Deodorization of dimethyl sulfide using a discharge approach at room temperature

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

Formation of particulate sulfur species (sulfate and methanesulfonate) during summer over the Eastern Mediterranean: A modelling approach

To improve our understanding of the mechanisms of particulate sulfur formation (non sea-salt sulfate, nss-SO₄²⁻) and methanesulfonate (MS_x used here to represent the sum of gaseous methanesulfonic acid, MSA, and particulate methanesulfonate, MS⁻) in the eastern Mediterranean and to evaluate the relative contribution of biogenic and anthropogenic sources to the S budget, a chemical box model coupled offline with an aerosol–cloud model has been used.Based on the measurements of gaseous dimethyl sulfide (DMS) and methanesulfonic acid (MSA) and the MSA sticking coefficient determined during the Mediterranean Intensive Oxidant Study (MINOS) experiment, the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to be about 0.3%. Consequently, MSA production from gas-phase oxidation of DMS is too small to explain the observed levels of MS⁻. On the other hand, heterogeneous reactions of dimethyl sulfoxide (DMSO) and its gas-phase oxidation product methanesulfinic acid (MSIA) can account for most of the observed MS⁻ levels. The modelling results indicate that about 80% of the production of MS⁻ can be attributed to heterogeneous reactions.Observed submicron nss-SO₄²⁻ levels can be fully explained by homogeneous (photochemical) gas-phase oxidation of sulfur dioxide (SO₂) to sulfuric acid (H₂SO₄), which is subsequently scavenged by (mainly submicron) aerosol particles. The predominant oxidant during daytime is hydroxyl radical (OH) showing very high peak levels in the area during summer mostly under cloudless conditions. Therefore, during summer in the east Mediterranean, heterogeneous sulfate production appears to be negligible. This result is of particular interest for sulfur abatement strategy. On the other hand only about 10% of the supermicron nss-SO₄²⁻ can be explained by condensation of gas-phase H₂SO₄, the rest must be formed via heterogeneous pathways.Marine biogenic sulfur emissions contribute up to 20% to the total oxidized sulfur production (SO₂ and H₂SO₄) in good agreement with earlier estimates for the area.     

Atmospheric methanethiol emitted from a pulp and paper plant on the shore of Lake Baikal

On-site measurement of methanethiol (CH₃SH) was performed for three years on ships and cars near a pulp and paper plant standing on the shore of Lake Baikal in Siberia, Russia, to investigate the behavior and impact of atmospheric CH₃SH emitted from a point source. Despite its strong odor, there are few reports on atmospheric CH₃SH, while many investigations have been carried out on dimethyl sulfide (DMS). In this work, CH₃SH and DMS were measured every 15 min by a recently developed automated instrument based on single column trapping/separation and chemiluminescence measurement. Hydrogen sulfide, sulfur dioxide and ozone were also measured simultaneously by individual instruments. Of these sulfur compounds, CH₃SH was dominant and its concentration sometimes reached several tens of ppbv. The concentration of CH₃SH was high at night, because of the lack of photodecomposition and local winds from the mountain to the lake. Such time variation was marked in the summer. The CH₃SH level decreased significantly downwind, while decreases in concentrations of other compounds such as DMS and SO₂ were relatively small. From these temporal and spatial variations, the behavior of CH₃SH is described in this paper. The impact of CH₃SH near the Siberian big sources is discussed with the presented data.     

Photochemical oxidation and dispersion of gaseous sulfur compounds from natural and anthropogenic sources around a coastal location

The photochemical oxidation and dispersion of reduced sulfur compounds (RSCs: H₂S, CH₃SH, DMS, CS₂, and DMDS) emitted from anthropogenic (A) and natural (N) sources were evaluated based on a numerical modeling approach. The anthropogenic emission concentrations of RSCs were measured from several sampling sites at the Donghae landfill (D-LF) (i.e., source type A) in South Korea during a series of field campaigns (May through December 2004). The emissions of natural RSCs in a coastal study area near the D-LF (i.e., source type N) were estimated from sea surface DMS concentrations and transfer velocity during the same study period. These emission data were then used as input to the CALPUFF dispersion model, revised with 34 chemical reactions for RSCs. A significant fraction of sulfur dioxide (SO₂) was produced photochemically during the summer (about 34% of total SO₂ concentrations) followed by fall (21%), spring (15%), and winter (5%). Photochemical production of SO₂ was dominated by H₂S (about 55% of total contributions) and DMS (24%). The largest impact of RSCs from source type A on SO₂ concentrations occurred around the D-LF during summer. The total SO₂ concentrations produced from source type N around the D-LF during the summer (a mean SO₂ concentration of 7.4 ppbv) were significantly higher than those (≤0.3 ppbv) during the other seasons. This may be because of the high RSC and SO₂ emissions and their photochemistry along with the wind convergence.     

Ambient and Source SO2 Detector Based on a Fluorescence Method

The principle of this detector is based on the measurement of the intensity of the ultraviolet fluorescence of SO₂ produced by absorption of the Zn 2138 Å or Cd 2288 Å line. The fluorescence intensity was found to be linear from 0.1 to 500 ppm of SO₂ in air with the Zn lamp and from 0.1 to 1600 ppm with the Cd lamp. The detection limit at present is about 20 ppb. There is no detectable interference from O₃, H₂S, NO₂, CO₂, CO, or H₂, although the presence of a large concentration of CS₂ (500 times as much as SO₂) NO (500 times) or C₂H₄ (4000 times) interferes with the measurement. The presence of 2% H₂0 reduces the signal by 25%, while up to 1 % CH₄ has almost no effect.     

Abatement of Sulfur Hexafluoride Emissions from the Semiconductor Manufacturing Process by Atmospheric-Pressure Plasmas

Abstract

Sulfur hexafluoride (SF₆) is an important gas for plasma etching processes in the semiconductor industry. SF₆ intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF₆ abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes—dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)—were employed and evaluated. Experimental results indicated that as much as 91% of SF₆ was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF₆, 12% oxygen (O₂), and 40% argon (Ar), with nitrogen (N₂) as the carrier gas. Four additives, including Ar, O₂, ethylene (C₂H₄), and H₂O_(g), are effective in enhancing SF₆ abatement in the range of conditions studied. DBD achieves a higher SF₆ removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF₆ is mainly converted to SOF₂,SO₂F₄, sulfur dioxide (SO₂), oxygen difluoride (OF₂), and fluoride (F₂). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF₆ emissions.     

Carbonyl sulfide,dimethyl sulfide and carbon disulfide in the Pearl River Delta of southern China: Impact of anthropogenic and biogenic sources

Reduced sulfur compounds (RSCs) such as carbonyl sulfide (OCS), dimethyl sulfide (DMS) and carbon disulfide (CS₂) impact radiative forcing, ozone depletion, and acid rain. Although Asia is a large source of these compounds, until now a long-term study of their emission patterns has not been carried out. Here we analyze 16 months of RSC data measured at a polluted rural/coastal site in the greater Pearl River Delta (PRD) of southern China. A total of 188 canister air samples were collected from August 2001 to December 2002. The OCS and CS₂ mixing ratios within these samples were higher in autumn/winter and lower in summer due to the influence of Asian monsoon circulations. Comparatively low DMS values observed in this coastal region suggest a relatively low biological productivity during summer months. The springtime OCS levels in the study region (574 ± 40 pptv) were 25% higher than those on other East Asia coasts such Japan, whereas the springtime CS₂ and DMS mixing ratios in the PRD (47 ± 38 pptv and 22 ± 5 pptv, respectively) were 3–30 times lower than elevated values that have been measured elsewhere in East Asia (Japan and Korea) at this time of year. Poor correlations were found among the three RSCs in the whole group of 188 samples, suggesting their complex and variable sources in the region. By means of backward Lagrangian particle release simulations, air samples originating from the inner PRD, urban Hong Kong and South China Sea were identified. The mean mixing ratio of OCS in the inner PRD was significantly higher than that in Hong Kong urban air and South China Sea marine air (p < 0.001), whereas no statistical differences were found for DMS and CS₂ among the three regions (p > 0.05). Using a linear regression method based on correlations with the urban tracer CO, the estimated OCS emission in inner PRD (49.6 ± 4.7 Gg yr^?1) was much higher than that in Hong Kong (0.32 ± 0.05 Gg yr^?1), whereas the estimated CS₂ and DMS emissions in the study region accounted for a very few percentage of the total CS₂ and DMS emission in China. These findings lay the foundation for better understanding sulfur chemistry in the greater PRD region of southern China.     

Sulfuric odorous compounds emitted from pig-feeding operations

The objective of the study was to quantify the concentration and emission levels of sulfuric odorous compounds emitted from pig-feeding operations. Five types of pig-housing rooms were studied: gestation, farrowing, nursery, growing and fattening rooms. The concentration range of sulfuric odorous compounds in these pig-housing rooms were 30–200 ppb for hydrogen sulfide (H₂S), 2.5–20 ppb for methyl mercaptan (CH₃SH), 1.5–12 ppb for dimethyl sulfide (DMS; CH₃SCH₃) and 0.5–7 ppb for dimethyl disulfide (DMDS; CH₃S₂CH₃), respectively. The emission rates of H₂S, CH₃SH, DMS and DMDS were estimated by multiplying the average concentration (mg m⁻³) measured near the air outlet by the mean ventilation rate (m³ h⁻¹) and expressed either per area (mg m⁻² h⁻¹) or animal unit (AU; liveweight of the pig, 500 kg) (mg pig⁻¹ h⁻¹). As a result, the emission rates of H₂S, CH₃SH, DMS and DMDS in the pig-housing rooms were 14–64, 0.8–7.3, 0.4–3.4 and 0.2–1.9 mg m⁻² h⁻¹, respectively, based on pig's activity space and 310–723, 18–80, 9–39 and 5–22 mg AU⁻¹ h⁻¹, respectively, based on pig's liveweight, which indicates that their emission rates were similar, whether based upon the pig's activity space or liveweight. In conclusion, the concentrations and emission rates of H₂S were highest in the fattening room followed by the growing, nursery, farrowing and gestation rooms whereas those of CH₃SH, DMS and DMDS concentrations were largest in the growing room followed by the nursery, gestation and farrowing rooms.     

Removal of SO2 from Simulated Flue Gases Using Non-Thermal Plasma-Based Microgap Discharge

Abstract

The removal of sulfur dioxide (SO₂) from simulated flue gases streams (N₂/O₂/H₂O/SO₂) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al₂O₃) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH·) radicals were produced using the ionization of O₂ and H₂O to further the conversion of SO₂ into sulfuric acid (H₂SO₄) at 120° C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O₂ and H₂O increased the production of OH· radicals resulting in enhanced removal of SO₂ from gas streams. With the test and analysis, a number of H₂SO₄ droplets were produced in experiment. Therefore, a new method for removal of SO₂ in semidry method without ammonia (NH₃) additive was found.     

A simulation of sulfur wet deposition and its dependence on the inflow of sulfur species to storms

Numerical precipitation scavenging models are used to investigate the relationship between the inflow concentrations of sulfur species to precipitation systems and the resulting sulfur wet deposition. Simulations have been made for summer and winter seasons using concentration ranges of SO₂, aerosol SO₄²⁻, H₂O₂ and O₃ appropriate for the eastern U.S. summer simulations use one-dimensional timedependent convective cloud and scavenging models; winter simulations use two-dimensional steady-state warm-frontal models. Sulfur scavenging mechanisms include nucleation scavenging of aerosol, aqueous reactions of H₂O₂, O₃ and HCHO with S(IV), and nonreactive S(IV) scavenging. Over the wide range of conditions that have been examined, the relation between sulfur inflow and sulfur wet deposition varies from nearly linear to strongly nonlinear. The degree of nonlinearity is most affected by aerosol SO₄²⁻ levels and relative levels of SO₂ vs H₂O₂. Higher aerosol SO₄²⁻ levels (as found in summer) produce a more linear relation. The greatest nonlinearity occurs when SO₂ exceeds H₂O₂. Winter simulations show more nonlinearity than summer simulations.     

FT-IR product study on the photo-oxidation of dimethyl sulphide in the presence of NOx—temperature dependence

The products of the OH radical-initiated oxidation of dimethyl sulphide (DMS) have been investigated as a function of temperature (284, 295, and 306 K) and different initial NO_x (NO+NO₂) concentrations: initial NO was varied between 434 and 2821 ppb and NO₂ between 135 and 739 ppb. The experiments were performed at 1000 mbar total pressure in synthetic air using the photolysis of H₂O₂ as the OH-radical source and FT-IR spectroscopy to monitor reactants and products. The major sulphur-containing products identified were SO₂, dimethyl sulphoxide (DMSO), dimethyl sulphone (DMSO₂), methane sulphonic acid (MSA), methane sulphonyl peroxynitrate (MSPN) and OCS. The variation of the product yields with temperature and NO_x concentration are consistent with the occurrence of both addition and abstraction channels in OH radical-initiated oxidation of DMS. Distinct trends in the yields of the various products have been observed as a function of temperature, initial NO_x conditions and also reaction time as NO is consumed in the system. Increasing the initial NO concentration was found to depress the DMSO, SO₂ and OCS formation yields and enhance those of DMSO₂, MSA and MSPN. The yield–time behaviour of DMSO₂ is supportive of a formation mechanism involving addition of O₂ to a (CH₃)₂SOH adduct, formed via the addition channel, followed by sequential reactions with NO and O₂. The mechanisms controlling the concentration–time profiles of the individual products under the present experimental conditions are discussed in detail and consideration is given to possible implications for the photo-oxidation of DMS under ambient conditions.     

Monitoring of atmospheric reduced sulfur compounds and their oxidation in two coastal landfill areas

In this study, the distribution characteristics of reduced sulfur compounds (RSCs) in ambient air were investigated in two coastal landfill (LF) facilities and their surrounding areas. The photochemical conversion of RSCs to sulfur dioxide (SO₂) was also evaluated using a photochemical box model (PCBM). Measurements of RSCs were carried out from both in and around areas of two coastal LFs in Gunsan (G) and Donghae (D) city, Korea during several field campaigns (May through December 2004). The dominant RSCs at the Gunsan landfill (G-LF) were found to be DMS and H₂S, whereas those at the Donghae landfill (D-LF) were H₂S and DMDS. The concentrations of DMS at these study sites were likely to be affected not only by LF processes but also by an oceanic source, while such a pattern was more prominent at the D-LF. The chemical species of RSCs that can exert significant influences on the photochemical production of SO₂ in the LF environment were identified to be H₂S, DMS, or DMDS.     

Carbon Disulfide and Hydrogen Sulfide Removal with a Peat Biofilter

ABSTRACT

Simultaneous removal of H₂S and CS₂ was studied with a peat biofilter inoculated with a Thiobacillus strain that oxidizes both compounds in an acidic environment. Both sulfurous gases at concentrations below 600 mg S/m³ were efficiently removed, and the removal efficiencies were similar, 99%, with an empty bed retention time (EBRT) of more than 60 sec. Concentrations greater than 1300-5000 mg S/m³ caused overloading of the filter material, resulting in high H₂SO₄ production, accumulation of elemental sulfur, and reduced removal efficiency. The highest sulfur removal rate achieved was 4500 g-S/day/m³ filter material. These results indicate that peat is suitable as a biofilter material for the removal of a mixture of H₂S and CS₂ when concentrations of gases to be purified are low (less than 600 mg/m³), but it is still odorous and toxic to the environment and humans.     

A Device for Measuring Volatile Organic-Carbon Emissions from Cooling-Tower Water

A manual method for measuring reduced sulfur compounds in kraft pulp mill and sulfur recovery plant emissions was evaluated. The method involves removing SO₂ from the gas stream (if present) with a citric acid-potassium citrate buffer that passes reduced sulfur compounds; thermal oxidation of all reduced sulfur compounds to SO₂; collection of the SO₂ in H₂O₂; and a titrimetric analysis of the H₂O₂ for SO₄ ^2?. A heated filter removes alkaline particulate matter that would produce a negative interference if absorbed by the buffer. When used at kraft pulp mills, the method agrees closely with Reference Method 16, provided that nonregulated reduced sulfur compounds, such as carbonyl sulfide, are not present in the emissions. At sulfur recovery plants, nonregulated reduced sulfur compounds, such as thiophene, are likely to be present in the emissions and will produce a positive bias in the results obtained with this method. The precision of the method ranges from 1 to 7 percent relative standard deviation.     

The Kinetics of Catalytic Incineration of Dimethyl Sulfide and Dimethyl Disulfide over an MnO/Fe2O3 Catalyst

ABSTRACT

The catalytic incineration of dimethyl sulfide and dimethyl disulfide [(CH₃)₂S and (CH₃)₂S₂] over an MnO/Fe₂O₃ catalyst was carried out in a bench-scale catalytic incinerator. Three kinetic models (i.e., the power-rate law, the Mars and Van Krevelen model, and the Langmuir-Hinshelwood model) were used to analyze the results. A differential reactor design was used for best fit of kinetic models in this study. The results show that the Langmuir-Hinshelwood model may be feasible to describe the catalytic incineration of (CH₃)₂S and (CH₃)₂S₂. This suggests that the chemical adsorption of O₂ molecules is important in this incineration.     

Analysis of Kraft-Mill,Sulfur-Containing Gases with GLC lonization Detectors

The technique includes the use of two chromatographic columns in series to separate O₂, N₂, CO, CO₂, H₂O, H₂S, SO₂ and CH₃SH. Column 1, containing Triton 45 on Chromosorb, separates H₂O, H₂S, SO₂ and CH₃SH. Column 2, packed with Molecular Sieve, separates O₂, N₂, CO and CO₂. The conditions required to obtain adequate sensitivity and separation are discussed.     

空速和二氧化碳对沼气脱硫剂硫容确定的影响

为了弄清空速与二氧化碳含量对氧化铁脱硫剂硫容确定的影响,分别在实验气源为纯硫化氢,空速为40、80、120和160 h-1以及实验气源为二氧化碳含量分别在0%、20%、40%和80%,其余为硫化氢,空速为80 h-1条件下,对T502(粗脱硫剂)和HXT-2(精脱硫剂)2种氧化铁脱硫剂进行了不同测试条件对氧化铁硫容确定影响的研究。研究结果表明,T502和HXT-2氧化铁脱硫剂硫容测试结果随着空速和二氧化碳含量增加而减少,结果显示了在空速较低条件下(120h-1),二氧化碳含量在40%以下时对氧化铁脱硫剂硫容测试结果影响不大,但二氧化碳含量在40%以上时,对氧化铁脱硫剂硫容测试结果影响显著。     

Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway

Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H₂O₂), alkaline ozonation (O₃, pH = 11), peroxone (O₃/H₂O₂), and Fenton reagent oxidation (Fe²⁺/H₂O₂). UV/H₂O₂ was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C₇ to C₂), while sulfate (SO₄ ^2?) and fluoride (F^?) were found to be the final products. The high yields of SO₄ ^2? and F^? indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H₂O₂ condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential “flake off” of CF₂ unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.     

Performance Characterization and Optimization of the AgNO3-Filter/FMA Fluorimetric Method for Atmospheric H2S Measurements

This sensitive, albeit precarious, method for measuring ppb-ppt (V/V) concentrations of H₂S was examined for various sources of potential error within the procedure. Filter preparation, filter storage, filter extraction, fluorimetric reagent stabilities, matrix differences between standards and samples, and possible interferences from other sulfur-containing compounds were separately studied for their effects on the analytical performance of the method. The overall method showed no Interference from SO₂, CS₂, COS, CH₃SH, CH₃SCH₃, and SO₄ ^-2. To minimize bias and obtain a reliable estimate of precision, the method should be calibrated with H₂S standards rather than liquid bisulfide standards. The measurement precision is a function of the quantity of H₂S collected as Ag₂S and/or AgSH on the impregnated filters. Because of the method’s linear dynamic range, sufficient air should be sampled to achieve filter loadings of 15 to 35 ng S/filter. A quality control method based on fluorescein mercuric acetate (FMA) is presented that ensures data quality while reducing the otherwise frequent need for fluori-metric calibration.     

Variability of SO2, CO,and light hydrocarbons over a megacity in Eastern India: effects of emissions and transport

The Indo-Gangetic plain (IGP) has received extensive attention of the global scientific community due to higher levels of trace gases and aerosols over this region. Satellite retrievals and model simulations show that, in particular, the eastern part IGP is highly polluted. Despite this attention, in situ measurements of trace gases are very limited over this region. This paper presents measurements of SO₂, CO, CH₄, and C₂–C₅ NMHCs during March 2012–February 2013 over Kolkata, a megacity in the eastern IGP, with a focus on processes impacting their levels. The mean SO₂ and C₂H₆ concentrations during winter and post-monsoon periods were eight and three times higher compared to pre-monsoon and monsoon. Early morning enhancements in SO₂ and several NMHCs during winter connote boundary layer effects. Daytime elevations in SO₂ during pre-monsoon and monsoon suggest impacts of photo-oxidation. Inter-species correlations and trajectory analysis evince transport of SO₂ from regional combustion sources (e.g., coal burning in power plants, industries) along the east of the Indo-Gangetic plain impacting SO₂ levels at the site. However, C₂H₂ to CO ratio over Kolkata, which are comparable to other urban regions in India, show impacts of local biofuel combustions. Further, high levels of C₃H₈ and C₄H₁₀ evince the dominance of LPG/petrochemicals over the study location. The suite of trace gases measured during this study helps to decipher between impacts of local emissions and influence of transport on their levels.