A study of volatile organic sulfur emissions causing urban odors

Levels of hydrogen sulfide and sulfur containing organic compounds were studied in the air at the deltas of the polluted creeks in the city of Izmir, Turkey in summer 2001. High concentrations of these malodorous compounds were measured in the air samples. Presence of these compounds in the air was connected with the dark appearance and rising gas bubbles in the studied segments of the creeks. These creeks were like open sewers carrying wastewaters from the industry and residential areas into the inner Izmir Bay until September 2001.Within the scope of this study organic sulfur compounds such as methane thiol, ethane thiol, 2-propane thiol, 2-butane thiol, dimethylsulfide, dimethyldisulfide, thiophene, diphenylsulfide and hydrogen sulfide were studied in the air at selected urban sites where odor nuisance was recognized. Flux measurements from polluted surfaces were preferred rather than direct ambient air measurements. Organic sulfur emission fluxes from the creek surfaces were found above the values reported in the literature. Their concentrations and fluxes were higher in June field program. A limited number of measurements of reduced sulfur compound emission concentrations from the wastewater treatment plant equalization tank and the sludge drying beds as well as the landfill soil surface were also included in the study.Concentrations of total organic sulfur compounds and certain individual components such as dimethylsulfide and hydrogen sulfide in emitted gases from river surfaces were correlated with ambient SO(2) concentrations.     

Sulfur organic compounds in bottom sediments of the eastern Gulf of Finland

Background, Aims and Scope Despite the large number of studies on the forms of sulfur in marine deposits, investigations on sulfur organic compounds are still rare. It is known that the processes leading to formation of intermediate and final sulfur compounds (including organic ones) in modern deposits are the results of microbiological transformation of sulfur containing proteins, as well as the microbiological reduction of sulfate ions. The latter are finally reduced by anaerobic sulfate-reducing bacteria to H₂S, HS⁻ and S²⁻; the total sum of these is referred to as ‘hydrogen sulfide’ in chemical oceanography. Further, the formation of reduced sulfur organic derivatives (sulfides and polysulfides) is the result of interaction of the organic substance destruction products with the sulfide ions. In such cases, the main source of organic substances, as well as sulfates for the sulfur reducing processes, is the pore water in the sediments. The choice of the target of our study is based on the fact that the eastern part of the Gulf of Finland water area receives the bulk of the anthropogenic load of the St. Petersburg region. Low vertical intermixing of the water thickness is observed there (thus creating a deficiency of oxygen near the bottom), and the bottom sea current transfers the polluted salty water of the Baltic Sea into the Neva Bay. The whole of the above are the preconditions for the formation of sulfur-bearing organic compounds. A great number of bottom sediment samples for analytical surveys were collected in the Eastern Gulf of Finland during research expeditions in the years of 1997 and 2001. These were screened for structures of sulfur organic microcontaminants, including organic forms of sulfur, using advanced instrumentation and experienced personnel in our two, cooperating laboratories. This work is a part of the research being carried out on organic micro-admixtures present in bottom sediments, and is the summary of our findings on previously unstudied sulfur organic substances there. Materials and Methods A number of sulfur organic compounds present in nineteen bottom sediment samples from the Eastern Gulf of Finland (EGF) were characterized by high performance gas chromatography connected to low and high resolution mass spectrometers (GC/LRMS and GC/HRMS). The structure screening was carried out as compared with literature and library mass spectra, and taking the GC retention times into account. In the cases of an absence of mass spectra not in the literature, interpretation of the most probable structures was performed with the help of high resolution mass-spectrometric data, fragmentation rules for sulfur-bearing organic substances and ICLU simulation of spectra. These data were registered to form a conclusive ‘fingerprint’ for identification and confirmation of the structure of each novel compound found, e.g. by later syntheses of authentic model compounds. The relative contents of sulfur organic compounds were determined from MS response ratios of each compound to 2-fluorine naphthalene (internal standard). Results This paper is a completion of work, which has been published in part as three papers in the European Journal of Mass Spectrometry. As the total study result, 43 sulfur-bearing compounds were characterized. The mass spectra of 20 of them were found in the literature. The most probable structures for the 23 compounds whose mass-spectra were not available in the literature data were proposed. All of those 23 compounds were detected in bottom sediments for the first time, and 5 of them were described as originating from plants or being generated by chemical synthesis products, while the remaining 18 substances were previously unknown. The structures of these were deduced to be most probably the following (in order of their GC retention): dichloromethyl thiylsulfenylchloride, chloromethyl dichloromethyl disulfide, 3,4-dithiacyclohexene, 1,2,4-trithiacycloheptane, 1,2,3-trithiacyclohexane, tetrathiacyclopentane, 3,4,5-trithiacyclohexene, 1,2,4-trithiacyclohexane, cyclopropylhydrotrisulfide, 1,2-dithiane-3-thiol, 1,3-dithiane-2-thiol, bis(trichloromethyl)-tri-sulfide, 1,2,4,5-tetrathiacyclohexane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathia-cyclo-hexane, pentathiacyclohexane, and 1,2,4,6-tetrathiacyclooctane. The highest amounts of sulfur organic compounds were found in the deepest, bottom areas in the open part of the sea, where the salinity was highest, and oxygen deficiency occurred as well. Also, some coastal places with a high solid matter deposition rate had elevated contents of sulfur organic compounds. Discussion From the 43 sulfur organic compounds found, the HRMS data provided the atomic composition of the molecular ions for 16 compounds with a high confidence (see Table 3). The LRMS spectra could be identified with catalogue or literature spectra in 29 cases. The MS information obtained was insufficient in two cases: 1) The obvious molecular ion (at m/z 110) of compound 1 was not visible in LRMS. 2) For compound 43, the HRMS measurement, due to the low intensity (2%) of the molecular ion (m/z 210), could not exclude the presence of 2 oxygen atoms (instead of one sulfur atom) in the molecule. Major fragments, however, of our 43, certainly contained no oxygen atoms according to HRMS. The limited LRMS data in the literature, for an isomer of 43, had m/z values of all fragments different from those of the compound found by us. The retention times (RT) formed one more evidence for identity between compounds in different samples. The use of different non-polar columns in GC and similar, but not identical, temperature programs produced eluted peaks of novel and known compounds in each sample (mixture) in GC/HRMS and GC/LRMS. These gave sets of RTs which were in a very significant linear correlation (measured example R = 0.999866, p = 1.85E-06, N = 5). Therefore, the RTs in the HRMS analysis systems could be converted to values comparable with those from the LRMS device. The RT values, HRMS m/z values, LRMS spectra, and ICLU simulation results for each organic sulfur compound form an identification ‘fingerprint’. The interpretation of these experimental data, with supporting use of fragmentation rules, allow the giving of a provisional name and structure to the ‘suspect’. In this study and in environmental surveys of micropollutants in general, the compounds suspected of anthropogenic or natural origin occur at low levels in complex mixtures. Therefore, no bulk amount of an authentic, pure model substance for the suspect is available quite often. The most probable name and structure from the fingerprint data are very useful in guiding the preparation of the model substance for a conclusive identification. Similarly, the unknown criminal can be identified in advance by forensic science and his fingerprint, DNA, etc. as registered before the arrest. The analogy can be found in the literature and CAS register of organic polysulfides, which in great part consists of the results of sensitive mixture analysis methods. Conclusions Sediment of the Eastern Gulf of Finland is over large areas anaerobic, as indicated by the existence of novel, non-oxygenated sulfur organic microcontaminants. These substances were most abundant in anoxic and saline, deep bottom regions, and, in addition, in one coastal area near industrial discharges. This occurrence, and also the limited information about sulfur organic compounds in scientific literature, is considered evidence for the dominantly natural processes in their formation. Recommendations and Perspectives The importance and necessity of investigating the sulfur organic compounds in the bottom sediments, result from the fact that their presence can be an indicator of stable anaerobic processes. Similarly, the oxygen disappearance (anoxia) in the marine water, due to a high concentration of the sulfate ions and relatively high content of organic matter, is practically always connected with the appearance of hydrogen sulfide and sulfides. The generation of sulfur organic compounds precedes the formation of the new, or expansion of the existing anaerobic (‘hydrogen sulfide’) zones, which lead to such environmental disasters as mass destruction of hydrobionts. Many organic compounds of sulfur, including sulfides and polysulfides, are toxic to the aquatic organisms. Therefore, in addition to the danger of mass wholesale deaths of marine fauna in the bottom sediments region, there exists a probability of secondary pollution of the water thickness as well, due to the entry of those substances from bottom sediments in the water when the environmental conditions are changed (stormy weather, floods, geological activity of the earth’s crust, etc.).     

Co-treatment of hydrogen sulfide and methanol in a single-stage biotrickling filter under acidic conditions

Biofiltration of waste gases is cost-effective and environment-friendly compared to the conventional techniques for treating large flow rates of gas streams with low concentrations of pollutants. Pulp and paper industry off-gases usually contain reduced sulfur compounds, such as hydrogen sulfide and a wide range of volatile organic compounds (VOCs), e.g., methanol. It is desirable to eliminate both of these groups of compounds. Since the co-treatment of inorganic sulfur compounds and VOCs in biotrickling filters is a relatively unexplored area, the simultaneous biotreatment of H2S and methanol as the model VOC was investigated. The results showed that, after adaptation, the elimination capacity of methanol could reach around 236 g m(-3) h(-1) with the simultaneous complete removal (100%) of 12 ppm H2S when the empty bed residence time is 24 s. The pH of the system was around 2. Methanol removal was hardly affected by the presence of hydrogen sulfide, despite the low pH. Conversely, the presence of the VOC in the waste gas reduced the efficiency of H2S biodegradation. The maximal methanol removal decreased somewhat when increasing the gas flow rate. This is the first report on the degradation of methanol at such low pH in a biotrickling filter and on the co-treatment of H2S and VOCs under such conditions.     

Kinetics and stoichiometry of aerobic sulfide oxidation in wastewater from sewers-effects of pH and temperature.

Kinetics and stoichiometry of aerobic chemical and biological sulfide oxidation in wastewater from sewer networks were studied. In this respect, the effects of temperature and pH were investigated in the ranges 10 to 20 degrees C and 5 to 9, respectively. The temperature dependency of sulfide oxidation kinetics was described using an Arrhenius relationship. The effect of pH on the rate of chemical sulfide oxidation is related to the dissociation of hydrogen sulfide (H2S) to hydrogen sulfide ion (HS(-)), with HS(-) being more readily oxidized than H2S. Biological sulfide oxidation exhibited the highest rates at ambient wastewater pH, and the reaction was inhibited at both low and high pH values. Chemical sulfide oxidation was found to produce thiosulfate and sulfate, while elemental sulfur was the main product of biological sulfide oxidation. Based on the investigations, general rate equations and stoichiometric constants were determined, enabling the processes to be incorporated to conceptual sewer process models.     

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.     

Monitoring odorous sulfur emissions using self-organizing maps for handling ion mobility spectrometry data

Possibilities for monitoring emissions of reduced sulfur compounds in pulp and paper mills were investigated using ion mobility spectrometry (IMS) and a self-organizing map (SOM) algorithm. The reduced sulfur compounds measured were hydrogen sulfide (H2S), dimethyl sulfide (DMS), and methyl mercaptan (MM). Attention was paid to momentary concentrations because there is no monitoring device able to measure peak concentrations of reduced sulfur compounds under field conditions. These methods were evaluated by measuring the reduced sulfur compounds first in the laboratory and then at a process monitoring site at a pulp factory. The aim was to find out whether it would be possible to use the laboratory measurements to recognize the same reduced sulfur compounds at the monitoring site. Data collection was followed by analysis using the SOM algorithm and Sammon's mapping. The results showed that the IMS spectra of reduced sulfur compounds and their mixtures can be distinguished from each other by computationally intelligent methods and that the spectra from the process monitoring site corresponded with the laboratory measurements to a certain extent.     

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.     

Canadian Activities in Ambient Air Quality Criteria and Development of Standards

Within recent years, increasing attention has been directed to the determination of contaminant levels in urban and industrial areas involving particulate matter (dustfall, suspended matter and smoke), sulfur dioxide, hydrogen sulfide, fluorides, ozone or oxidant, oxides of nitrogen and polycyclic aromatic hydrocarbons. However, with regard to criteria and evaluation of effects, none of these pollutants has been studied as thoroughly as sulfur dioxide. Presently, three provinces in Canada have adopted acts or regulations dealing with the control of air pollution. The Ontario Act, passed in 1958 and amended in 1963 and 1964, is the most comprehensive in scope. The Damage by Fumes Arbitration Act of Ontario provides for the awarding of compensation where crops, trees or other vegetation is damaged by sulfur fumes arising from the smelting or roasting of nickel-copper ore or iron ore or from the treatment of sulfides for the production of sulfur of sulfuric acid for commercial purposes. Regulations have also been enacted in Manitoba and Alberta. A provincial act is under consideration in Saskatchewan.     

The removal of hydrogen sulfide in solution by ferric and alum water treatment residuals

This work investigated the characteristics and mechanisms of hydrogen sulfide adsorption by ferric and alum water treatment residuals (FARs) in solution. The results indicated that FARs had a high hydrogen sulfide adsorption capacity. pH 7 rather than higher pH (e.g. pH 8-10) was favorable for hydrogen sulfide removal. The Yan model fitted the breakthrough curves better than the Thomas model under varied pH values and concentrations. The Brunauer-Emmett-Teller surface area and the total pore volume of the FARs decreased after the adsorption of hydrogen sulfide. In particular, the volume of pores with a radius of 3-5 nm decreased, while the volume of pores with a radius of 2 nm increased. Therefore, it was inferred that new adsorption sites were generated during the adsorption process. The pH of the FARs increased greatly after adsorption. Moreover, differential scanning calorimetry analysis indicated that elemental sulfur was present in the FARs, while the derivative thermal gravimetry curves indicated the presence of sulfuric acid and sulfurous acid. These results indicated that both oxidization and ligand exchange contribute to the removal of hydrogen sulfide by FARs. Under anaerobic conditions, the maximum amount of hydrogen sulfide released was approximately 0.026 mg g(-1), which was less than 0.19% of the total amount adsorbed by the FARs. The hydrogen sulfide that was released may be re-adsorbed by the FARs and transformed into more stable mineral forms. Therefore, FARs are an excellent adsorbent for hydrogen sulfide.     

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.     

Improved vacuum-UV (VUV)-initiated photomineralization of organic compounds in water with a xenon excimer flow-through photoreactor (Xe2* lamp, 172 nm) containing an axially centered ceramic oxygenator

Xenon excimer (Xe2*) lamps can be used for the oxidation and mineralization of organic compounds in aqueous solution. This vacuum-ultraviolet (VUV) photochemical method is mainly based on the photochemically initiated homolysis of water that produces hydrogen atoms and hydroxyl radicals. The efficiency of substrate oxidation and mineralization is limited markedly due to the high absorbance of water at the emission maximum of the Xe2* lamp (lambda(max)=172 nm). This photochemical condition generates an extreme heterogeneity between the irradiated volume V(irr) and the non-irradiated ("dark") bulk solution. During VUV-initiated photomineralization of organic substrates, the fast scavenging of hydrogen atoms and of carbon-centered radicals by dissolved molecular oxygen produces a permanent oxygen deficit within V(irr) and adjacent compartments. Hence, at a constant photon flux the concentration of dissolved molecular oxygen within the zones of photo and thermal radical reactions limits the rate of mineralization, i.e. the rate of TOC diminution. Thus, a simple and convenient technique is presented that overcomes this limitation by injection of molecular oxygen (or air) into the irradiated volume by use of a ceramic oxygenator (aerator). The tube oxygenator was centered axially within the xenon excimer flow-through lamp. Consequently, the oxygen or air bubbles enhanced the transfer of dissolved molecular oxygen into the VUV-irradiated volume leading to an increased rate of mineralization of organic model compounds, e.g. 1-heptanol, benzoic acid and potassium hydrogen phthalate.     

Determination of Sulfur Oxides in the Flue Gases of the Pulping Processes

The body of information presented in this paper is directed to the operating personnel and process engineers employed in the power and recovery departments of a chemical pulping operation. The proper evaluation of the total analytical and sampling system (TASS), to be used in the determination of sulfur oxides is as important as a proper analytical and recording system (ARS). The presence of other sulfur gaseous compounds and particulates could greatly influence the results of the determination.

The analytical method employed determines sulfur dioxide and trioxide from an aliquot of the trapping solution, 3% hydrogen peroxide and 8 0% isopropyl alcohol respectively. The aliquot is titrated with barium perchlorate in the presence of Thorin indicator. The results of evaluating the method indicated negligible interference from the presence of hydrogen sulfide, mercaptans and nitrogen oxides. A blank correction of 15 parts per million (ppm) is recommended whenever 100 ppm of hydrogen sulfide or more are simultaneously present in the gas stream. Particulaies are shown to interfere either by addition or subtraction. Sulfate particulates that will add to the determination must be removed, but in doing so, care must be exerted to avoid surface-contacting conditions that promote reaction between carbonates and the sulfur oxides. The integrated method of sampling and analysis will permit determinations from a flue gas with sulfur oxides concentrations of 30 ppm and above. The relative standard deviation improves from 10% at 100 ppm SO₂ to 2.6% at 1000 ppm SO₂. In both cases, sulfides were present.     

Removal of insoluble heavy metal sulfides from water

The necessity of heavy metal removal from wastewater has led to increasing interest in absorbents. We have developed a new approach to obtain high metal adsorption capacity by precipitating metal sulfides with sodium sulfide on the surface of bentonite and adhere them to the absorbent. This method allowed to remove approximately 90% of cadmium as CdS from 10(-4)-10(-6) M CdCl2 solutions. Additional reactions are related to the removal of excess sodium sulfide by the release of hydrogen sulfide and oxidation to sulfur using carbogen gas (5% CO2, 95% O2) followed by aeration.     

Volatile organic sulfur compounds in a stratified lake

Three volatile organic sulfur compounds (VOSCs), dimethyl sulfide (DMS), carbon disulfide (CS(2)), and dimethyl disulfide (DMDS), were detected in the stratified water column of a lake (Linsley Pond) in Connecticut. The compounds DMS and DMDS appeared in both the oxic and the anoxic portions of the water column, CS(2) was primarily found in anoxic hypolimnion. Algal metabolism and/or bacterial degradation of sulfur-containing amino acids or other organic materials are potential sources of VOSCs in the oxic lake water. Reactions of hydrogen sulfide with organic compounds and microbial degradation of organic matter may be responsible for the production of VOSCs in the anoxic lake water. The vertical distribution patterns of these three VOSCs varied from month to month in the summer, but the daily profiles obtained in one 5-day period in the summer displayed consistency. No clear diurnal pattern for any of the three VOSCs was observed. Based on observation that these VOSCs were not present in surface and near surface waters of Linsley Pond, freshwater inputs of reduced sulfur compounds to the atmosphere may be insignificant.     

Online oxygen control for sulfide oxidation in anaerobic treatment of high-sulfate wastewater.

A new technique for sulfide control was investigated in an upflow-anaerobic filter (UAF) treating high-strength, sulfate-rich wastewater. The technique used periodic oxygen injection using oxidation-reduction potential (ORP) as a controlling parameter to regulate oxygen injection. The UAF was operated at a constant influent total-organic carbon of 6740 mg/L but with different influent sulfates of 1000, 3000, and 6000 mg/L. At 1000 and 3000 mg/L influent sulfates, the produced sulfide did not impose any inhibition to methane-producing bacteria (MPB). However, at 6000 mg/L influent sulfate, the produced dissolved sulfide of 804 mg S/L (free sulfide = 280 mg S/L) severely inhibited the methanogenesis, but not the sulfidogenesis. Upon oxygen injection at elevated ORP of -265 mV, sulfides were almost completely eliminated with a concomitant improvement in methane yield by 46%. If oxygenation was excessive because of an oversetting of ORP, the excess oxygen could be used rapidly by facultative heterotrophs, thereby protecting the MPB from oxygen stress. Regarding online sulfide oxidation, it was found that the biogas and injected oxygen needed to pass through an aqueous layer containing trace metals, which were found to have a significant catalytic effect on abiotic sulfide oxidation.     

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.     

Rapid oxidation of sulfide mine tailings by reaction with potassium ferrate

The chemistry of sulfide mine tailings treated with potassium ferrate (K2FeO4) in aqueous slurry has been investigated. The reaction system is believed to parallel a geochemical oxidation in which ferrate ion replaces oxygen. This chemical system utilized in a pipeline (as a plug flow reactor) may have application eliminating the potential for tailings to leach acid while recovering the metal from the tailings. Elemental analyses were performed using an ICP spectrometer for the aqueous phase extract of the treated tailings; and an SEM-EDX for the tailing solids. Solids were analyzed before and after treatments were applied. ICP shows that as the mass ratio of ferrate ion to tailings increases, the concentration of metals in the extract solution increases; while EDX indicates a corresponding decrease in sulfur content of the tailing solids. The extraction of metal and reduction in sulfide content is significant. The kinetic timeframe is on the order of minutes.     

Process Modifications for Air Pollution Control in Neutral Sulfite Semi-Chemical Mills

The body of information presented in this paper is directed to those individuals concerned with the air pollution control problems of the pulp and paper industry operation. Process modifications introduced at two Company mills, at Big Island, Va. and Tomahawk, Wis., where neutral sulfite semichemical pulping of hardwoods is performed at rates of 550 and 630 tons per day, respectively, are discussed. The methodology and concepts used to minimize total reduced sulfur and total sulfur oxide emissions from the recovery furnace of one of the operations are explained. In another major improvement already implemented in the Big Island Mill conventional hydrogen sulfide emissions from the sulfiting tower, on the order of 8–10 lb as sulfur per ton of pulp, have been completely eliminated by a process modification technique. Other aspects of the operations are described, and a forecast of possible emission levels for mills with a newer technology is made.     

Generation pattern of sulfur containing gases from anaerobically digested sludge cakes.

Eleven dewatered sludge cakes collected from anaerobic digesters at different treatment plants were evaluated for the amount, type, and pattern of odorous gas production. All but one of the sludge cakes were from mesophilic anaerobic digesters. One was from a thermophilic digester. The pattern and quantities of sulfur gases were found to be unique for each of the samples with regard to the products produced, magnitude, and subsequent decline. The main odor-causing chemicals were volatile sulfur compounds, which included hydrogen sulfide, methanethiol, and dimethyl sulfide. Volatile sulfur compound production peaked in 3 to 8 days and then declined. The decline was a result of conversion of organic sulfur compounds to sulfide. In one side-by-side test, a high-solids centrifuge cake generated more odorous compounds than the low-solids centrifuge cake. The data show that anaerobic digestion does not eliminate the odor potential of anaerobically digested dewatered cakes.     

Feasibility study on high-temperature sorption of hydrogen sulfide by natural soils

In this study, seven natural soils were tested for the sorption of hydrogen sulfide from coal gasification gas at high temperature. Results indicate that the LP natural soil has the best performance and the highest sulfur sorption capacity. After extracting free iron oxides, most natural soils have no sorption efficiency. The free iron oxides, therefore, proved to be the major components that react with hydrogen sulfide to form iron sulfides. The sulfur sorption capacity, either determined by EA or breakthrough time, is very close to the theoretical value based on the stoichiometric calculation with the content of free iron oxides. Moreover, the presence of CO is a positive effect while H2 is a negative effect. This can be explained via the water-shift reaction. On the basis of the results of temperature-programmed sulfidation (TPS), the starting temperature for the sorption of hydrogen sulfide is between 623-673 K. From the analyses of temperature-programmed oxidation (TPO) and XPS, the iron polysulfides are the major products and approximately 90% regeneration efficiency can be theoretically achieved while the temperature is controlled higher than 813 K. In the regeneration tests, the results show that the LP natural soil can be regenerated and thus reused after the oxidation process. No significant degeneration occurs on the LP natural soil after five sorption/regeneration cycles. The sulfur sorption capacity of the tenth regenerated soil can be achieved at least 80% compared to the fresh one. The experimental analyzed SO2 concentration from the regeneration process is almost identical to the theoretical calculated equilibrium concentration of the process. Maghemite is the main product after the regeneration process.