A method was developed for the simultaneous determination of the following nine volatile sulfur compounds in gas samples: carbon disulfide, carbonyl sulfide, ethyl sulfide, ethyl methyl sulfide, hydrogen sulfide, isopropanethiol, methanethiol, methyl disulfide and methyl sulfide. The target compounds were preconcentrated by solid-phase microextraction (SPME) and determined by gas chromatography combined with mass spectrometry. Experimental design was employed to optimize the extraction time and temperature and concurrent detection of the nine compounds was achieved by using an SPME fiber coated with Carboxen-polydimethylsiloxane (75 ╡m). Detection limits ranged from 1 ppt (v/v) for carbon disulfide to 350 ppt (v/v) for hydrogen sulfide and calibration functions were linear up to 20 ppb (v/v) for all the compounds investigated.

Procedures were assessed for quantifying nine volatile sulfur compounds found in complex gaseous samples collected at a biogas-production plant and a sewage treatment plant. The target compounds were extracted by solid-phase microextraction (using the 75-╡m Carboxen-polydimethylsiloxane fiber coating) at 22░C for 20 min, and analyzed by GC-MS. Detection limits ranged between 1 pptv (v/v) for carbon disulfide and 470 pptv (v/v) for hydrogen sulfide. High amounts of organic compounds were found during full-scan analysis of the samples and standard additions to individual sub-samples revealed that the analysis was subject to matrix effects. However, the functions obtained by standard additions were still linear and quantification was possible for all the compounds tested except hydrogen sulfide. No detectable losses were observed during storage in the sampling containers, made of Tedlar film, over a storage period of 20 h. However, water permeated through the walls and the relative humidity in the bag increased during storage until it reached the ambient level. Finally, it was shown that the drying agent, CaCl2, caused no detectable losses of any of the compounds. ⌐ 2002 Elsevier Science B.V. All rights reserved.

The present study was conducted to develop a rapid, matrix-independent technique for simultaneous analysis of nine different volatile sulfur compounds (VSCs) in complex gas matrices.The potential of using solid-phase microextraction (SP:ME) in this context was investigated, and, to achieve the best sensitivity and avoid artifact formation and competitive adsorption, pel'formance ofthe following fiber coatings was tested: Carboxen/polydimethylsiloxane (CARIPDMS),divinylbenzene/ polydimethyl-siloxane (DVBIPDMS), and Carboxen/divinylbenzene/polydimethylsiloxane (CAR/DVBIPDMS). The optimal injector temperature and desorption time for each fiber were dete1n1ined by experimental design. The samples analyzed were collected in Tedlar bags at a biogas facility and a sewage treatment plant to represent background levels and point-source emissions. The samples were subsequently dried over CaClz and preconcenti·ated bySPME, and the target compounds were analyzed by GC-MS. CARIPDMS induced the lowest level of artifact formation and initially also exhibited the broadest range of linear adsorption kinetics. Anextraction time of 2.5 min gave no matrix effects, despite the complexity of the samples, and the analytes were accurately quantified using extemal calibration curves below odor thresholds.Detection limits ranged from 0.008 (CS2) to 2.5 (H2S) ppbv, and the relative standard deviation was 4-16%.

The extraction of pure hydrogen from the fermentation of household waste by a mixed anaerobic bacterial flora is demonstrated. Simulated household waste (600 g) was fermented in a bioreactor, which was continuously sparged with nitrogen (30 ml/min) fed in from the bottom. The gas stream from the biorector passes through a sulphide trap (ZnO) and then through a heated palladium-silver membrane reactor to separate hydrogen from the gas stream. In this way, waste remediation and biological hydrogen production is combined in a process where a large proportion of the hydrogen produced can be collected, free of other gaseous species from the fermentation. © 2001 International Association for Hydrogen Energy.

The potential of solid-phase microextraction (SPME) for time-weighted average (TWA) sampling of volatile sulfur compounds in air at ppb concentrations was investigated. The target compounds (hydrogen sulfide, methanethiol (MeSH), ethanethiol (EtSH), dimethyl sulfide (Me2S), and dimethyl disulfide (Me2S2)) were extracted using SPME with a Carboxen-poly(dimethylsiloxane) fiber coating, and diffusion was controlled by keeping the fiber retracted within the needle of the sampling device. The effects of several important experimental variables (air velocity, direction of air flow, analyte concentration, humidity, temperature, extraction time) were studied. The uptake by the fiber was not affected by the direction of the air flow or the air velocity. The effects of concentration, humidity, temperature, and extraction time were examined in experiments with a central composite face design. The results showed that all or most of the investigated parameters had a significant impact on the uptake rates of H2S, MeSH, EtSH, and Me2S, which invalidated time-weighted average sampling of these compounds by SPME under the tested conditions. Moreover, reverse diffusion of H2S, MeSH, and EtSH occurred at 40% relative humidity. For Me2S2, the uptake rate had a variation of only 8% within the whole experimental domain, and the experimental value derived for the uptake rate was consistent with the theoretical value. This result was confirmed by comparative analyses of industrial samples by the standard addition method. Therefore, SPME appears to be a suitable technique for TWA sampling of Me2S2 using the Carboxen-poly(dimethylsiloxane) fiber coating. Finally, in an investigation of potential losses during storage of the fiber, no significant losses of the target compounds were detected after 3 days at -80 °C.

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.