations.

Determination of the available acid-generating potential of waste rock, part II: Waste management involvement

Open-pit mining operations often produce large amounts of waste rock that are characterized by large particle size distributions (PSD). Waste rock are normally deposited in surface piles that contain grains varying from a few microns to meters in size. Furthermore, the mineralogical and textural properties of the waste rock are influenced by their PSD. The diameter of physical locking of sulfides (DPLS) is a newly suggested parameter that was defined using an automated mineralogy system to separate waste rock according to their geochemical reactivity. Three lithologies (A, B, and C) were extracted from an open-pit gold mine and their geochemical behaviors, with respect to degree of sulfide liberation, were evaluated using column kinetic tests. The main results of this study showed that fine fractions of the studied waste rock were more sulfidic compared to coarse fractions. Moreover, sulfide liberation was negligible for fractions >2.4 mm. Consequently, 2.4 mm was defined as the critical diameter of sulfide reactivity for the three studied waste rock. Column kinetic tests were used to confirm this hypothesis and to assess the geochemical behavior of the three lithologies. Geochemical analyses of leachates from the column tests showed that pH values remained between 7 and 8 and the instantaneous concentrations of metals such as iron (Fe) and zinc (Zn) were below environmental limits over the entire test duration (543 days). Considering sample reactivity, the data showed that the fine fractions primarily control the geochemical behavior of total samples. Sulfide oxidation rates were high for fractions <2.4 mm, whereas they were negligible for fractions >2.4 mm; total samples showed intermediate rates. For example, in lithology B, pyrite oxidation rates were 12.46 μmol/kg/day, 2.43 μmol/kg/day, and 0.27 μmol/kg/day for the fine fraction (<2.4 mm), total sample (<5 cm), and coarse fraction (>2.4 mm) respectively. Sulfide and carbonate contents and their liberation were defined as key factors controlling the geochemical behavior of the studied waste rock, which was confirmed by the correlation factor between calcium leaching vs. carbonate liberation and between sulfur leaching vs. sulfide liberation. The coarse, unreactive fraction (>2.4 mm) comprised a high proportion of the total sample weight (up to 90 wt. %). Screening waste rock, after blasting, according to the critical diameter of sulfide reactivity could be an efficient technique for global waste rock management that will reduce the economic costs related to waste rock pile reclamation.

Final products and kinetics of biochemical and chemical sulfide oxidation under microaerobic conditions.

Hydrogen sulfide is a toxic and usually undesirable by-product of the anaerobic treatment of sulfate-containing wastewater. It can be removed through microaeration, a simple and cost-effective method involving the application of oxygen-limiting conditions (i.e., dissolved oxygen below 0.1 mg L-1). However, the exact transformation pathways of sulfide under microaerobic conditions are still unclear. In this paper, batch experiments were performed to study biochemical and chemical sulfide oxidation under microaerobic conditions. The biochemical experiments were conducted using a strain of Sulfuricurvum kujiense. Under microaerobic conditions, the biochemical sulfide oxidation rate (in mg S L-1 d-1) was approximately 2.5 times faster than the chemical sulfide oxidation rate. Elemental sulfur was the major end-product of both biochemical and chemical sulfide oxidation. During biochemical sulfide oxidation elemental sulfur was in the form of white flakes, while during chemical sulfide oxidation elemental sulfur created a white suspension. Moreover, a mathematical model describing biochemical and chemical sulfide oxidation was developed and calibrated by the experimental results.