Oxidation Of Hydrogen Sulfide Research Articles

Acceleration of Diffusion in Ab Initio Nanoreactor Molecular Dynamics and Application to Hydrogen Sulfide Oxidation.

The computational description of chemical reactivity can become extremely complex when multiple different reaction products and intermediates come into play, forming a chemical reaction network. Therefore, computational methods for the automated construction of chemical reaction networks have been developed in the last decades. One of these methods, ab initio nanoreactor molecular dynamics (NMD), is based on external forces enhancing reactivity by e.g., periodically compressing the system and allowing it to relax. However, during the relaxation process, a significant simulation time is required to allow energy to dissipate and molecules to diffuse, making this part of the NMD simulation computationally intensive. This work aims to improve NMD by accelerating the diffusion process in the relaxation phase. We systematically investigate the speedup of reaction discovery gained by diffusion acceleration, leading to a factor of up to 28 in discovery frequency. Diffusion-accelerated nanoreactor molecular dynamics (DA-NMD) is then used to construct a reaction network of hydrogen sulfide oxidation under atmospheric conditions, where reactions are automatically detected by a change in the bond order and bond distance. A reaction network of 108 molecular species and 399 elementary reactions was constructed starting from hydrogen sulfide, hydroxy radicals, and molecular oxygen covering a broad variety of sulfur-oxygen chemistry and oxidation states of the sulfur atom ranging from -II to +VI.

Hydrogen sulfide oxidation by sulfide:quinone reductase supports mitochondrial ATP production when complex I is inhibited

Hydrogen sulfide oxidation by sulfide:quinone reductase supports mitochondrial ATP production when complex I is inhibited

Reaction of peroxynitrite with thiols, hydrogen sulfide and persulfides

Three decades of research on the biochemistry of peroxynitrite (ONOOH/ONOO−) have established that this stealthy oxidant is formed in biological systems, and that its main targets are carbon dioxide (CO2), metalloproteins and thiols (RSH). Peroxynitrous acid reacts directly with thiols (precisely, with thiolates, RS−), forming sulfenic acids (RSOH). In addition, the free radicals derived from peroxynitrite, mainly carbonate radical anion (CO3•−) and nitrogen dioxide (NO2•) formed from the reaction of peroxynitrite anion with CO2, oxidize thiols to thiyl radicals (RS•). These two pathways are under kinetic competition. The primary products of thiol oxidation can follow different decay routes; sulfenic acids usually react with other thiols forming disulfides, while thiyl radicals can react with oxygen, with other thiols and with other reductants such as ascorbic acid. Peroxynitrite is also able to oxidize hydrogen sulfide (H2S/HS−) and persulfides (RSSH/RSS−). Among the different biological thiols, peroxiredoxins stand out as main peroxynitrite reductases due to their very high rate constants of reaction with peroxynitrite together with their abundance. Rooted in kinetic concepts, evidence is emerging for the role of peroxiredoxins in peroxynitrite detoxification, with potential implications in diseases in which peroxynitrite is involved.

Reactive adsorption and catalytic oxidation of gaseous hydrogen sulfide using a prototype air purifier built with bismuth-doped titanium dioxide

A prototype air purifier (AP) module has been constructed using bismuth-doped titanium dioxide (Bix-P25: x(%) as Bi/Ti molar ratios of 1.1, 2.1, 3.3, 5.3, and 8.7). The reactive adsorption property of Bix-P25 materials is evaluated against H2S gas at a recirculation rate of 160 L min−1 in a 17 L closed chamber. The AP (Bi5.3-P25) exhibits superior performance against 10 ppm H2S in dry air under dark conditions (i.e., without light irradiation), with a removal efficiency (XH2S)= 99% in 5 mins, reaction kinetic rate (r (at X = 10%))= 7.3 mmol h−1g−1, and partition coefficient= 0.18 mol kg−1 Pa−1. As such, its superiority is evident over the reference AP (P25) filter with XH2S < 10%. The clean air delivery rate (CADR) of AP (Bi5.3-P25) increases noticeably from 9.9 to 17.8 L min−1 with increasing relative humidity (RH) from 0 to 80%, respectively. In contrast, the CADR decreases from 9.9 to 5.8 L min−1 as the H2S increases from 10 to 20 ppm. According to density functional theory (DFT), the presence of H2O vapor enhances the hydroxylation of Bix-P25 surface to promote H2S mineralization through the formation of TiS3 (i.e., thermodynamic reaction of S atom with the catalytic surface). Complete removal of H2S on the Bi5.3-P25 surface is also confirmed consistently through gas chromatography-mass spectrometry (GC-MS), in-situ diffuse reflection infrared spectroscopy (in-situ DRIFTS), and elemental analysis (EA). This work represents the first utilization of Bix-P25 materials fabricated on an AP platform toward the desulfurization of H2S at room temperature (RT). The practical utility of Bix-P25 is overall validated by its eminent role in reactive adsorption and catalytic oxidation (RACO) of H2S from the air.

Single Amino Acids as Sole Nitrogen Source for the Production of Lipids and Coenzyme Q by Thraustochytrium sp. RT2316-16.

This work analyzes the production of total lipids and the content of CoQ9 and CoQ10 in the biomass of Thraustochytrium sp. RT2316-16 grown in media containing a single amino acid at a concentration of 1 g L-1 as the sole nitrogen source; glucose (5 g L-1) was used as the carbon source. Biomass concentration and the content of total lipids and CoQ were determined as a function of the incubation time; ten amino acids were evaluated. The final concentration of the total biomass was found to be between 2.2 ± 0.1 (aspartate) and 3.9 ± 0.1 g L-1 (glutamate). The biomass grown in media containing glutamate, serine or phenylalanine reached a content of total lipids higher than 20% of the cell dry weight (DW) after 72, 60 and 72 h of incubation, respectively. The highest contents of CoQ9 (39.0 ± 0.7 µg g-1 DW) and CoQ10 (167.4 ± 3.4 mg g-1 DW) in the biomass of the thraustochytrid were obtained when glutamate and cysteine were used as the nitrogen source, respectively. Fatty acid oxidation, which decreased the total lipid content during the first 12 h of incubation, and the oxidation of hydrogen sulfide when cysteine was the nitrogen source, might be related to the content of CoQ10 in the biomass of the thraustochytrid.

Oxygen-assisted catalytic oxidation of hydrogen sulfide in crude oil

Oxygen-assisted catalytic oxidation of hydrogen sulfide in crude oil

Conjugated organic ligand enhancing chelating iron-based deep eutectic solvents for catalytic oxidation of hydrogen sulfide

In recent years, non-aqueous iron-based ionic liquid (Fe-IL) desulfurization technology has garnered widespread attention for its avoidance of the excessive oxidation of hydrogen sulfide in aqueous systems. However, the hydrogen bond network in ionic liquids restricts molecular motion, resulting in poor reactivity of Fe-IL. In this work, the chelated Fe-ILs (BmimFeEDTA and BZKFeEDTA) were synthesized and dissolved in PEG200 to construct chelated iron-based deep eutectic solvents (Bm-Fe-DES, BZK-Fe-DES). 1,3-Dimethyl-2-imidazolidinone (DMI), as a conjugated active ligand, was introduced to enhance the catalytic oxidation of H2S by the two Fe-DESs. After five cycles, both Fe-DES/DMI systems exhibited excellent desulfurization and regeneration performance. POM and FT-IR analyses revealed that BZKFeEDTA with a long carbon chain exhibited a more ordered spatial structure, which was more conducive to the cycling of Fe(III) and Fe(II). CV, Py-IR, bond length analysis, and LUMO-HOMO energy gap indicated that DMI weakens the limitation of EDTA to Fe(III) by coordinating with Fe(III), which significantly enhances the catalytic activity of Fe-DES. UV–vis and CPA analysis demonstrated the transfer of π electrons from DMI to the EDTA ligand, facilitating the loss of electrons from [Fe(II)EDTA]2-. Therefore, the two types of chelated iron-based deep eutectic solvents prepared in this work have great application potential in the field of hydrogen sulfide catalytic oxidation.

Modeling and simulation of a novel chemical process for clean hydrogen and power generation

The present work aims to develop a novel chemical process for clean hydrogen and power production and simulate it accordingly through a unique thermodynamic equilibrium model. This particular process is based on a partial oxidation of hydrogen sulfide (H2S) at superadiabatic conditions to study its respective chemical products. The simulation of superadiabatic partial oxidation of H2S is developed through the present model for the first time in the Aspen Plus. The process is further studied by varying different operating variables with an overall goal of optimizing the H2S conversion into hydrogen. The developed model predicts a satisfactory H2 production flow rate coupled with a low-sulfur dioxide (SO2) output within the superadiabatic partial oxidation regime at an operating pressure below 0.5 bar. The H2S conversion into H2 is then found to be 23.48 % at 0.25 bar. The overall energy and exergy efficiencies of the system are found to be 87.51 % and 70.08 % respectively. The dissociation of H2S in the presence of stoichiometric air results in elemental sulfur and hydrogen production rates of 0.0019 kg/s and 0.0012 kg/s, respectively.

Detection of Sulfur Oxidizing Bacteria to Oxidize Hydrogen Sulfide in Biogas from Pig Farm by NGS and DNA Microarray Technique

A high concentration of hydrogen sulfide (H2S) released from pig farming is one of the major environmental problems affecting surrounding communities. In modern pig farms, the bioscrubber is used to eliminate H2S, which is found to be driven mainly by the sulfur-oxidizing bacteria (SOB) community. Therefore, in this study, molecular biology techniques such as next-generation sequencing (NGS) and DNA microarray are proposed to study the linkage between enzyme activity and the abundance of the SOB community. The starting sludge (SFP1) and recirculating sludge (SFP2) samples were collected from the bioscrubber reactor in the pig farm. The abundance of microbial populations between the two sampling sites was considered together with the gene expression results of both soxABXYZ and fccAB. Based on the NGS analysis, the members of phylum Proteobacteria such as Halothiobacillus, Acidithiobacillus, Thiothrix, Novosphingobium, Sulfuricurvum, Sulfurovum, Sulfurimonas, Acinetobacter, Thiobacillus, Magnetospirillum, Arcobacter, and Paracoccus were predominantly found in SFP2. The presence of Cyanobacteria in SFP pig farms is associated with increased biogas yields. The microarray results showed that the expression of soxAXBYZ and fccAB genes involved in the oxidation of sulfide to sulfate was increased in Halothiobacillus, Paracoccus, Acidithiobacillus, Magnetospirillum, Sphingobium, Thiobacillus, Sulfuricurvum, Sulfuricurvum, Arcobacter, and Thiothrix. Both NGS and DNA microarray data supported the functional roles of SOB in odor elimination and the oxidation of H2S through the function of soxABXYZ and fccAB. The results also identified the key microbes for H2S odor treatment, which can be utilized to monitor the stability of biological treatment systems and the toxicity of sulfide minerals by oxidation.

Authigenic carbonate and native sulfur formation in Messinian (upper Miocene) marine sediments: Sedimentological, petrographical and geochemical constraints

Carbonate concretions accompanied by elemental sulfur were found in an early Messinian (Late Miocene) marine succession of NW Italy. The rocks were studied with an integrated approach including sedimentological, petrographical, stable isotope (carbon, oxygen, and multiple sulfur isotopes), and lipid biomarker analyses. Unlike other examples from Messinian strata of the Mediterranean area, the studied carbonate and sulfur concretions did not derive from the diagenetic replacement of sulfate minerals. Three lithofacies were distinguished: a) laminated lithofacies representing aphotic carbonate stromatolites enclosing fossils of filamentous sulfide-oxidizing bacteria; b) brecciated lithofacies deriving from the brecciation of carbonate stromatolites by mud injections; c) sulfur-bearing lithofacies deriving from the precipitation of thin laminae of elemental sulfur at or close to the sediment-water interface. The carbon and oxygen stable isotope composition of authigenic carbonate minerals and lipid biomarkers indicate that the initial formation of the laminated lithofacies was favored by organoclastic sulfate reduction in the shallow subsurface close to the sediment-water interface, producing sulfide that sustained dense microbial mats of sulfide-oxidizing bacteria at the seafloor. Calcification of the mats and consequent formation of stromatolites were possibly favored by nitrate-driven sulfide oxidation at the seafloor. The subsequent brecciation of the stromatolites was apparently the consequence of sulfate-driven anaerobic oxidation of methane (SD-AOM) in an underlying sulfate-methane transition zone (SMTZ). Focused fluid flow from below, possibly resulting from destabilization of gas hydrates, was not only responsible for the brecciation of the stromatolites, but also for the delivery of bicarbonate ions and the consequent precipitation of additional, 13C-depleted calcite (δ13C values as low as −52‰). Along with bicarbonate, also hydrogen sulfide was produced by SD-AOM at the SMTZ and was transported upwards. The oxidation of hydrogen sulfide at or close to the seafloor promoted the formation of elemental sulfur characterized by δ34S values and Δ33S values close to coeval seawater sulfate.

Insight into the effective electrocatalytic sulfide removal from aqueous solutions using surface oxidized stainless-steel anode and its desulfurization mechanism

The electrochemical oxidation of hydrogen sulfide (H2S) has shown its potential for the real application of H2S emission control in wastewater treatment. In this study, a surface corrosion treatment of stainless steel (SS) was optimized by regulate Ni content in the oxide film on the SS AISI 304 surface for sulfide removal. The X-ray photoelectron spectroscopy and linear sweeping voltammetry results indicated a higher Ni content in the oxide film of surface-oxidized stainless steel (SOSS) attributed to a higher sulfide removal potential. Sulfide removal experiment results showed that SS-150 (with 150 s anodic pretreatment) anodes achieved the highest Ni content of 69% with the best sulfide removal efficiency, i.e., 97% within 48 h, which increased by 20% compared to the untreated SS. This study also demonstrated a strategy for in situ removal of deposited sulfur on the anodes by cathodic treatment at −0.38 V vs. RHE to alleviate the common issue of sulfur passivation. Density functional theory (DFT) calculation revealed that NiOOH was the major active species in SS-150 oxide film for a faster sulfide removal rate. The study developed a SS surface modification process for Ni content regulation that contributed to better sulfide removal efficiency.

Engineering bifunctional sites in covalent polymers for boosting photocatalytic H2S oxidation

The development of catalyst for photocatalytic hydrogen sulfide (H2S) oxidation with excellent efficiency and regeneration properties is a significant challenge. Herein, the pyridine units as bifunctional sites are incorporated in covalent polymers (CPs) by CN coupling reaction, which exhibit photocatalytic H2S selective oxidation to sulfur conversion (95 %) under visible light in a continuous flow system, more than twice that of the pristine sample (40 %). Meanwhile, the photocatalytic H2S conversion rate had a linear function relationship with pyridinic N content, demonstrating the substantial role of pyridine in photocatalytic H2S oxidation process. According to experimental results, the pyridine unit not only acted as the structural base site to improve the H2S chemisorption, but also served as electron withdrawing unit to construct electron donor-acceptor (D-A) structure with benzene, which optimized the light absorption, charge separation and migration. In addition, series in-situ measurements and electron density difference simulations revealed the significant role of electron D-A structure in H2S adsorption and activation process. By exploring the effect of pyridine unit in CPs on H2S conversion process, this work provides a new idea for the subsequent study of photocatalytic H2S oxidation.

Sulfide catabolism in hibernation and neuroprotection

The mammalian brain is exquisitely vulnerable to lack of oxygen. However, the mechanism underlying the brain's sensitivity to hypoxia is incompletely understood. In this narrative review, we present a case for sulfide catabolism as a key defense mechanism of the brain against acute oxygen shortage. We will examine literature on the role of sulfide in hypoxia/ischemia, deep hibernation, and leigh syndrome patients, and present our recent data that support the neuroprotective effects of sulfide catabolism and persulfide production. When oxygen levels become low, hydrogen sulfide (H2S) accumulates in brain cells and impairs the ability of these cells to use the remaining, available oxygen to produce energy. In recent studies, we found that hibernating ground squirrels, which can withstand very low levels of oxygen, have high levels of sulfide:quinone oxidoreductase (SQOR) and the capacity to catabolize hydrogen sulfide in the brain. Silencing SQOR increased the sensitivity of the brain of squirrels and mice to hypoxia, whereas neuron-specific SQOR expression prevented hypoxia-induced sulfide accumulation, bioenergetic failure, and ischemic brain injury in mice. Excluding SQOR from mitochondria increased sensitivity to hypoxia not only in the brain but also in heart and liver. Pharmacological agents that scavenge sulfide and/or increase persulfide maintained mitochondrial respiration in hypoxic neurons and made mice resistant to ischemic injury to the brain or spinal cord. Drugs that oxidize hydrogen sulfide and/or increase persulfide may prove to be an effective approach to the treatment of patients experiencing brain injury caused by oxygen deprivation or mitochondrial dysfunction.

Oxidation of hydrogen sulfide and CO2 mixtures: Laser-based multi-speciation and kinetic modeling

Hydrogen sulfide (H2S), encountered in sour natural gas and in fossil fuel refineries, has adverse health and environmental impacts, but also the potential to be a source of clean hydrogen. This work addresses knowledge gaps and inconsistencies in H2S oxidation measurements and model predictions, emphasizing the scarcity of detailed kinetic modeling of H2S oxidation in the presence of carbon dioxide (CO2), a significant component of acid gas. This study leverages a shock tube coupled with laser absorption techniques to investigate the oxidation of mixtures of acid gas (H2S and CO2) with high H2S concentrations, equivalence ratios between 1.5 and 3.0, over the temperature range of 1300 – 1900 K and pressure near 1.3 bar. A detailed kinetic mechanism is proposed and validated through the measurement of time-histories of SO2, H2O, and CO, during fuel-rich acid gas oxidation. For the species measurements, we first conducted a comprehensive wavelength analysis for interference-free detection of the target species, providing new temperature-dependent absorption cross-section measurements of SO2 at its strongest IR band; moreover, we proposed a new laser-based thermometry technique for temperature time-history measurements behind reflected shock waves. The proposed kinetic mechanism is updated based on our recently calculated rate constants for reactions involving sulfurous species using high-level quantum chemistry and master equation calculations. The model outperforms former models at predicting measured time histories across the range of experimental conditions and elucidates different stages of the formation of target species. Important reactions in the new kinetic model are identified and discussed with reference to literature models, highlighting the reasons for the differences in model predictions.

Oxidation of Hydrogen Sulfide to Polysulfide and Thiosulfate by a Carbon Nanozyme: Therapeutic Implications with an Emphasis on Down Syndrome (Adv. Mater. 10/2024)

Oxidation of Hydrogen Sulfide to Polysulfide and Thiosulfate by a Carbon Nanozyme: Therapeutic Implications with an Emphasis on Down Syndrome (Adv. Mater. 10/2024)

Adsorption and partial catalytic oxidation of hydrogen sulfide to elemental sulfur using facilely prepared materials derived from sludge of groundwater treatment

AbstractRealizing the use of biogas as fuel or a gas engine, it is needed to upgrade to natural gas standards when it comes to pure biomethane, meaning impurities must be removed to a certain low concentration. Among these tasks, hydrogen sulfide (H2S) removal steadfastly gets the most attention. In the present work, partial catalytic oxidation was used to convert H2S to less harmful forms. Adsorbents/catalysts applied to this process were prepared from the sludge of a groundwater treatment plant using a simple combination of drying and calcination methods. As a relevant result, the as‐prepared sample (dried at 105°C for 24 h) exhibited high activity, with 90 ± 2% H2S conversion after 120 min of reaction time, while the sample calcined at about 500°C for 5 h (TP‐500) showed the highest H2S conversion (96 ± 2%); the lowest 28 ± 1% belonged to the case of TP‐700. The main compositions of the TP‐500 sample were crystalline calcite and amorphous iron oxides. The average size of calcite crystallites was ~45 nm, with a specific surface area of ~76 m2/g. Moreover, the presence of oxygen in the catalytic process and the “self‐outflow process” of sulfur desorption were the vital keys that allowed the partial H2S oxidation to take place continuously. After a reaction time of 2 h, the adsorption capacity of the best sample was 460.8 mg/g. Thus, it is obvious that inexpensive catalysts derived from sludge precursors can be effectively used for H2S removal from mixtures with air, supporting the treatment of raw biogas in the coming time.

From microbial heterogeneity to evolutionary insights: A strain-resolved metagenomic study of H2S-induced changes in anaerobic biofilms

The hidden layers of genomic diversity in microbiota of biotechnological interest have been only partially explored and a deeper investigation that overcome species level resolution is needed. CO2-fixating microbiota are prone to such evaluation as case study. A lab-scale trickle-bed reactor was employed to successfully achieve simultaneous biomethanation and desulfurization on artificial biogas and sulfur-rich biogas, and oxygen supplementation was also implemented. Under microaerophilic conditions, hydrogen sulfide removal efficiency of 81% and methane content of 95% were achieved. Methanobacterium sp. DTU45 emerged as predominant, and its metabolic function was tied to community-wide dynamics in sulfur catabolism. Genomic evolution was investigated in Gammaproteobacteria sp. DTU53, identified as the main contributor to microaerophilic desulfurization. Positive selection of variants in the hydrogen sulfide oxidation pathway was discovered and amino acid variants were localized on the sulfide entrance channel for sulfide:quinone oxidoreductase. Upon oxygen supplementation strain selection was the primary mechanism driving microbial adaptation, rather than a shift in species dominance. Selective pressure determined the emergence of new strains for example on Gammaproteobacteria sp. DTU53, providing in depth evidence of functional redundancy within the microbiome.

Geochemical transformations of sulfur and their role in the formation of different types and subtypes of saline lakes in Southeastern Transbaikalia

This study focused on the chemistry and isotopes of sulfur in lakes. The bottom sediments and water columns of lakes were found to contain reduced forms of sulfur, including hydrogen sulfide ions, elemental sulfur, and thiosulfate ions, along with sulfate ions. It was determined that elemental sulfur in lakes is present mainly in the form of suspensions and colloids, and the proportion of elemental sulfur in polysulfides increases with increasing water pH. It was shown that sulfate reduction results in the greatest isotope fractionation, with a light sulfur isotope accumulating in hydrogen sulfide ions and a heavy sulfur isotope accumulating in sulfate ions. It was confirmed that the abiotic reaction of hydrogen sulfide with oxygen yields a mixture of products that are depleted in 34S and enriched in 34S in hydrogen sulfide. In contrast, the microbial oxidation of HS− → S0 yields zerovalent sulfur, which is 2–4‰ heavier than the initial product. It was shown that the loss of sulfate ions due to bacterial reduction is most significant in subtype-I and subtype-III chloride and soda lakes. In contrast, in subtype-II sulfate and soda lakes, an increase in sulfate ions was noted due to the oxidation of hydrogen sulfides in water-bearing rocks and bacterial hydrogen sulfide. This finding indicated that in addition to evaporation, the formation of a particular type and subtype of saline lake involves the processes of aluminosilicate hydrolysis, sulfate reduction and hydrogen sulfide oxidation.

Quantum chemistry and kinetics of hydrogen sulphide oxidation.

A fundamental understanding of the acid gas (H2S and CO2) chemistry is key to efficiently implement the desulphurisation process and even the production of clean fuels such as hydrogen or syngas. In this work, we developed a new kinetic model for the pyrolysis and oxidation of hydrogen sulphide by merging two previously reported models with the goal of covering a wider range of conditions and including the effect of carbon dioxide. The resulting model, which consists of 75 species and 514 reactions, was used to conduct rate of production and sensitivity analysis in plug flow reactor simulations, and the results were used to determine the most prominent reactions in which hydrogen sulphide, molecular hydrogen, and sulphur monoxide are involved. The resulting list of important reactions was screened and the kinetics of three of them, i.e., SO2 + S2 → S2O + SO, S2O + S2 → S3 + SO, and SO + SH → S2 + OH, was found to warrant further investigation. With the goal of improving the accurancy of our new kinetic model, we carried out a robust quantum chemistry and Rice-Ramsperger-Kassel-Marcus master equation study to obtain, for the first time, the forward and reverse rate constants for those three reactions at temperatures and pressures of interest for combustion and atmospheric chemistry. This work is the first step of a kinetic study that is aimed at improving the understanding of the chemistry of the pyrolysis and oxidation of H2S, highlighting the importance of sulphur-sulphur interactions and providing a fundamental basis for future kinetic models of H2S not only in the field of combustion, but also in atmospheric chemistry.

Redox-mediated photocatalysis towards separate hydrogen production and sulfide oxidation.

We present a redox-mediated photocatalysis for separate hydrogen production and sulfide oxidation. The process involves photocatalytic hydrogen production and Fe(CN)64- oxidation, followed by spontaneous Fe(CN)63- reduction and sulfide oxidation to valued sulfur. In this approach, Fe(CN)64-/3- redox mediators were recycled, and the produced sulfur wouldn't interfere with the photocatalytic performance.