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Catalytic oxidation of gaseous reduced sulfur compounds using coal fly ash.

Activated carbon has been shown to oxidize reduced sulfur compounds, but in many cases it is too costly for large-scale environmental remediation applications. Alternatively, we theorized that coal fly ash, given its high metal content and the presence of carbon could act as an inexpensive catalytic oxidizer of reduced sulfur compounds for "odor" removal. Initial results indicate that coal fly ash can catalyze the oxidization of H(2)S and ethanethiol, but not dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) at room temperature. In batch reactor systems, initial concentrations of 100-500 ppmv H(2)S or ethanethiol were reduced to 0-2 ppmv within 1-2 and 6-8 min, respectively. This was contrary to control systems without ash in which concentrations remained constant. Diethyl disulfide was formed from ethanethiol substantiating the claim that catalytic oxidation occurred. The presence of water increased the rate of adsorption/reaction of both H(2)S and ethanethiol for the room temperature reactions (23-25 degrees C). Additionally, in a continuous flow packed bed reactor, a gaseous stream containing an inlet H(2)S concentration of 400-500 ppmv was reduced to 200 ppmv at a 4.6s residence time. The removal efficiency remained at 50% for approximately 4.6h or 3500 reactor volumes. These results demonstrate the potential of using coal fly ash in reactors for removal of H(2)S and other reduced sulfur compounds.

Adsorption↗

Volatile sulfur compounds in Cheddar cheese determined by headspace solid-phase microextraction and gas chromatograph-pulsed flame photometric detection.

The aim of this study was to develop a methodology for the analysis of volatile sulfur compounds (VSCs) in Cheddar cheese. Solid-phase microextraction (SPME) was employed to extract VSCs from the cheese matrix using a CAR-PDMS fiber. This extraction method was combined with gas chromatography-pulsed flame photometric detection (GC-PFPD) to achieve high sensitivity for sulfur compounds. The impact of extraction parameters, including time, temperature and sample size, was evaluated to determine the best conditions to analyze sulfur compounds in Cheddar cheese. Hydrogen sulfide, methanethiol, and dimethyl sulfide were found to constitute the majority of the overall sulfur profile while dimethyl disulfide and dimethyl trisulfide were present in lesser amounts. Artifact formation of volatile sulfur compounds was found to be minimal. Two commercial cheese samples were analyzed and differences in sulfur content were observed. Overall, SPME-GC-PFPD was found to be a highly sensitive technique for the analysis of sulfur compounds in Cheddar cheese.

Artifacts↗

[Corrosion of pipe steel samples and conjugated conversion of sulfur compounds by thiobacteria Halothiobacillus neapolitanus DSM 15147].

The kinetics of conversion of sulfur compounds by Halothiobacillus neapolitanus DSM 15147 bacteria was studied in the presence of steel samples. It was shown that the presence of steel altered the known pathway of sulfur compound oxidation by thiobacteria. Production of atomic hydrogen via the interaction between biogenic sulfuric acid and steel enhanced secondary production of intermediates and decreased the content of sulfate produced previously. The process was accompanied by pH elevation and continuation of intense growth of the thiobacterium culture. Thiobacteria formed a corrosive medium, which caused metal destruction. The protective properties of anticorrosive coatings 225 LS and 640 mk were tested. It was shown that these coatings protected steel from the destructive effect of biogenic sulfuric acid.

Corrosion↗

Volatile sulfur compounds in irradiated precooked turkey breast analyzed with pulsed flame photometric detection.

Ionizing radiation is an effective processing technology for pathogen inactivation on various foods. However, the generation of off-odor is a concern for some irradiated meats. This study was conducted to investigate volatile sulfur compounds of precooked ready-to-eat turkey breast as functions of radiation dose and subsequent storage. Precooked turkey breast was exposed to 0, 1, 2, 3, 4, and 5 kGy of gamma radiation and stored for 14 days at 5 degrees C. Volatile sulfur compounds were extracted using solid phase microextraction (SPME), followed by gas chromatographic separation and pulsed flame photometric detection. Irradiation dramatically increased concentrations of hydrogen sulfide, sulfur dioxide, methanethiol, and dimethyl disulfide. The rate of increase was higher at low doses (0-2 kGy) than at higher doses of 3-5 kGy. Carbon disulfide was the only volatile sulfur compound that was reduced by irradiation. Concentrations of all volatile sulfur compounds decreased in both irradiated and nonirradiated samples stored at 5 degrees C.

Animals↗

In vitro volatile sulfur compound production of oral bacteria in different culture media.

OBJECTIVE: The purpose of this study was to detect the relative contribution of Porphyromonas gingivalis, Fusobacterium nucleatum, and Prevotella intermedia in the production of oral malodor. METHOD AND MATERIALS: The volatile sulfur compounds produced by these bacteria in vitro were measured semiquantitatively by a portable sulfide monitor. RESULTS: Samples from the tongue, tonsils, and pharynx showed a significantly higher production (550 ppb) of volatile sulfur compounds during the first 6 hours after anaerobic incubation in broths (brain-heart infusion, Columbia, and Trypticase Soy) than after incubation in agar media (300 ppb) (P < 0.001). After 24 hours, values in broths and agars leveled off at 350 ppb (P = 0.3) and remained constant during the next 6 days. Measurement of separate pure cultures showed that maximal volatile sulfur compound production was reached 6 hours after incubation (450 ppb for the 3 bacteria). Higher volatile sulfur compound values were measured in brain-heart infusion. When measurements of mixed cultures of the 3 pathogens were performed every 15 minutes, the maximal value was reached after only 30 minutes of incubation (nearly 500 ppb). CONCLUSION: The in vitro volatile sulfur compound production of oral samples is preferably measured in broths. Maximal sulfur production from mixed cultures is reached after 30 minutes of incubation. Samples should always be inoculated at the same dilution.

Culture Media↗

Production of volatile sulfur compounds during the decomposition of algal mats.

Blue-green algal mats incubated anaerobically rapidly produce large amounts of volatile sulfur compounds, including hydrogen sulfide, methyl mercaptan, and dimethyl sulfide. The major organic sulfur compound is methyl mercaptan, in contrast to previous results with marine eucaryotic algae. Light inhibited production of volatile sulfur compounds, apparently because the algae then produced O2, rendering the system aerobic.

Anaerobiosis↗

[Oxidation of inorganic sulfur compounds by obligatory organotrophic bacteria].

New data obtained by the author and other researchers on two different groups of obligately heterotrophic bacteria capable of inorganic sulfur oxidation are reviewed. Among culturable marine and (halo)alkaliphilic heterotrophs oxidizing sulfur compounds (thiosulfate and, much less actively, elemental sulfur and sulfide) incompletely to tetrathionate, representatives of the gammaproteobacteria, especially from the Halomonas group, dominate. Some of denitrifying species from this group are able to carry out anaerobic oxidation of thiosulfate and sulfide using nitrogen oxides as electron acceptors. Despite the low energy output of the reaction of thiosulfate oxidation to tetrathionate, it can be utilized for ATP synthesis by some tetrathionate-producing heterotrophs; however, this potential is not always realized during their growth. Another group of marine and (halo)alkaliphilic heterotrophic bacteria capable of complete oxidation of sulfur compounds to sulfate mostly includes representatives of the alphaproteobacteria most closely related to nonsulfur purple bacteria. They can oxidize sulfide (polysulfide), thiosulfate, and elemental sulfur via sulfite to sulfate but neither produce nor oxidize tetrathionate. All of the investigated sulfate-forming heterotrophic bacteria belong to lithoheterotrophs, being able to gain additional energy from the oxidation of sulfur compounds during heterotrophic growth on organic substrates. Some doubtful cases of heterotrophic sulfur oxidation described in the literature are also discussed.

Adenosine Triphosphate↗

The South Karelia Air Pollution Study: changes in respiratory health in relation to emission reduction of malodorous sulfur compounds from pulp mills.

The authors assessed the health effects of emission reduction of malodorous sulfur compounds in a prospective cohort study with a controlled natural experiment. A total of 810 subjects (83%) participated in the follow up: 316 from the severely polluted, 306 from the moderately polluted, and 188 from the nonpolluted communities. In the severely polluted community, the annual ambient air concentration of total reduced sulfur compounds decreased from 11 microg/m3 to 6 microg/m3. Compared with the nonpolluted community, the relative decrease in acute respiratory infections, adjusted for a change in smoking habits, was 0.53 episodes/person-year (95% confidence interval = 0.22, 0.83) in the severely polluted community and 0.36 episodes/person-year (95% confidence interval = 0.06, 0.66) in the moderately polluted community. In addition, the frequency of nasal symptoms (p = .004) and cough (p = .037) decreased significantly. The results are consistent with the hypothesis that exposure to malodorous sulfur compounds increases the risk of acute respiratory infections and symptoms of the respiratory tract.

Acute Disease↗

South Karelia Air Pollution Study: daily symptom intensity in relation to exposure levels of malodorous sulfur compounds from pulp mills.

In a longitudinal study, we assessed the relation between daily exposure to ambient air malodorous sulfur compounds from pulp production and experience of symptoms in a small population living in the vicinity of a pulp mill. Special emphasis was laid on exposure-response pattern, where the intensity of the symptoms of interest was assessed in six consecutive questionnaires after three predefined levels of exposure to malodorous sulfur compounds [total reduced sulfur (TRS)] (reference: daily mean < 10 micrograms/m3, medium exposure: 10-30 micrograms/m3 high exposure: > 30 micrograms/m3). The study population included 81 adults, who responded to the baseline questionnaire (response rate 81%). The outcomes of interest were eye, respiratory, and central nervous symptoms. The mean daily intensity of the outcome symptoms, but not of control symptoms, was significantly higher on days of medium and high exposure compared with the reference days (paired t test). The probability ratios between experiencing more or fever symptoms during the medium and high exposure compared with reference days were increased for all the symptoms of interest with a consistent exposure response pattern. The probability ratios were for eye symptoms 3.17, 95% confidence intervals (CI) 1.21 to 7.47 (medium exposure), and 5.0, 95% CI 1.66 to 12.65 (high exposure); for nasal symptoms 3.13, 1.25 to 7.25 (medium), and 8.50, 3.19 to 18.64 (high); and for pharyngeal symptoms 2.0, 0.92 to 4.14 (medium) and 5.20, 1.95 to 11.99 (high). The results suggest that relatively low daily levels of malodorous sulfur compounds (TRS > 10 micrograms/m3) cause exposure-related short-term adverse effects.

Adult↗

Preparation of cerium-loaded Y-zeolites for removal of organic sulfur compounds from hydrodesulfurizated gasoline and diesel oil.

Ce(IV)-loaded Y-zeolites (CeY) were prepared for selective removal of the trace amount of organic sulfur compounds from hydrodesulfurization (HDS)-treated diesel oil. The CeY samples can be obtained from NH4-Y-zeolite (NH4Y) using liquid-phase ion-exchange and solid-state ion-exchange methods. The ion-exchange reactions, structures, and selective adsorptions of organic sulfur compounds of the CeY samples were investigated using XRD, IR, XPS, TEM, and GC sulfur analyzer. The organic sulfur compound uptakes strongly depend on the amount and the valency of Ce in the zeolite structure. Ce(IV) shows much higher adsorptive ability than Ce(III). A CeY-S sample prepared by solid-state ion-exchange reaction of NH4Y and Ce(NO3)3 with Ce/NH4 mole ratio of 0.63 at 250 degrees C showed a maximum sulfur uptake from a model solution of HDS-treated gasoline containing thiophene [S = 5 ppm (ppm = mg/L)]. A desulfurization from a HDS-treated diesel oil containing organic sulfur compounds (S = 1.87 ppm) and H2S (S = 0.73 ppm) was investigated with a combination of the CeY-S and a CuO adsorbent for removal of H2S by a batch method. The sulfur content was reduced to below 0.01 ppm for the first time. This method provides a promising desulfurization process to prepare a clean fuel for fuel cells.

Journal Article↗

Quantification of trace volatile sulfur compounds in milk by solid-phase microextraction and gas chromatography-pulsed flame photometric detection.

Volatile sulfur compounds have been reported to be responsible for the sulfurous off-flavors generated during the thermal processing of milk; however, their analysis has been a challenge due to their high reactivity, high volatility, and low sensory threshold. In this study, reactive thiols were stabilized and the volatile sulfur compounds in milk were extracted by headspace solid-phase microextraction, and analyzed by gas chromatography and pulsed-flame photometric detection. Calibration curves for 7 sulfur-containing compounds were constructed in milk by the standard addition technique. Raw, pasteurized, and UHT milk samples with various fat contents were analyzed. Compared with raw and pasteurized samples, UHT milk contained substantially higher concentrations of hydrogen sulfide, methanethiol, carbon disulfide, dimethyl trisulfide, and di-methyl sulfoxide. The high odor activity values calculated for methanethiol and dimethyl trisulfide suggested that these 2 compounds, in addition to di-methyl sulfide reported in a previous study, could be the most important contributors to the sulfurous note in UHT milk.

Animals↗

Quantification and reduction of organic sulfur compound formation in a commercial wood pulping process.

This study experimentally quantified the formation of organic sulfur compounds in a commercial SuperBatch kraft pulping process using a laboratory pilot-scale digester. The results indicate that wood chips not only can adsorb HS- but also methyl mercaptan (MM) in the black liquor used for pretreatment during the two pretreatment stages. The absorption rate of MM is much faster than that of HS-. In the third stage of SuperBatch pulping, the rate of formation of MM and dimethyl sulfide (DMS) is very similar to that found in conventional batch kraft pulping processes. The study examined the applicability of the phase transition cooking (PTC) concept for reducing organic sulfur compounds in pulping, previously developed in laboratory batch pulping using a bomb-type digester, in a SuperBatch process. It was confirmed that there is a phase transition point (PTP) corresponding to PTC in SuperBatch pulping beyond which further delignification significantly increases the formation of volatile organic sulfur compounds. The results indicate that a 40% reduction of TRS formation can be achieved by using PTC.

Adsorption↗

Identification of organic sulfur compounds transferred to fish from petroleum suspension.

The authors attempted to determine if the organic sulfur compounds usually contained in a crude oil could serve as a marker of oil pollution in fish. Eels (Anguilla Japonica Temminck et Schlegel) were maintained in a controlled laboratory environment of water with a suspension of crude oil. Gas chromatography-mass spectrometry and mass chromatography of eel flesh extract showed the presence of organic sulfur compounds of alkyl-(from mono- to pentametyl) benzothiophenes, dibenzothiophene and alkyl-(from mono- to trimethyl) dibenzothiophenes, and other organic sulfur compounds of alkyl-(from mono- to pentamethyl) naphthalenes.

Animals↗

Limitations to the use of solid-phase microextraction for quantitation of mixtures of volatile organic sulfur compounds.

A study of the range of volatile organic sulfur compounds produced by brassica plants has highlighted limitations to the use of Carboxen/PDMS fibers for their analysis by solid-phase microextraction (SPME). These fibers are sometimes advocated for the analysis of sulfur gases, but a quantitative comparison of analytical data derived by SPME and by direct gas sampling of standard mixtures of volatile low molecular weight sulfur compounds at 0.01-10 mg/L has identified potential errors associated with their use. Higher molecular compounds displace lower molecular weight compounds as a consequence of competition for active sites on the fiber, and the relative proportions of the components adsorbed onto the fiber depend on their ratio in the headspace. As their relative concentrations change from sample to sample, the varying interactions result in irregular analytical responses, reflected in erratic calibration curves. Standards containing single components are not valid; only a standard containing all components found in the sample to be analyzed, and at the same relative concentrations, is appropriate. In practice, this may preclude the use of the fibers for quantitative analysis of multicomponent mixtures.

Journal Article↗

Sulfur compounds reduce potato toxins during extrusion cooking.

Free sulfhydryl groups in sulfur compounds have been reported to act directly on natural toxins to reduce toxicity. The objective of this study was to reduce protease inhibitors and glycoalkaloids in simulated snack foods by the addition of sulfur-containing compounds prior to extrusion. Thiamine, methionine, and benzyl disulfide were added to potato flakes at levels of 0.5% or 1.0% prior to twin-screw extrusion. Total and free thiols and protease inhibitors were monitored before and after extrusion by colorimetric assays. Potato glycoalkaloids were analyzed by HPLC and by immunoassay. Extrusion reduced potato flake disulfide bonds; disulfide bonds were higher in samples containing added sulfur compounds. Trypsin inhibitor activity was reduced by as much as 79% by extrusion plus methionine. Extrusion significantly reduced carboxypeptidase inhibitor, but only when benzyl disulfide and 0.5% methionine were not added. One percent methionine and thiamine resulted in 60% reductions in glycoalkaloids.

Alkaloids↗

Utilization of sulfur compounds by Streptococcus bovis.

Prescott, J. M. (A. &. M. College of Texas, College Station). Utilization of sulfur compounds by Streptococcus bovis. J. Bacteriol. 82:724-728. 1961.-Two strains of Streptococcus bovis utilize a variety of compounds as their only source of sulfur, yet exert a definite selectivity in their nutritional requirements for this element. Among sulfur-containing amino acids and related compounds, cystine and cysteine support excellent growth, but cysteic acid and cysteine sulfinic acid do not; methionine is completely inactive as an only sulfur source, but growth is provided by lanthionine, djenkolic acid, allo-cystathionine, homocystine, homocysteine, and glutathione. Several organic sulfur compounds other than amino acids are effective sulfur sources, among which are thioglycolate, thiomalate, thiourea, and thiouracil. In contrast, thiodiglycolate, thiodiglycol, and (phenylthio) acetic acid fail to support growth. Of the inorganic sulfur sources tested, sulfide and thiosulfate are utilized, but sulfite and sulfate are not; it thus appears that the state of oxidation is a critical factor in the utilization of sulfur by these strains of S. bovis. A complex amino acid mixture, without sulfur-containing amino acids, produces more rapid and reproducible growth than either arginine or ammonium acetate when used as a nitrogen source for testing the sulfur compounds. Growth rates are frequently better when the sulfur sources are autoclaved than when they are sterilized by filtration, although the qualitative responses to the compounds are generally similar.

Alanine↗

Capillary GC/MS determination of organic sulfur compounds detected in oyster and mussel caught in the sea as an oil pollution index.

The organic sulfur compounds usually contained in crude oil were used as a marker of oil pollution in shellfish. The oyster (Crassostrea gigas) and mussel (Mytilus edulis) were caught in the Seto Inland Sea of Japan. Capillary-column gas chromatography/mass spectrometry (GC/MS) of extracts showed the presence of organic sulfur compounds of dibenzothiophene and alkyl dibenzothiophenes (C1-C3). The concentration factor of organic sulfur compounds in the oyster and mussel was determined by gas chromatography using a flame photometric detector.

Animals↗