Volatile Organic Sulfur Compounds Research Articles

Spatial and seasonal variability in volatile organic sulfur compounds in seawater and the overlying atmosphere of the Bohai and Yellow seas

Abstract. Volatile organic sulfur compounds (VSCs), including carbon disulfide (CS2), dimethyl sulfide (DMS), and carbonyl sulfide (COS), were surveyed in the seawater of the Bohai and Yellow seas and the overlying atmosphere during spring and summer of 2018 to understand the production and loss of VSCs and their influence factors. The concentration ranges of COS, DMS, and CS2 in the surface seawater were 0.14–0.42, 0.41–7.74, and 0.01–0.18 nmol L−1 during spring and 0.32–0.61, 1.31–18.12, and 0.01–0.65 nmol L−1 during summer, respectively. The COS concentrations exhibited positive correlation with dissolved organic carbon (DOC) concentrations in seawater during summer, which verified the photochemical production of COS from chromophoric dissolved organic matter (CDOM). High DMS concentrations occurred near the Yellow River, Laizhou Bay, and Yangtze River estuary, coinciding with high nitrate and chlorophyll (Chl) a concentrations due to river discharge during summer. The COS, DMS, and CS2 concentrations were the highest in the surface seawater and decreased with the depth. The mixing ratios of COS, DMS, and CS2 in the atmosphere were 255.9–620.2, 1.3–191.2, and 5.2–698.8 pptv during spring and 394.6–850.1, 10.3–464.3, and 15.3–672.7 pptv in summer, respectively. The ratios of mean oceanic concentrations and atmospheric mixing ratios for summer to spring in COS, DMS, and CS2 were 1.8, 3.1, 3.7 and 1.6, 4.6, 1.5, respectively. The ratios of the mean sea-to-air fluxes for summer to spring in COS, DMS, and CS2 were 1.2, 2.1, and 4.3. The sea-to-air fluxes of VSCs indicated that the marginal seas are important sources of VSCs in the atmosphere. The results support a better understanding of the contribution of VSCs in marginal seas.

Quorum Sensing Regulates the Production of Methanethiol in Vibrio harveyi.

Methanethiol (MeSH) and dimethyl sulfide (DMS) are important volatile organic sulfur compounds involved in atmospheric chemistry and climate regulation. However, little is known about the metabolism of these compounds in the ubiquitous marine vibrios. Here, we investigated MeSH/DMS production and whether these processes were regulated by quorum-sensing (QS) systems in Vibrio harveyi BB120. V. harveyi BB120 exhibited strong MeSH production from methionine (Met) (465 nmol mg total protein-1) and weak DMS production from dimethylsulfoniopropionate (DMSP) cleavage. The homologs of MegL responsible for MeSH production from L-Met widely existed in vibrio genomes. Using BB120 and its nine QS mutants, we found that the MeSH production was regulated by HAI-1, AI-2 and CAI-1 QS pathways, as well as the luxO gene located in the center of this QS cascade. The regulation role of HAI-1 and AI-2 QS systems in MeSH production was further confirmed by applying quorum-quenching enzyme MomL and exogenous autoinducer AI-2. By contrast, the DMS production from DMSP cleavage showed no significant difference between BB120 and its QS mutants. Such QS-regulated MeSH production may help to remove excess Met that can be harmful for vibrio growth. These results emphasize the importance of QS systems and the MeSH production process in vibrios.

Odorous organic gas emission characteristics from cooked food wastes during aerobic decomposition

Emission of volatile organic compounds (VOCs) from food waste is a key trouble for surrounding residents. Herein, the VOC emission patterns from headspace (gaseous) and produced leachate (aqueous) during decomposition of cooked milk cabbage, tilapia fish, and their mixture (Mix) were investigated in self-made reactors. The average amount of gaseous VOCs from fish (2888.7 mg/kg dry matter (DM)) was higher than Mix (2152.9 mg/kg DM) and cabbage (374.2 mg/kg DM). The dominant VOCs were volatile organic sulfur compounds (VOSCs) and oxygenated VOCs, accounting for 65.8 and 32.5 %, 71.8 and 25.2 %, 39.0 and 36.7 % of total VOC yields in fish, Mix, and cabbage, respectively. From leachate, average leaching fluxes of VOCs followed the order of: Mix (2487.9 μg/(L kg) DM) > fish (2374.7 μg/(L kg) DM) > cabbage (368.7 μg/(L kg) DM). VOSCs were also the major VOCs from leachate, accounting for 87.9, 98.6, and 98.5 % of total VOCs in leachate, respectively. Lactobacillus and Weissella were the dominant genera in cabbage, while Bacteroides were dominant in fish and Mix. Physicochemical factors were significantly related to bacterial composition shifts over time. Furthermore, Lysinibacillus and Vibro were positively correlated with gaseous dimethyl disulfide, while Lactobacillus, Weissella, Savagea, Ignatzschineria, Acinetobacter, and Pseudomonas showed strong relationship with dominant gaseous and aqueous VOCs. These findings provide significant references for understanding distribution and controlling of VOCs released during cooked food waste fermentation.

Interaction of a Porphyrin Aluminum Metal-Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT Computations.

The study presents complementary experiments and quantum chemical DFT computations to reveal the molecular-level interactions of an advanced nanomaterial, porphyrin aluminum metal-organic framework (compound 2), with the volatile organic sulfur compound diethyl sulfide (DES). First, the intermolecular host-guest interactions during the sorption of DES were explored under dynamic conditions, using the vapor of DES in flowing air. The in situ time-dependent ATR-FTIR spectroscopy in a controlled atmosphere was significantly improved though the use of a new facilely built spectroscopic mini-chamber. The binding site of DES in compound 2 involves the μ(O-H) and COO- groups of the linker of the sorbent. Further, the chemical kinetics of the sorption of DES was investigated, and it follows the Langmuir adsorption kinetic model. That is, depending on the time interval, the process obeys either the pseudo-first- or pseudo-second-order rate law. For the Langmuir adsorption of the pseudo-first order, the rate constant is robs = 0.165 ± 0.017 min-1. Next, the interaction of compound 2 with the saturated vapor of DES yields the adsorption complex compound 3 [Al-MOF-TCPPH2]2(DES)7. The adsorbed amount of DES is very large at 36.5 wt.% or 365 mg/g sorbent, one of the highest values reported on any sorbent. The molecular modes of bonding of DES in the complex were investigated through quantum chemical DFT computations. The adsorption complex was facilely regenerated by gentle heating. The advanced functional material in this work has significant potential in the environmental remediation of diethyl sulfide and related volatile organic sulfur compounds in air, and it is an interesting target of mechanistic studies of sorption.

Isopropylthiol emission by bloom-forming Microcystis: Biochemistry, ecophysiology and semiochemistry of a volatile organosulfur compound

Microcystis species not only produce toxic cyanobacterial blooms, but can be a significant source of taste and odour. Previous studies have associated foul-smelling volatile organic sulfur compounds (VOSCs) with Microcystis blooms, but have largely attributed these compounds to bacterial bloom decomposition. However, earlier reports of the production of isopropylthio compounds by several Microcystis strains suggests that these cyanobacteria may themselves be a source of these VOSCs. Sulphur compounds have been shown to play important semiochemical roles in algal cell protection and grazer interactions in marine systems, but little is known about the production and chemical ecology of freshwater cyanobacterial VOSCs. To address this knowledge gap, we undertook the first detailed investigation of the biochemistry, ecophysiology and semiochemistry of these compounds and their production by Microcystis, and tested the hypothesis that they act as multifunctional semiochemicals in processes related to cell protection and grazer defence. Using short-term incubations and an adapted headspace-GC–MS technique, we investigated VOSC production by axenic and non-axenic strains, and verified that isopropylthio compounds are in fact produced by these cyanobacteria, identifying 5 isopropyl moiety-containing VOSCs (isopropylthiol (ISH), isopropylmethyl sulfide, isopropyl methyl disulfide, diisopropyl disulfide (ISSI) and diisopropyl trisulfide) as well as methanethiol in three strains. Further studies with the axenic strain Microcystis PCC 7806 using different light regimes, metabolic inhibitors (sodium azide, DCMU), the antioxidant enzyme catalase and stable labelled precursors (hydrogencarbonate, acetates and sulfate) demonstrated that ISH is a true exo-metabolite, synthesized via the acetate pathway. It is actively produced and continuously excreted by the cyanobacteria during growth, with minimal internal storage or post-lysis catalytic generation. The molar ratios of the redox pair ISH/ISSI are not directly involved in the photosynthetic and respiratory electron transport chains, but dependant on the redox state of the cell - likely mediated by reactive oxygen species (ROS), as shown by a marked effect of catalase. These results, along with toxicological and behavioural assays using the two aquatic invertebrates Thamnocephalus platyurus and Daphnia magna indicate that ISH plays multiple important physiological and ecological roles. It acts as an effective antioxidant against high ROS levels, as often experienced in surface blooms, it elicits avoidance-related behavioural responses in grazer communities and at high levels, it can be toxic to some invertebrates.

Formation of volatile organic sulfur compounds by low thermal maturation of source rocks: A geochemical proxy for natural gas

Volatile organic sulfur compounds (VOSC) are trace components of natural gas that can provide substantial information regarding gas origins, migration, and key processes such as H2S generation and its occurrence in natural gas reservoirs. In the current study we demonstrate the applicability of VOSC as a proxy for gas-source rock correlations and identification of interactions between H2S and other natural gas components. We studied the molecular and isotopic compositions of VOSC formed during low-level thermal maturation (%Ro equivalent = 0.60–0.71) of six different immature source rocks covering a variety of kerogens (types I, II, II-S and III). Anhydrous pyrolysis experiments (300 °C, 72h) were performed on all the source rocks studied, and the produced gases were analyzed for their molecular compositions and compound specific sulfur isotopes of the various VOSC formed. The formed gases were either dominated by CH4 (32.2–49.9%) or CO2 (31.9–46.2%) and contained a variety of alkanes in the C2–C5 range. H2S formed in 6 out of 8 experiments at concentrations ranging from 0.6 to 4.3%. The results demonstrated formation of VOSC in all experiments, regardless of kerogen types or source rock lithologies. The formation of thiols (16–121.2 ppm) in the produced gas was restricted to those experiments that contained H2S. This indicates that thiols formation is limited to gas-phase interactions between H2S and hydrocarbons. In contrast, thiophenes formed in all experiments (14.9–1778.8 ppm) regardless of H2S presence. Thiols preserved the δ34S signal of their associated H2S due to gas-phase interactions between the two, while thiophenes showed no interaction with the associated H2S and instead preserved the δ34S signature of the bulk kerogen (within 3.5‰ on average) of each source rock. This work demonstrates the applicability of thiophenes to act as a gas-source rock proxy for natural gas and thiols as a proxy for identification of present or paleo-interactions between natural gas and H2S.

Biofilm metagenomic characteristics behind high coulombic efficiency for propanethiol deodorization in two-phase partitioning microbial fuel cell

Hydrophobic volatile organic sulfur compounds (VOSCs) are frequently found during sewage treatment, and their effective management is crucial for reducing malodorous complaints. Microbial fuel cells (MFC) are effective for both VOSCs abatement and energy recovery. However, the performance of MFC on VOSCs remains limited by the mass transfer efficiency of MFC in aqueous media. Inspired by two-phase partitioning biotechnology, silicone oil was introduced for the first time into MFC as a non-aqueous phase (NAP) medium to construct two-phase partitioning microbial fuel cell (TPPMFC) and augment the mass transfer of target VOSCs of propanethiol (PT) in the liquid phase. The PT removal efficiency within 32 h increased by 11–20% compared with that of single-phase MFC, and the coulombic efficiency of TPPMFC (11.01%) was 4.32–2.68 times that of single-phase MFC owing to the fact that highly active desulfurization and thiol-degrading bacteria (e.g., Pseudomonas, Achromobacter) were attached to the silicone oil surface, whereas sulfur-oxidizing bacteria (e.g., Thiobacillus, Commonas, Ottowia) were dominant on the anodic biofilm. The outer membrane cytochrome-c content and NADH dehydrogenase activity improved by 4.15 and 3.36 times in the TPPMFC, respectively. The results of metagenomics by KEGG and COG confirmed that the metabolism of PT in TPPMFC was comprehensive, and that the addition of a NAP upregulates the expression of genes related to sulfur metabolism, energy generation, and amino acid synthesis. This finding indicates that the NAP assisted bioelectrochemical systems would be promising to solve mass-transfer restrictions in low solubility contaminates removal.

Tracking the origin of Ordovician natural gas in the Ordos basin using volatile sulfur compounds

Molecular and compound specific isotope analysis of volatile organic sulfur compounds (VOSC), alkanes and CO2 in natural gases from the Ordovician Majiagou Formation of the Daniudi field (Ordos basin, China) was performed. The analysis of VOSC demonstrated abundant thiols, sulfides and thiophenes in several samples while others had low concentrations of sulfides only. Molecular analysis of main alkanes and non-hydrocarbons showed the samples vary by the nitrogen and H2S concentrations. Thiols in the gas were at isotopic equilibrium with H2S bearing isotopic signature similar to that of Ordovician anhydrites within the reservoirs, hence the source of H2S was likely thermochemical sulfate reduction (TSR) of these anhydrites. In contrast, gas samples that lacked thiols also lacked H2S. Since all gases came from the same formation and similar thermal regime, the lack of thiols and H2S indicates that the occurrence of TSR in the field was limited, likely by contact between hydrocarbons to the anhydrites. The isotopic signature (δ34S) of thiophenes in the gas samples suggests the source of the gas is unlikely to be Carboniferous or Permian coals which were previously suggested as the source rocks for the gas. The δ13C and δ2H of alkanes further supports this suggestion as it demonstrates Carboniferous and Permian gases are unlikely to undergo TSR and generate the gas present in the Ordovician reservoirs. Instead, the δ13C and δ2H of alkanes hint that the gas source is shale rather than coal.This study demonstrates the applicability of compound specific sulfur isotope analysis of VOSC in identification of H2S sources, performing gas-source rock correlation and acting as a complementary proxy in case where routine analysis of hydrocarbons (δ13C and δ2H) is insufficient for identification of the gas source.

Oxygen vacancies mediated flower-like BiOX microspheres for photocatalytic purification of methyl mercaptan odor: Significant distinction induced by halogen elements

Odor pollution, represented by low-concentration volatile organic sulfur compounds (VOSCs), has become a difficult issue in the field of air pollution control. Photocatalytic oxidation technology is applicable for the treatment of low-concentration VOSCs. However, currently available photocatalysts often suffer from limited efficiency and severe deactivation. Herein, flower-like BiOX (X = Cl, Br, I) microspheres abundant with oxygen vacancies (OVs) were developed for the removal of the model pollutant CH3SH. BiOI exhibited the optimal CH3SH oxidation performance, with the removal efficiency stabilizing at 75% within 180-min simulated solar-light irradiation, while BiOCl and BiOBr deactivated from 38% and 55% to 20% and 22%, respectively. Mechanism analysis found, OVs and I- synergistically endowed BiOI with better CH3SH adsorption and activation, enhanced light harvesting, quicker charge transfer, and more affluent •OH and •O2- productions. Photogenerated e- and •OH took a predominantly irreplaceable part in CH3SH oxidation, followed by •O2- and h+. New pathways of CH3SH photocatalytic oxidation was proposed, and dimethyl trisulfide was firstly found as its oxidation product. Besides, the oxidation products SO42- was proved to be converted to •SO4- radicals to further promote CH3SH oxidation, and the largest production of •SO4- over BiOI might be responsible for its excellent performance. Furthermore, the strong adsorption and substantial accumulation of CH3SO3H on BiOCl and BiOBr might be the key cause of their rapid deactivation. This work would inspire the construction of more effective photocatalysts for the purification of VOSCs odor.

Shifts of the Rate-Limiting Step in Airlift Microbial Electrolysis Cells for Gaseous Propanethiol Degradation

The hydrophobicity and biotoxicity of volatile organic sulfur compounds hinder them from being efficiently biodegraded. Herein, combining the advantages of the airlift (AL) bioreactor and microbial electrolysis cell (MEC) on mass transfer and bioreaction enhancement, we proposed AL-MEC systems for gaseous propanethiol (PT) degradation for the first time, in which the electrodes were modified by polypyrrole (PPy) and polypyrrole/carbon nanotubes (PPy/CNTs) to further strengthen the biodegradation process. The resulting PPy-AL-MEC and PPy/CNTs-AL-MEC possessed the best PT removal efficiencies of 84.0 and 94.4%, respectively (PT, 50 mg m–3; empty bed residence time (EBRT), 90 s; anode potential, 0.5 V vs. SHE), which were much higher than 68.8% in a control system with an unmodified graphite electrode (GS-AL-MEC). Moreover, the kinetics analysis reveals that the rate-limiting step shifted from biodegradation in GS-AL-MEC to mass transfer in PPy/CNTs-AL-MEC, while that in PPy-AL-MEC also shifted to mass transfer at an EBRT ≥ 45 s.

Effect of thermal maturation on the isotopic compositions of volatile organic sulfur compounds released from a kerogen by hydrous and anhydrous pyrolysis

Volatile organic sulfur compounds (VOSCs) may provide an alternative and improved approach in the evaluation of source and thermal maturity of natural gas. However, the role of water in the generation and decomposition of VOSCs is still ambiguous. Hydrous pyrolysis experiments were conducted on the isolated type Ⅱ-S kerogen of a source rock collected from the Ghareb Formation, Israel at 200–360 ℃ for 72 h (Easy%Ro = 0.32–1.20). The evolved gases were quantified for C1-C5 hydrocarbons, CO2, H2S and VOSCs. Compound specific isotope analysis were conducted both on the VOSCs and H2S (δ34S), and also on the C1-C5 hydrocarbons and CO2 (δ13C, δ2H). The results show that thiols concentration increased from 200 ℃ to 300 ℃ and then decreased from 300 ℃ to 360 ℃. The formed thiols isotopically co-vary with H2S from 200 ℃ to 340 ℃ and present the opposite trend with H2S from 340 ℃ to 360 ℃. The δ34S values of thiols are usually 3–7‰ lighter than the parent kerogen and 0.5–4‰ heavier than H2S. The concentrations of thiophenes generally increased with thermal stress with peak generation at 360 ℃, the δ34S values of thiophenes are mostly < 2–4‰ lighter than the parent kerogen and 2–8‰ heavier than H2S through the experiments. The δ13C and δ2H values of gaseous hydrocarbons are gradually enriched in heavy isotopes with increased thermal maturity. VOSCs dominated by thiols and thiophenes are generated by two ways: 1. the interactions between H2S and hydrocarbon molecules (synthetic pathway), 2. thermal cracking of OMs including kerogen and associated bitumen primary cracking and hydrocarbon secondary cracking (thermal cracking pathway). The synthetic pathway played the major role in the generation of thiols at the immature and early mature stages (200–300 ℃, Easy%Ro = 0.32–0.71), the cracking pathway has the dominant effect on the occurrence of thiols at higher thermal maturity levels (300–360 ℃, Easy%Ro = 0.71–1.20). The main pathway of thiophenes formation throughout the experiments is by the thermal cracking pathway. In the hydrous experiments, water promotes the synthetic pathway that generated thiols and retarded the thermal cracking pathway that forms thiophenes, but had no significant impact on δ34S values of individual VOSCs, δ13C and δ2H values of gaseous hydrocarbons. Therefore, combining with carbon and hydrogen isotopic compositions of gaseous hydrocarbons, molecular and sulfur isotopic compositions of individual VOSCs in the gas phase can provide valuable clues for petroleum systems in sedimentary basins including gas sources, generation pathways, thermal maturity levels and petroleum secondary transformations, such as thermochemical sulfate reduction in the subsurface reservoirs.

Roasting and Cacao Origin Affect the Formation of Volatile Organic Sulfur Compounds in 100% Chocolate.

Chocolate is a highly appreciated food that develops its characteristic flavors in large part during the roasting of cacao beans. Many functional classes have been noted for their importance to chocolate flavor, including volatile organic sulfur compounds (VSCs). Despite this, the effect of roasting on the concentration of VSCs has never been thoroughly assessed. Here, we studied the effects of roasting temperature, time, and cacao origin on the formation of VSCs. Twenty-seven 100% chocolate samples made from cacao from three different origins and roasted according to an I-optimal experimental design were analyzed by comprehensive gas chromatography with sulfur-selective detection (GCxGC-SCD). For two compounds, dimethyl disulfide and dimethyl trisulfide, the effects of roasting time, roasting temperature, and cacao origin were modelled using response surface methodology and semi-quantified relative concentration. Overall, roasting increased the number of sulfur-containing volatiles present in chocolate, with a total of 28 detected, far more than previously thought. Increased roasting time and especially roasting temperature were found to significantly increase the concentration of VSCs (p < 0.05), while cacao origin effects were only seen for dimethyl disulfide (p < 0.05). The identity of most VSCs remains tentative, and more research is needed to unravel the impact of these volatiles on flavor perception in chocolate.

Synergy effects of Methylomonas koyamae and Hyphomicrobium methylovorum under methanethiol stress.

Methanotrophs are able to metabolize volatile organic sulfur compounds (VOSCs), excrete organic carbon during CH4 oxidation, and influence microbial community structure and function of the ecosystem. In return, microbial community structure and environmental factors can affect the growth metabolism of methanotrophs. In this study, Methylomonas koyamae and Hyphomicrobium methylovorum were used for model organisms, and methanethiol (MT) was chosen for a typical VOSC to investigate the synergy effects under VOSC stress. The results showed that when Hyphomicrobium methylovorum was co-cultured with Methylomonas koyamae in the medium with CH4 used as the carbon source, the co-culture had better MT tolerance relative to Methylomonas koyamae and oxidized all CH4 within 120h, even at the initial MT concentration of 2000mgm-3. The optimal co-culture ratios of Methylomonas koyamae to Hyphomicrobium methylovorum were 4:1-12:1. Although MT could be converted spontaneously to dimethyl disulfide (DMDS), H2S, and CS2 in air, faster losses of MT, DMDS, H2S, and CS2 were observed in each strain mono-culture and the co-culture. Compared with Hyphomicrobium methylovorum, MT was degraded more quickly in the Methylomonas koyamae culture. During the co-culture, the CH4 oxidation process of Methylomonas koyamae could provide carbon and energy sources for the growth of Hyphomicrobium methylovorum, while Hyphomicrobium methylovorum oxidized MT to help Methylomonas koyamae detoxify. These findings are helpful to understand the synergy effects of Methylomonas koyamae and Hyphomicrobium methylovorum under MT stress and enrich the role of methanotrophs in the sulfur biogeochemical cycle. KEY POINTS: • The co-culture of Methylomonas and Hyphomicrobium has better tolerance to CH3SH. • Methylomonas can provide carbon sources for the growth of Hyphomicrobium. • The co-culture of Methylomonas and Hyphomicrobium enhances the removal of CH4 and CH3SH.

Inoculation with black soldier fly larvae alters the microbiome and volatile organic compound profile of decomposing food waste

The black soldier fly (BSF; Hermetia illucens) is used in sustainable processing of many types of organic waste. However, organic waste being decomposed by BSF produces strong odors, hindering more widespread application. The odor components and how they are produced have yet to be characterized. We found that digestion of food waste by BSF significantly alters the microbial flora, based on metagenomic analyses, and the odor components generated, as shown by thermal desorption gas chromatography mass spectrometry analysis. Inoculation with BSF significantly decreased production of volatile organic sulfur compounds (dimethyl disulfide and dimethyl trisulfide), which are known to be released during methionine and cysteine metabolism by Lactobacillus and Enterococcus bacteria. BSF inoculation significantly changed the abundance of Lactobacillus and Enterococcus and decreased microbial diversity overall. These findings may help in optimizing use of BSF for deodorization of composting food waste.

Profile of atmospheric VOC over the Yellow Sea, China: A tale of distribution, constraints, and sources

In the winter of 2018–2019, 75 air samples were collected through four ship-borne measurements in the Yellow Sea (YS) to assess the levels, confinement processes, and source distribution of volatile organic compounds (VOCs). A total of 41 were eventually detected, which mainly were non-methane hydrocarbons (NMHCs), volatile halogenated hydrocarbons (VHCs), oxygenated volatile organic compounds (OVOCs), and volatile organic sulfur compounds (VSCs). Aromatics (31.93 %) and alkenes (11.04 %) in the atmosphere of the YS accounted for a larger proportion of NMHCs compared with the coastal areas. C3-C5 alkanes, propylene, and chloroform exhibited strong latitudinal gradients and opposite latitudinal distributions in the North and South YS, highlighting the strong contribution of regional outflow to YS's atmosphere. The level of Σ41VOCs increased significantly during the heavy pollution period with some chemical monomers detected, which was further enhanced by the emissions from industrial parks near the Liaodong Peninsula and the Shandong Peninsula. Five main VOC sources were identified by the Positive matrix factorization (PMF) model, which were industrial emissions (13.33 %), fuel use and volatilization (6.67 %), Freon R-22 emissions (33.33 %), oil and gas production (20.00 %), and solvent volatilization (26.67 %). These observations revealed the strong causal relationship between coastal air mass transport and the atmosphere in the marginal sea and emphasized that full attention should be paid to the unintentional and unorganized emission of chemical monomers in the industrial process.

Experimental study on removal of mercaptans from gas streams by 1-butyl-3-methyl-imidazolyl alanine

Mercaptans as volatile organic sulfur compounds would cause environmental pollution. Researches are focused on the removal of mercaptans by solvent absorption method. In this work, a new efficient absorbent of 1-butyl-3-methylimidazolyl alanine ([Bmim]Ala) was prepared and evaluated by the removal of mercaptans from the model gas containing methyl mercaptan (MeSH, 307.6 mg/m3), ethyl mercaptan (EtSH, 201.1 mg/m3) and propyl mercaptan (PrSH, 149.9 mg/m3) in nitrogen. The results showed that the removal rate of MeSH, EtSH and PrSH was 97.77, 98.12 and 100.00%, respectively, at a temperature of 35 °C and a pressure of 1.00 bar for 2 min. After 6 recycling times, [Bmim]Ala remained a good performance for the removal of mercaptans. The desulfurization mechanism was proposed that the absorption sites were mainly on the alanine anion (Ala−) and Ala− could be replaced by the thiol anion (RS−) to form a new ionic liquid 1-butyl-3-methylimidazolyl thiolate ([Bmim]+RS−). Meanwhile, since the electrostatic interaction between -COO− in Ala− and H-g on the imidazolium cation could be destroyed by the -SH group, the -COO− group would interact with mercaptans to form a strong H-bond. The amino in Ala− and the -SH group could form Lewis acid-base compounds.

A zinc-containing porphyrin aluminum MOF in sorption of diethyl sulfide vapor: mechanistic experimental and computational study.

We report a mechanistic study of the interactions in the sorption of volatile organic sulfur compound (VOSC) diethyl sulfide (DES) by zinc porphyrin aluminum MOF (actAl-MOF-TCPPZn) compound 3. First, interactions were studied under dynamic conditions with the vapor of DES in flowing air, using in situ time-dependent ATR-FTIR spectroscopy in a controlled atmosphere with a new facile spectroscopic mini-chamber. The first binding site includes μ(O-H) and COO- groups as detected by characteristic peak shifts. Control experiments with a model compound, which lacks porosity and these groups, show no peak shifts. An additional insight was obtained by DFT computations using small clusters. The kinetics of sorption of DES by compound 3 is of the Langmuir adsorption model and pseudo-first order with rate constant robs = 0.442 ± 0.056 min-1. Sorption of DES under static conditions in saturated vapor results in stoichiometric adsorption complex [Al-MOF-TCPPZn]1(DES)4 characterized by spectroscopic, structural and gravimetric methods; the adsorbed amount is very high (381 mg g-1 sorbent). The repetitive sorption and desorption of DES are conducted, with facile regeneration. Finally, the mechanistic details were determined by Raman and photoluminescence (PL) spectroscopy using a confocal Raman microscope. Photoexcitation of compound 3 at 405 nm into the Soret band of the metalloporphyrin linker shows the characteristic PL peaks of Q-bands: the purely electronic Q(0-0) and first vibronic Q(0-1) bands. Upon interaction with DES, preferential quenching of PL from the Q(0-0) band occurs with a significant increase of the signal of the vibronic Q(0-1) band, reflecting bonding to the metalloporphyrin ring. Compound 3 is of interest to mechanistic studies of VOSCs, their removal from air, and optical chemo-sensing.

Superior dimethyl disulfide degradation in a microbial fuel cell: Extracellular electron transfer and hybrid metabolism pathways

To enhance the biological degradation of volatile organic sulfur compounds, a microbial fuel cell (MFC) system with superior activity is developed for dimethyl disulfide (DMDS) degradation. The MFC achieves a removal efficiency near 100% within 6 h (initial concentration: 90 mg L−1) and a maximum biodegradation rate constant of 0.743 mM h−1. The DMDS removal load attains 2.684 mmol h−1 L−1, which is 6.18–2440 times the loads of conventional biodegradation processes reported. Meanwhile, the maximum power density output and corresponding current density output are 5.40 W m−3 and 40.6 A m−3, respectively. The main mechanism of extracellular electron transfer is classified as mediated electron transfer, supplemented by direct transfer. Furthermore, the mass balance analysis indicates that methanethiol, S0, S2−, SO42−, HCHO, and CO2 are the main intermediate and end products involved in the hybrid metabolism pathway of DMDS. Overall, these findings may offer basic information for bioelectrochemical degradation of DMDS and facilitate the application of MFC in waste gas treatment. Environmental implicationDimethyl disulfide (DMDS), which features poor solubility, odorous smell, and refractory property, is a typical pollutant emitted from the petrochemical industry. For the first time, we develop an MFC system for DMDS degradation. The superior DMDS removal load per unit reactor volume is 6.18–2440 times those of conventional biodegradation processes in literature. Both the electron transfer route and the hybrid metabolism pathway of DMDS are cleared in this work. Overall, these findings give an in-depth understanding of the bioelectrochemical DMDS degradation mechanism and provide an efficient alternative for DMDS removal.

Performance and mechanism of innovative two-phase partitioning microbial fuel cell for effective propanethiol treatment

A two-phase partitioning microbial fuel cell (TPPMFC) was first time constructed to enhance the mass transfer and removal efficiency of hydrophobic volatile organic sulfur compounds by adding silicone particles as solid non-aqueous phase. The results indicated that the output voltage was gradient increased with the concentration of selected mode propanethiol increased from 100 mg/L to 500 mg/L, but the complete degradation cycle of PT was extended from 12 h to 78 h. The obvious enhancement of microbial fuel cell performance was achieved with 2 % (v/v) 0.4 mm silicone particle. The output voltage increased by 95.6 % ± 12 %, the removal efficiency of 500 mg/L of propanethiol increased from 67 % ± 3 % to 91 % ± 4 % within 24 h, and the maximum power density was 26.23 mW/m2 (72.5 % improvement). The live microorganism on the anodic biofilm was maintained at 95 % after a long-term operation, which was benefited from the fluid shear force caused by agitated anolyte and solid non-aqueous phase. Moreover, the dominant microbial in the TPPMFC were Pseudomonas, sulfate-reduced Aquamicrobium, and Acinetobacter, and the propanethiol was biodegraded by them via two different pathways compared with the traditional ones. Finally, the mechanisms of propanethiol removal and power generation in the TPPMFC were analyzed. It is believed that the results provide insight into the application of two-phase distribution technology for the removal of hydrophobic volatile organic compounds in bioelectrochemical systems.

Online detection of trace volatile organic sulfur compounds in a complex biogas mixture with proton-transfer-reaction mass spectrometry

Online monitoring of trace contaminants, especially sulfur-containing compounds, is critical in biogas plants to protect downstream process steps, e.g., fuel cells or catalysts. The high biogas purity requirement for fuel cell applications and the presence of a myriad of unknown contaminants at different concentration levels require untargeted measurement techniques with high sensitivity and high dynamic range. Here, we present an online, real-time measurement of trace contaminants in the cleaning stream of a biogas plant with a Vocus proton-transfer-reaction mass spectrometer (Vocus-PTR-MS). We identified more than 300 Volatile Organic Compounds (VOCs) in the raw biogas in the 30–400 m/z range, with total concentrations varying in 54.6–548.3 ppmv on different days. Among these, more than 30 were Volatile Organic Sulfur Compounds (VOSCs), with total concentration in the range of 0.3–9.3 ppmv during measurement days and dimethyl sulfide (C2H6S, DMS) was the most dominant VOSC. Typical biogas tracers were also identified in the ambient air around the biogas plant at low ppbv levels. These results confirm that VOCUS-PTR-MS can be a rapid, scientific online tool of choice to monitor a biogas facility and, hence, shows excellent ability to characterize biogas production.