Effect of dimethyl disulfide on the sulfur formation and microbial community composition during the biological H2S removal from sour gas streams.

Removal of organic and inorganic sulfur compounds from sour gases is required because of their toxicity and atmospheric pollution. The most common are hydrogen sulfide (H2S) and methanethiol (MT). Under oxygen-limiting conditions about 92 mol% of sulfide is oxidized to sulfur by haloalkaliphilic sulfur-oxidizing bacteria (SOB), whilst the remainder is oxidized either biologically to sulfate or chemically to thiosulfate. MT is spontaneously oxidized to dimethyl disulfide (DMDS), which was found to inhibit the oxidation of sulfide to sulfate. Hence, we assessed the effect of DMDS on product formation in a lab-scale biodesulfurization setup. DMDS was quantified using a newly, in-house developed analytical method. Subsequently, a chemical reaction mechanism was proposed for the formation of methanethiol and dimethyl trisulfide from the reaction between sulfide and DMDS. Addition of DMDS resulted in significant inhibition of sulfate formation, leading to 96 mol% of sulfur formation. In addition, a reduction in the dominating haloalkaliphilic SOB species, Thioalkalivibrio sulfidiphilus, was observed in favor of Thioalkaibacter halophilus as a more DMDS-tolerant with the 50 % inhibition coefficient at 2.37 mM DMDS.

Reduction of hydrogen sulfide gas in a small wastewater collection system using sodium hydroxide.

The Kennebunk Sewer District collection system experienced H2 S-induced corrosion downstream of terminus manholes for the Wells Road and Boothby Road pumping stations. An automated odor control system using sodium hydroxide (NaOH) was developed to mitigate further corrosion. System performance was quantified by recording the [H2 S] in the terminus manholes before and after NaOH treatment. Preliminary evaluation at the Wells Road facility demonstrated significant (p < 0.001) reduction in the average [H2 S] between the treatment (4.8 ± 0.3 ppm) and control (67 ± 1.5 ppm). Permanent systems installed at both facilities in 2017 yielded similar positive results. The average [H2 S] in the Wells and Boothby Road terminus manholes reduced from 89.4 ± 1.0 to 8.0 ± 0.1 ppm and from 7.9 ± 0.2 to 0.82 ± 0.06 ppm, respectively. This work demonstrates the ability of the NaOH system presented here to minimize emission of corrosive H2 S gas in small collection systems. PRACTITIONER POINTS: Biologically-produced hydrogen sulfide (H2 S) gas corrodes sewer collection system components and results in premature asset failure. Maintaining wastewater pH above 8.5 by injecting sodium hydroxide (NaOH) minimizes H2 S emission by shifting the molar distribution of sulfur species and partially inhibiting the anaerobes that produce H2 S. The practical application of this approach may be limited to small wastewater collection systems.

Performance of a compost and biochar packed biofilter for gas-phase hydrogen sulfide removal.

The main aim of this study was to evaluate the performance of an aerobic biofilter packed with compost for the removal of gas-phase hydrogen sulfide (H2S). After 52 d of operation, the biofilter was re-packed by replacing a certain portion (25%, v/v) of the existing compost with biochar and its performance was tested. The steady and transient performance of the biofilter was evaluated by varying the H2S concentrations from 0.1 to 2.9 g m-3 at an empty bed residence time (EBRT) of 119 and 80 s, respectively. The maximum elimination capacity (ECmax) of the compost and compost + biochar biofilter were ∼19 and 33 g m-3 h-1, respectively, with >99% removal efficiency at an EBRT of 119 s. The compost biofilter showed a quick response to shock loads and the critical load to the biofilter during the shock loading step was ∼81 g m-3 h-1.

Total sulfane sulfur bioavailability reflects ethnic and gender disparities in cardiovascular disease.

Hydrogen sulfide (H2S) has emerged as an important physiological and pathophysiological signaling molecule in the cardiovascular system influencing vascular tone, cytoprotective responses, redox reactions, vascular adaptation, and mitochondrial respiration. However, bioavailable levels of H2S in its various biochemical metabolite forms during clinical cardiovascular disease remain poorly understood. We performed a case-controlled study to quantify and compare the bioavailability of various biochemical forms of H2S in patients with and without cardiovascular disease (CVD). In our study, we used the reverse-phase high performance liquid chromatography monobromobimane assay to analytically measure bioavailable pools of H2S. Single nucleotide polymorphisms (SNPs) were also identified using DNA Pyrosequencing. We found that plasma acid labile sulfide levels were significantly reduced in Caucasian females with CVD compared with those without the disease. Conversely, plasma bound sulfane sulfur levels were significantly reduced in Caucasian males with CVD compared with those without the disease. Surprisingly, gender differences of H2S bioavailability were not observed in African Americans, although H2S bioavailability was significantly lower overall in this ethnic group compared to Caucasians. We also performed SNP analysis of H2S synthesizing enzymes and found a significant increase in cystathionine gamma-lyase (CTH) 1364 G-T allele frequency in patients with CVD compared to controls. Lastly, plasma H2S bioavailability was found to be predictive for cardiovascular disease in Caucasian subjects as determined by receiver operator characteristic analysis. These findings reveal that plasma H2S bioavailability could be considered a biomarker for CVD in an ethnic and gender manner. Cystathionine gamma-lyase 1346 G-T SNP might also contribute to the risk of cardiovascular disease development.

Analysis of endogenous H2S and H2Sn in mouse brain by high-performance liquid chromatography with fluorescence and tandem mass spectrometric detection.

Previous studies indicated that bound sulfur species (BSS), including hydrogen polysulfide (H2Sn), have various physiological functions in mammalian cells. Although H2Sn molecules have been considered as secondary metabolites derived from hydrogen sulfide (H2S) based on in vitro studies or predetermined reaction formula, the physiological form of BSS and their endogenous concentration remain unclear. In the present study, we aimed to improve the usual method using monobromobimane (mBB) followed by high performance liquid chromatographic (HPLC) analysis for HS－ for simultaneous determination of H2S, H2S2, H2S3 and cysteine persulfide in biological samples. We demonstrated that mBB derivatization of H2S and H2Sn standards under alkaline conditions (pH 9.5) induced significant decreases in H2S2 and H2S3 levels and a significant increase in the H2S level in an incubation time-dependent manner. Conversely, the derivatization of mBB adducts of H2S2 and H2S3 were stable under neutral conditions (pH 7.0), which is physiologically relevant. Therefore, we re-examined the method using mBB and applied an improved method for the evaluation of H2S, H2S2, and H2S3 in mouse brain under physiological pH conditions. The concentrations of H2S and H2S2 were 0.030 ± 0.004µmol/g protein and 0.026 ± 0.002µmol/g protein, respectively. Although the level of H2S3 was below the quantification limit of this method, H2S3 was detected in mouse brain. Using the method established here, we reveal for the first time the existence of endogenous H2S2 and H2S3 in mammalian brain tissues. H2S2 and H2S3 exert anti-oxidant activity and anti-carbonyl stress effects through the regulation of redox balance in neuronal cells. Thus, our observations provide novel insights into the physiological functions of BSS in the brain and into neuronal diseases involved in redox imbalance.

A near-infrared "turn-on" fluorescent probe with a self-immolative linker for the in vivo quantitative detection and imaging of hydrogen sulfide.

Hydrogen sulfide is a critical biological messenger, but few biologically compatible methods are available for its detection in vivo. Here, we describe the design and synthesis of a novel azide-functionalized near-infrared probe, NIR-Az, for a hydrogen sulfide assay in which a self-immolative linker is incorporated between the azide moiety and phenolic dihydroxanthene fluorophore from a cyanine dye. A large "turn-on" near-infrared fluorescence signal results from the reduction of the azide group of the fluorogenic moiety to an amine, in which the self-immolative linker also enhances the accessibility of NIR-Az to hydrogen sulfide. NIR-Az can select hydrogen sulfide from among 16 analytes, including cysteine, glutathione, and homocysteine. By exploiting the superior properties of NIR-Az, such as its good biocompatibility and rapid cell internalization, we successfully demonstrated its usefulness in monitoring both the concentration- and time-dependent variations of hydrogen sulfide in living cells and animals (detection limit less than 0.26µM), thereby providing a powerful approach for probing hydrogen sulfide chemistry in biological systems.

Simultaneous inhibition of sulfate-reducing bacteria, removal of H2S and production of rhamnolipid by recombinant Pseudomonas stutzeri Rhl: Applications for microbial enhanced oil recovery.

Sulfate-reducing bacteria (SRB) are widely existed in oil production system, and its H2S product inhibits rhamnolipid producing bacteria. In-situ production of rhamnolipid is promising for microbial enhanced oil recovery. Inhibition of SRB, removal of H2S and production of rhamnolipid by recombinant Pseudomonas stutzeri Rhl were investigated. Strain Rhl can simultaneously remove S(2-) (>92%) and produce rhamnolipid (>136mg/l) under S(2-) stress below 33.3mg/l. Rhl reduced the SRB numbers from 10(9) to 10(5)cells/ml, and the production of H2S was delayed and decreased to below 2mg/l. Rhl also produced rhamnolipid and removed S(2-) under laboratory simulated oil reservoir conditions. High-throughput sequencing data demonstrated that addition of strain Rhl significantly changed the original microbial communities of oilfield production water and decreased the species and abundance of SRB. Bioaugmentation of strain Rhl in oilfield is promising for simultaneous control of SRB, removal of S(2-) and enhance oil recovery.

Molecular dynamics investigation of separation of hydrogen sulfide from acidic gas mixtures inside metal-doped graphite micropores.

The separation of poisonous compounds from various process fluids has long been highly intractable, motivating the present study on the dynamic separation of H2S in acidic-gas-mixture-filled micropores. The molecular dynamics approach, coupled with the isothermal-isochoric ensemble, was used to model the molecular interactions and adsorption of H2S/CO2/CO/H2O mixtures inside metal-doped graphite slits. Due to the difference in the adsorption characteristics between the two distinct adsorbent materials, the metal dopant in the graphitic micropores leads to competitive adsorption, i.e. the Au and graphite walls compete to capture free adsorbates. The effects of competitive adsorption, coupled with changes in the gas temperature, concentration, constituent ratio and slit width on the constituent separation of mixtures were systematically studied. The molecule-wall binding energies calculated in this work (those of H2S, H2O and CO on Au walls and those of H2O, CO and CO2 on graphite walls) show good agreement with those obtained using density functional theory (DFT) and experimental results. The z-directional self-diffusivities (Dz) for adsorbates inside the slit ranged from 10(-9) to 10(-7) m(2) s(-1) as the temperature was increased from 10 to 500 K. The values are comparable with those for a typical microporous fluid (10(-8)-10(-9) m(2) s(-1) in a condensed phase and 10(-6)-10(-7) m(2) s(-1) in the gaseous state). The formation of H-bonding networks and hydrates of H2S is disadvantageous for the separation of mixtures. The results indicate that H2S can be efficiently separated from acidic gas mixtures onto the Au(111) surface by (i) reducing the mole fraction of H2S and H2O in the mixtures, (ii) raising the gas temperature to the high temperature limit (≥400 K), and (iii) lowering the slit width to below the threshold dimension (≤23.26 Å).

Removal of hydrogen sulfide at ambient conditions on cadmium/GO-based composite adsorbents.

Cadmium-based materials with various hydroxide to carbonate ratios and their composites with graphite oxide were synthesized by a fast and simple precipitation procedure and then used as H2S adsorbents at ambient conditions in the dark or upon a visible light exposure. The structural properties and chemical features of the adsorbents were analyzed before and after hydrogen sulfide adsorption. The results showed that the high ratio of hydroxide to carbonate led to an improved H2S adsorption capacity. In moist conditions cadmium hydroxide was the best adsorbent. Moreover, it showed photoactive properties. While the incorporation of a graphene-based phase slightly decreased the extent of the improvement in the H2S adsorption capacity in moist conditions caused by photoactivity, its presence in the composites enhanced the performance in dry conditions. This was linked to photoactivity of CdS that can split H2S resulting in the formation of water in the system. The graphene-based phase enhanced the electron transfer and delayed the recombination of photoinduced charges. Carbonate-based materials showed a very good adsorption capacity in dark conditions in the presence of moisture. Upon the light exposure, CdS likely photocatalyzes the reduction of carbonate ions to formates/formaldehydes. Their deposition on the surface limits the number of sites available to H2S adsorption.

The mechanism of coal gas desulfurization by iron oxide sorbents.

This study aims to understand the roles of hydrogen and carbon monoxide during the desulfurization process in a coal gasification system that H2S of the syngas was removed by Fe2O3/SiO2 sorbents. The Fe2O3/SiO2 sorbents were prepared by incipient wetness impregnation. Through the breakthrough experiments and Fourier transform infrared spectroscopy analyses, the overall desulfurization mechanism of the Fe2O3/SiO2 sorbents was proposed in this study. The results show that the major reaction route is that Fe2O3 reacts with H2S to form FeS, and the existence of CO and H2 in the simulated gas significantly affects equilibrium concentrations of H2S and COS. The formation of COS occurs when the feeding gas is blended with CO and H2S, or CO2 and H2S. The pathways in the formation of products from the desulfurization process by the reaction of Fe2O3 with H2S have been successfully established.

Removal of gas-phase ammonia and hydrogen sulfide using photocatalysis, nonthermal plasma, and combined plasma and photocatalysis at pilot scale.

This study focuses on the removal of gas-phase ammonia (NH3) and hydrogen sulfide (H2S) in a continuous reactor. Photocatalysis and surface dielectric barrier discharge (SDBD) plasma are studied separately and combined. Though the removal of volatile organic compounds by coupling plasma and photocatalysis has been reported on a number of studies in laboratory scale, this is as far as we know the first time that it is used to remove inorganic malodorous pollutants. While each separate process is able to degrade ammonia and hydrogen sulfide, a synergetic effect appears when they are combined at a pilot scale, leading to removal capacity higher than the sum of each separate process. The removal capacity is higher when the gas circulates at a higher flow rate and when pollutant concentration is higher. The presence of water vapor in the gas is detrimental to the efficiency of the process. Operating conditions also influence the production of nitrogen oxides and ozone.

Gas cleaning and hydrogen sulfide removal for COREX coal gas by sorption enhanced catalytic oxidation over recyclable activated carbon desulfurizer.

This paper proposes a novel self-developed JTS-01 desulfurizer and JZC-80 alkaline adsorbent for H2S removal and gas cleaning of the COREX coal gas in small-scale and commercial desulfurizing devices. JTS-01 desulfurizer was loaded with metal oxide (i.e., ferric oxides) catalysts on the surface of activated carbons (AC), and the catalyst capacity was improved dramatically by means of ultrasonically assisted impregnation. Consequently, the sulfur saturation capacity and sulfur capacity breakthrough increased by 30.3% and 27.9%, respectively. The whole desulfurizing process combined selective adsorption with catalytic oxidation. Moreover, JZC-80 adsorbent can effectively remove impurities such as HCl, HF, HCN, and ash in the COREX coal gas, stabilizing the system pressure drop. The JTS-01 desulfurizer and JZC-80 adsorbent have been successfully applied for the COREX coal gas cleaning in the commercial plant at Baosteel, Shanghai. The sulfur capacity of JTS-01 desulfurizer can reach more than 50% in industrial applications. Compared with the conventional dry desulfurization process, the modified AC desulfurizers have more merit, especially in terms of the JTS-01 desulfurizer with higher sulfur capacity and low pressure drop. Thus, this sorption enhanced catalytic desulfurization has promising prospects for H2S removal and other gas cleaning.

Hydrogen sulfide removal from sediment and water in box culverts/storm drains by iron-based granules.

A renewable granular iron-based technology for hydrogen sulfide removal from sediment and water in box culverts and storm drains is discussed. Iron granules, including granular ferric hydroxide (GFH), granular ferric oxide (GFO) and rusted waste iron crusts (RWIC) embedded in the sediment phase removed aqueous hydrogen sulfide formed from sedimentary biological sulfate reduction. The exhausted iron granules were exposed to dissolved oxygen and this regeneration process recovered the sulfide removal capacities of the granules. The recovery is likely attributable to the oxidation of the ferrous iron precipitates film and the formation of new reactive ferric iron surface sites on the iron granules and sand particles. GFH and RWIC showed larger sulfide removal capacities in the sediment phase than GFO, likely due to the less ordered crystal structures on their surfaces. This study demonstrates that the iron granules are able to remove hydrogen sulfide from sediment and water in box culverts and storm drains and they have the potential to be regenerated and reused by contacting with dissolved oxygen.

Three-dimensionally ordered macroporous iron oxide for removal of H2S at medium temperatures.

A series of iron oxide sorbents with novel structures of three-dimensionally ordered macropores (3DOM), ranging in size from 60 to 550 nm, were fabricated and creatively used as sorbents for the removal of H2S at medium temperatures of 300-350 °C. Evaluation tests using thermogravimetric analysis (TGA) and a fixed-bed reactor showed that, in comparison to the iron oxide sorbent prepared by a conventional mixing method, the fabricated iron oxide sorbent with a 3DOM structure exhibited much higher reactivity and efficiency, as well as high sorbent utilization with low regeneration temperature. The excellent performance of 3DOM iron oxide as a sulfur sorbent is attributed to its special texture, i.e., the open and interconnected macroporous, large surface area, and nanoparticles of iron oxide, which are revealed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and nitrogen adsorption techniques. The investigation results of the pore effect on the performance of the sorbent show that sorbents with pores size around 150 nm in diameter revealed the best performance. The reason is that pores of this size are large enough to allow gas to pass through even if the channel is partially blocked during the reaction process while remaining a large surface area that can provide more active sites for the reaction.

Improvement of H2S sensing properties of SnO2-based thick film gas sensors promoted with MoO3 and NiO.

The effects of the SnO2 pore size and metal oxide promoters on the sensing properties of SnO2-based thick film gas sensors were investigated to improve the detection of very low H2S concentrations (<1 ppm). SnO2 sensors and SnO2-based thick-film gas sensors promoted with NiO, ZnO, MoO3, CuO or Fe2O3 were prepared, and their sensing properties were examined in a flow system. The SnO2 materials were prepared by calcining SnO2 at 600, 800, 1,000 and 1,200 °C to give materials identified as SnO2(600), SnO2(800), SnO2(1000), and SnO2(1200), respectively. The Sn(12)Mo5Ni3 sensor, which was prepared by physically mixing 5 wt% MoO3 (Mo5), 3 wt% NiO (Ni3) and SnO2(1200) with a large pore size of 312 nm, exhibited a high sensor response of approximately 75% for the detection of 1 ppm H2S at 350 °C with excellent recovery properties. Unlike the SnO2 sensors, its response was maintained during multiple cycles without deactivation. This was attributed to the promoter effect of MoO3. In particular, the Sn(12)Mo5Ni3 sensor developed in this study showed twice the response of the Sn(6)Mo5Ni3 sensor, which was prepared by SnO2(600) with the smaller pore size than SnO2(1200). The excellent sensor response and recovery properties of Sn(12)Mo5Ni3 are believed to be due to the combined promoter effects of MoO3 and NiO and the diffusion effect of H2S as a result of the large pore size of SnO2.

Mechanisms of hydrogen sulfide removal with steel making slag.

In the present study, we experimentally investigated the removal of hydrogen sulfide using steel-making slag (SMS) and clarified the mechanism of hydrogen sulfide removal with the SMS. The results proved that SMS is able to remove hydrogen sulfide dissolved in water, and the maximum removal amount of hydrogen sulfide per unit weight of the SMS for 8 days was estimated to be 37.5 mg S/g. The removal processes of hydrogen sulfide were not only adsorption onto the SMS, but oxidation and precipitation as sulfur. The chemical forms of sulfide adsorbed onto the SMS were estimated to be sulfur and manganese sulfide in the ratio of 81% and 19%, respectively. It is demonstrated here that the SMS is a promising material to remediate organically enriched coastal sediments in terms of removal of hydrogen sulfide. Furthermore, using SMS is expected to contribute to development of a recycling-oriented society.

A comparison of TiO2 nanoparticles and nanotubes for catalytic gas phase destruction of H2S gas at high temperatures.

Reduction of H2S gas over Sulphur doped TiO2 nanoparticles and TiO2 nanotubes was studied in this work. Fixed bed catalytic system was used for the catalytic reduction of H2S gas at a high temperature of 450 degrees C under laboratory conditions. 99.97% reduction was achieved using S-doped TiO2. 2.89% Sulphur was adsorbed on S-doped TiO2 nanoparticles in the form of Ti(SO4)2, while 95.6% reduction was achieved in case of TiO2 nanotubes and the sulphur adsorption was 2.67%. The XRD, SEM, and EDX techniques were carried out to characterize the nanoparticles and nanotubes, while gas reduction analysis was carried out using GC-MS for gas samples.

Effect of precursor and preparation method on manganese based activated carbon sorbents for removing H2S from hot coal gas.

Activated carbon (AC) supported manganese oxide sorbents were prepared by the supercritical water impregnation (SCWI) using two different precursor of Mn(NO(3))(2) (SCW(N)) and Mn(Ac)(2)·4H(2)O (SCW(A)). Their capacities of removing H(2)S from coal gas were evaluated and compared to the sorbents prepared by the pore volume impregnation (PVI) method. The structure and composition of different sorbents were characterized by XRD, SEM, TEM, XPS and XANES techniques. It is found that the precursor of active component plays the crucial role and SCW(N) sorbents show much better sulfidation performance than the SCW(A) sorbents. This is because the Mn(3)O(4) active phase of the SCW(N) sorbents are well dispersed on the AC support, while the Mn(2)SiO(4)-like species in the SCW(A) sorbent can be formed and seriously aggregated. The SCW(N) sorbents with 2.80% and 5.60% manganese are favorable for the sulfidation reaction, since the Mn species are better dispersed on the SCW(N) sorbents than those on the PV(N) sorbents and results in the better sulfidation performance of the SCW(N) sorbents. As the Mn content increases to 11.20%, the metal oxide particles on AC supports aggregate seriously, which leads to poorer sulfidation performance of the SCW(N)11.20% sorbents than that of the PV(N)11.20% sorbents.

H2S gas biological removal efficiency and bacterial community diversity in biofilter treating wastewater odor.

The objective of this study was to assess the feasibility of using a biofilter system to treat hydrogen sulfide (H2S) contaminated air and to characterize its microbial community. The biofilter system was packed with peat. During the experimental work, the peat was divided in three layers (down, middle, and up). Satisfactory removal efficiencies of H2S were proved and reached 99% for the majority of the run time at an empty bed retention time (EBRT) of 60 s. The polymerase chain reaction-single strand conformation polymorphism (PCR-SSCP) method was used to uncover the changes in the microbial community between the different layers. Analysis of SSCP profiles demonstrated significant differences in community structure from a layer to another with a strong decrease in species diversity towards the up layer. It was found that the used support was suitable for microorganism growth, and may have a potential application in H2S biofiltration system.

[Performance of an innovative polyethylene carrier biotrickling filter treating hydrogen sulphide gas].

Characteristics of double-layer biotrickling filter using high density polythene rasching rings carrier treating waste gas containing hydrogen sulphide was studied. Results showed that biotrickling filter had significant advantages of low pressure drop and even load distribution along the reactor height. When removal efficiency was greater than 90%, gas retention time was 12 s, maximum inlet load was 110 g/(m3 x h), elimination capacity was 84 g/(m3 x h). At steady state, about 37%-55% of hydrogen sulfide load was removed from the lower layer. During long-term operation, pressure drop kept to less than 280 Pa x m(-1), the backwashing period was longer than two months, no biomass accumulation happened in the lower layer, and abnormal increase in pressure drop can be used as a indicator of backwashing. Reactor recovery and restart experimental results showed that removal efficiency recovered to 95% in 1 day after 6 days without H2S, pH dramatic variation of spray liquid had significant adverse impact on biotrickling bed reactor.