Annual cycle of gaseous sulfur emissions from a New England Spartina alterniflora marsh

A flow-through chamber was used to measure the net gaseous sulfur fluxes (emission minus uptake) to the atmosphere from an area of Spartina alterniflora in a New England salt marsh. The fluxes of hydrogen sulfide, dimethyl sulfide, carbonyl sulfide, carbon disulfide and dimethyl disulfide were measured monthly over a year to obtain the annual emission estimates. Peak releases of the various sulfur gases did not occur simultaneously but were measured from July through to October depending on the individual sulfur species. The total annual emission was estimated to be 5.8 g S m⁻² y⁻¹, with dimethyl sulfide (49% of the total) and hydrogen sulfide (35% of the total) the major components emitted. The emissions of the other sulfur gases were nearly 10-fold lower.     

Sulfur Gas Emissions From Stored Flue Gas Desulfurization Sludges

The emissions of volatile sulfur-containing compounds from 13 flue gas desulfurization (FGD) sludge field storage sites have been characterized. Sulfur gas emissions from the sludge surfaces were determined by measuring the sulfur gas enhancement of sulfur-free sweep air passing through a dynamic emission flux chamber placed over selected sampling sites. Samples of the enclosure sweep air were cryogenically concentrated in surface-deactivated Pyrex “U” traps. Analyses were conducted by wall-coated, open-tubular, capillary column, cyrogenic gas chromatography using a sulfur-selective, flame photometric detector. Several major variables associated with FGD sludge production processes were examined in relation to the measured range and variations in sulfur fluxes including: (a) the sulfur dioxide scrubbing reagent used, (b) sludge sulfite oxidation, (c) “unfixed” or “fixed” FGD sludge, and (d) ponding or landfill storage. The composition and concentration of the measured sulfur gas emissions were found to vary with the type of sludge, the effectiveness of rainwater drainage from the landfill surface, the method of impoundment, and the sulfate/sulfite ratio of the sludge. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide were identified in varying concentrations and ratios in the FGD sludge emissions. In addition, up to four unidentified organo- sulfur compounds were found in the emissions from four FGD sludges. The sulfur flux from one FGD storage pond was analyzed by gas chromatography-single ion monitoring mass spectrometry. In addition to the four identified sulfur compounds, this flux contained large concentrations of benzene, toluene, and α-pinene. The measured, total sulfur emissions ranged from less than 0.01 to nearly 0.3 kg of sulfur per day for an equivalent 100 acre (40.5 hectare) sludge impoundment surface.     

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.     

Treatment of odor by a seashell biofilter at a wastewater treatment plant

Biofilters are becoming an increasingly popular treatment device for odors and other volatiles found at wastewater treatment plants. A seashell media based biofilter was installed in April 2011 at Lake Wildwood Wastewater Treatment Plant located in Penn Valley, California. It was sampled seasonally to examine its ability to treat odorous compounds found in the air above the anaerobic equalization basin at the front end of the plant and to examine the properties of the biofilter and its recirculating water system. The odor profile method sensory panels found mainly sulfide odors (rotten eggs and rotten vegetable) and some fecal odors. This proved to be a useful guidance tool for selecting the required types of chemical sampling. The predominant odorous compounds found were hydrogen sulfide, methyl mercaptan and dimethyl sulfide. These compounds were effectively removed by the biofilter at greater than 99% removal efficiency therein reducing the chemical concentrations to below their odor thresholds. Aldehydes found in the biofilter were below odor thresholds but served as indicators of biological activity. Gas chromatography with mass spectrometry and gas chromatography with sensory detection showed the presence of dimethyl disulfide and dimethyl trisulfide as well, but barely above their respective odor thresholds. The neutrality of the pH of the recirculating water was variable depending on conditions in the biofilter, but a local neutral pH was found in the shells themselves. Other measurements of the recirculating water indicated that the majority of the bio-activity takes place in the first stage of the biofilter. All measurements performed suggest that this seashell biofilter is successful at removing odors found at Lake Wildwood. This study is an initial examination into the mechanism of the removal of odorous compounds in a seashell biofilter.

Implications:?This paper presents a thorough examination of a seashell media biofilter, a sustainable treatment technology used to remove reduced sulfide compounds. The durable performance of the seashell biofilter ensures that odors will be adequately controlled, preventing odor nuisance to surrounding residences, which is an emerging problem faced by waste management facilities. The odor profile method technique used in this study can be applied in many situations by waste management facilities and regulatory air management organizations for source tracking in relation to prevention and management of odor complaints, respectively.     

Cycling of volatile organic sulfur compounds in anaerobically digested biosolids and its implications for odors.

The objectives of this research were to elucidate the mechanisms for production and degradation of volatile organic sulfur compounds (VOSCs), key odor causing compounds produced by biosolids. These compounds included methanethiol (MT), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS). A series of experiments were used to probe various pathways hypothesized to produce and degrade these VOSCs. The production of MT was found to mainly occur from degradation of methionine and the methylation of hydrogen sulfide. DMS was formed through the methylation of MT. DMDS was formed by MT oxidation. All three of the VOSCs were readily degraded by methanogens and a cyclic pathway was proposed to describe the production and degradation of VOSCs. The research demonstrated that the main source of VOSCs was the biodegradation of protein within the biosolids and the results provided a framework for understanding the production of odor from anaerobically digested sludges before and after dewatering.     

Spatial and diel variability in the emissions of some biogenic sulfur compounds from a Florida Spartinaalterniflora coastal zone

Emission rates of the biogenic reduced sulfur gases dimethyl sulfide, dimethyl disulfide, carbon disulfide and hydrogen sulfide were measured from several environments within a Florida Spartina alterniflora coastal zone. Spatial and diel variability was observed in the emission rates of all the sulfur gases. The speciation and magnitude of sulfur emissions can be related to site elevation and the spatial variability of vegetation coverage. Dimethyl sulfide appears to be a metabolic byproduct of S. alterniflora.     

Sulfur Gas Emissions from Flue Gas Desulfurization Sludge Ponds

This paper presents initial measurement data on the emission of volatile, reduced sulfur-containing gases from flue gas desulfurization (FGD) storage ponds. Several different types of FGD stored sludges were studied including lime, limestone, and mixtures of fly ash and lime or limestone residues, some of which had been chemically stabilized. The volatile sulfur gas emissions were cryogenically concentrated and determined by wall-coated, open-tubular capillary column gas chromatography using a flame photometric detector. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and an unusual, unidentified sulfur-containing compound were found in the gaseous pond flux. Benzene, toluene, and α-pinene were also identified by gas chromatography-single ion monitoring mass spectrometry. The total reduced sulfur gas emission from a 100 acre pond approximated 2.0 kg day^?1 (as sulfur).     

Mitigation of odor causing emissions—Bench-scale investigation

Emissions of malodors are considered to be the greatest threat to the compost industry. In work presented here, several simple odor mitigation alternatives were investigated for their effectiveness in preventing the release of common odorants, such as terpenes, ammonia, and reduced sulfur compounds. The mitigation methods studied included the use of a blanket of finished compost, compost amendment mixed within the feedstock, odor neutralizing agents (ONAs), and oxygen release compounds (ORCs). Among the mitigation alternatives investigated in this study, the use of finished compost as a blanket and finished compost as an amendment yielded the most conclusive and significant results. Both of these alternatives yielded a substantial emission reduction for terpenes, ammonia, and reduced sulfur compounds. The application of finished compost blanket resulted in up to 95% reduction of terpene and 25% reduction of ammonia emissions. Blending the feedstock with finished compost also provided substantial reduction of terpene emissions ranging from 73.6 to 93.1% at the 24% blending ratio, and up to 85% ammonia reduction a the 35% blending ratio. Use of finished compost also provided 75% lower reduced sulfur compound emissions at the 12% blending ratio. Misting and application of odor neutralizing agents did not result in any consistent reduction in emissions for any of the odorous compounds tested.

Implications The odor emissions from composting are often considered to be the biggest threat to composting facilities. Because most facilities cannot afford enclosures and contained composting vessels, there is a need to inexpensively and effectively control the odor emissions from composting facilities. The findings of this research can lead the way for efforts to control odor easily and cost effectively. In fact, the application of a compost blanket for odor control is already gaining acceptance by the composting industry.     

Occurrence and abatement of volatile sulfur compounds during biogas production

Volatile sulfur compounds (VSCs) in biogas originating from a biogas production plant and from a municipal sewage water treatment plant were identified. Samples were taken at various stages of the biogas-producing process, including upgrading the gas to vehicle-fuel quality. Solid-phase microextraction was used for preconcentration of the VSCs, which were subsequently analyzed using gas chromatography in combination with mass spectrometry. Other volatile organic compounds present also were identified. The most commonly occurring VSCs in the biogas were hydrogen sulfide, carbonyl sulfide, methanethiol, dimethyl sulfide, and dimethyl disulfide, and hydrogen sulfide was not always the most abundant sulfur (S) compound. Besides VSCs, oxygenated organic compounds were commonly present (e.g., ketones, alcohols, and esters). The effect of adding iron chloride to the biogas reactor on the occurrence of VSCs also was investigated. It was found that additions of 500-g/m3 substrate gave an optimal removal of VSCs. Also, the use of a prefermentation step could reduce the amount of VSCs formed in the biogas process. Moreover, in the carbon dioxide scrubber used for upgrading the gas, VSCs were removed efficiently, leaving traces (ppbv levels). The scrubber also removed other organic compounds.     

Deodorization of Dimethyl Sulfide Using a Discharge Approach at Room Temperature

Abstract

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, formal-dehyde, 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.     

Degradation of aldrin and endosulfan in rotary drum and windrow composting

Removal efficiencies, kinetics and degradation pathways of aldrin, endosulfan α and endosulfan β in vegetable waste were evaluated during rotary drum and conventional windrow composting. The highest percentage removal of aldrin, endosulfan α and endosulfan β in rotary drum composting was 86.8, 83.3 and 85.3% respectively, whereas in windrow composting, it was 66.6%, 77.7% and 67.2% respectively. The rate constant of degradation of aldrin, endosulfan α and endosulfan β during rotary drum composting ranged from 0.410–0.778, 0.057–0.076 and 0.009–0.061 day^?1 respectively. The pathways of degradation of these pesticides in composting process were proposed. Metabolites dieldrin and 1 hydroxychlorodene formed during composting of aldrin in the vegetable waste indicated the occurrence of epoxidation reaction and oxidation of bridge carbon of aldrin containing the methylene group. Formation of chloroendic acid and chloroendic anhydride during composting of endosulfan containing vegetable waste support the occurrence of endosulfan sulfate and dehydration reaction respectively.     

Studies on a New Method of Simultaneously Removing Sulfur Dioxide and Oxides of Nitrogen from Combustion Gases

Simultaneous reduction of SO₂ and NO by catalyzed reaction with carbon monoxide at space rates approaching 10⁴ vol/vol/hr has been shown. The reaction of sulfur dioxide with carbon monoxide results in the formation of carbon dioxide and elemental sulfur. Nitric oxide reacts with carbon monoxide to form carbon dioxide and molecular nitrogen. Metals supported on alumina appear to be the preferred catalysts. Among the effective metals are copper, silver, and palladium. A side reaction of carbon monoxide with elemental sulfur to form carbonyl sulfide requires that the initial amount of carbon monoxide be stoichio-metric for the amount of sulfur dioxide plus nitric oxide present. A furnace employing this method would have to be operated at low excess air, near stoichiometric fuel/air, or possibly slightly on the rich side.     

Bacteria additives to the changes in gaseous mass transfer from stored swine manure

Abstract

A bacteria additives treatment experiment in assessing the changes in gaseous mass transfer from stored swine manure is presented. The experiment is tested for ammonia, methane, hydrogen sulfide, and carbon dioxide emission data sampled from pilot swine manure columns and analyzed by GC/MS. The result shows that bacteria additives slightly reduce the methane and carbon dioxide releases, while the same additives do not show any effect on the reduction of ammonia. The hydrogen sulfide contents of stored swine manure continued to be low. Gas concentrations emitted from treated and untreated stored swine manure were: 3.76 and 2.2 ppm for methane, 0.35 and 0.11 ppm for ammonia, and 1000 and 470 ppm for carbon dioxide, respectively. A simple model to estimate gas emission rates is also developed from the viewpoint of two‐film resistance theory. The average emission rates calculated from the model for methane, ammonia, and carbon dioxide are respectively: 0.01, 0.0005, and 13.98 g/min from untreated stored manure; while 0.07, 0.096, and 0.55 g/min from treated manure. The emission model also indicates that for most gaseous pollutants of environmental concern, liquid phase transfer coefficient controls the rate of volatile compounds emitted from stored swine manure and gas phase transfer coefficient has insignificant effect in the calculation of overall mass transfer coefficient.     

Occurrence of Carbon Monoxide during Organic Waste Degradation

Abstract

The concentrations of carbon monoxide (CO) and other gases were measured in the emissions from solid waste degradation under aerobic and anaerobic conditions during laboratory and field investigations. The emissions were measured as room temperature headspace gas concentrations in reactors of 1, 30, and 150 L, as well as sucked gas concentrations from windrow composting piles and a biocell, under field conditions. The aerobic composting laboratory experiments consisted of treatments with and without lime. The CO concentrations measured during anaerobic conditions varied from 0 to 3000 ppm, the average being 23 ppm, increasing to 133 ppm when methane (CH₄) concentrations were low. The mean/maximum CO concentrations during the aerobic degradation in the 2-L reactor were 101/194 ppm without lime, 486/2022 ppm with lime, and 275/980 ppm in the 150-L reactors. The presence of CO during the aerobic composting followed a rapid decline in O₂ concentrations Significantly higher CO concentrations were obtained when the aerobic degradation was amended with lime, probably because of a more extreme depletion of oxygen. The mean/maximum CO concentrations under field conditions during aerobic composting were 95/1000 ppm. The CO concentrations from the anaerobic biocell varied from 20 to 160 ppm. The hydrogen sulfide concentrations reached almost 1200 ppm during the anaerobic degradation and 67 ppm during the composting experiments. There is a positive correlation between the CO and hydrogen sulfide concentrations measured during the anaerobic degradation experiments.     

Effectiveness of porous covers for control of ammonia, reduced sulfur compounds, total hydrocarbons, selected volatile organic compounds, and odor from hog manure storage lagoons

Anaerobic lagoons are a major source of odor at concentrated animal feeding operations. Seven different kinds of artificial (geotextile and polyethylene foam) and natural (straw and redwood) permeable lagoon covers were evaluated for their potential to reduce odorous emissions generated by anaerobic waste lagoons. A novel floating sampling raft was constructed and used to simultaneously evaluate the effectiveness of lagoon covers on an operating swine waste lagoon. The air collected from the raft was evaluated for odor, total reduced sulfur (TRS) compounds, ammonia, total hydrocarbons, dimethyldisulfide, and trimethylamine. The emission rates from the lagoon were highly variable both temporally and spatially. All of the lagoon covers substantially reduced TRS emissions and odor. Geotextile fabric and a recycled foam cover exhibited the greatest reduction in total hydrocarbon emissions; natural covers were less effective. Because of consistently low emission rates of ammonia, no statistically significant reduction of ammonia emissions were observed from any of the lagoon covers.     

Quality assured measurements of animal building emissions: odor concentrations

Standard protocols for sampling and measuring odor emissions from livestock buildings are needed to guide scientists, consultants, regulators, and policy-makers. A federally funded, multistate project has conducted field studies in six states to measure emissions of odor, coarse particulate matter (PM(10)), total suspended particulates, hydrogen sulfide, ammonia, and carbon dioxide from swine and poultry production buildings. The focus of this paper is on the intermittent measurement of odor concentrations at nearly identical pairs of buildings in each state and on protocols to minimize variations in these measurements. Air was collected from pig and poultry barns in small (10 L) Tedlar bags through a gas sampling system located in an instrument trailer housing gas and dust analyzers. The samples were analyzed within 30 hr by a dynamic dilution forced-choice olfactometer (a dilution apparatus). The olfactometers (AC'SCENT International Olfactometer, St. Croix Sensory, Inc.) used by all participating laboratories meet the olfactometry standards (American Society for Testing and Materials and European Committee for Standardization [CEN]) in the United States and Europe. Trained panelists (four to eight) at each laboratory measured odor concentrations (dilution to thresholds [DT]) from the bag samples. Odor emissions were calculated by multiplying odor concentration differences between inlet and outlet air by standardized (20 degrees C and 1 atm) building airflow rates.     

Occurrence of carbon monoxide during organic waste degradation

The concentrations of carbon monoxide (CO) and other gases were measured in the emissions from solid waste degradation under aerobic and anaerobic conditions during laboratory and field investigations. The emissions were measured as room temperature headspace gas concentrations in reactors of 1, 30, and 150 L, as well as sucked gas concentrations from windrow composting piles and a biocell, under field conditions. The aerobic composting laboratory experiments consisted of treatments with and without lime. The CO concentrations measured during anaerobic conditions varied from 0 to 3000 ppm, the average being 23 ppm, increasing to 133 ppm when methane (CH4) concentrations were low. The mean/maximum CO concentrations during the aerobic degradation in the 2-L reactor were 101/194 ppm without lime, 486/2022 ppm with lime, and 275/980 ppm in the 150-L reactors. The presence of CO during the aerobic composting followed a rapid decline in O2 concentrations Significantly higher CO concentrations were obtained when the aerobic degradation was amended with lime, probably because of a more extreme depletion of oxygen. The mean/maximum CO concentrations under field conditions during aerobic composting were 95/1000 ppm. The CO concentrations from the anaerobic biocell varied from 20 to 160 ppm. The hydrogen sulfide concentrations reached almost 1200 ppm during the anaerobic degradation and 67 ppm during the composting experiments.     

Government Sponsored Air Pollution Research Relating to Agriculture

The absorption of hydrogen sulfide and methyl mercaptan by aqueous solutions of chlorine, sodium hydroxide, and chlorine plus sodium hydroxide was studied using a two-inch diameter absorption column packed with ¼ inch Intalox saddles. Absorption rates were noticeably affected by chemical reactions occurring in the aqueous chlorine and hydroxide media. These solutions were studied as a means of controlling sulfur-containing gas emissions from kraft paper mills. The absorption studies indicated that aqueous chlorine solutions at a pH above 12 were effective absorbents for hydrogen sulfide removal in absorption equipment designed to tolerate sulfur in suspension. The absorption of methyl mercaptan in aqueous chlorine solutions appeared to be impractical since dimethyl disulfide was apparently the only product formed and was stripped from the tower by the gas stream. Sodium hydroxide solution was an effective absorbent for both methyl mercaptan and hydrogen sulfide when hydroxide to sulfide or mercaptan feed ratios were greater than 1 or 1.8, respectively. The mercaptan absorption coefficient was approximately twice that for sulfide absorption.     

Odorous volatile organic sulfides in wastewater treatment plants in Guangzhou, China

Odorous volatile organic sulfides (VOSs) in headspace atmosphere and wastewaters were identified and quantified synchronously in two municipal wastewater treatment plants (WWTPs) in Guangzhou, China. Dimethyl sulfide (DMS), with concentrations ranging from 0.66 to 5.41 mg/m3, was the major VOS in air samples. Carbonyl sulfide (COS), carbon disulfide (CS2), and dimethyl disulfide (DMDS) ranged from 0.01 to 0.21, 0.03 to 0.44, and 0.06 to 1.61 mg/m3, respectively. Methanethiol was not found in any gas samples. The concentrations of DMS in wastewaters ranged from 23.68 to 308.17 mg/m3 and were also the highest values compared with other VOSs, for all of the treatment processes. Methanethiol was detected in all wastewater samples, except that from the aeration tank, which ranged from 113.08 to 216.82 mg/m3. The COS, carbon disulfide, and DMDS in wastewaters ranged from 0.11 to 2.21, 1.37 to 23.29, and 0.24 to 106.75 mg/m3, respectively. Odors from pollution related to VOS were different in the two plants, and they were strongly associated with the characteristics of incoming wastewater and treatment processes. The VOSs in ambient air samples from nearby residential areas downwind of the plant border were also measured, and the results strongly suggested that control measures are needed for odor pollution in the WWTPs to mitigate malodor in the surrounding neighborhoods.     

PTR-MS measurement of partition coefficients of reduced volatile sulfur compounds in liquids from biotrickling filters

Biological air filtration for reduction of emissions of volatile sulfur compounds (e.g., hydrogen sulfide, methanethiol and dimethyl sulfide) from livestock production facilities is challenged by poor partitioning of these compounds into the aqueous biofilm or filter trickling water. In this study, Henry’s law constants of reduced volatile sulfur compounds were measured for deionized water, biotrickling filter liquids (from the first and second stages of a two-stage biotrickling filter), and NaCl solutions by a dynamic method using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) at a temperature range of 3–45 °C. NaCl solutions were used to estimate salting-out constants up to an ionic strength of 0.7 M in order to evaluate the effect of ionic strength on partitioning between air and biofilter liquids. Thermodynamic parameters (enthalpy and entropy of phase exchange) were obtained from the measured partition coefficients as a function of temperature. The results show that the partition coefficients of organic sulfur compounds in the biotrickling filter liquids were generally very close to the corresponding partition coefficients in deionized water. Based on the estimated ionic strength of biofilter liquids, it is assessed that salting-out effects are of no importance for these compounds. For H₂S, a higher enthalpy of air–liquid partitioning was observed for 2nd stage filter liquid, but not for 1st stage filter liquid. In general, the results show that co-solute effects for sulfur compounds can be neglected in numerical biofilter models and that the uptake of volatile sulfur compounds in biotrickling filter liquids cannot be increased by decreasing ionic strength.