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Determination of Volatile Sulfur Compounds in Air and other Gas Matrices: Development and Applications of Solid-Phase Microextraction
Linköping University, The Tema Institute, Department of Water and Environmental Studies. Linköping University, Faculty of Arts and Sciences.
2003 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Volatile sulphur compounds (VSCs) are frequently emitted during bioindustrial activities, such as production of biogas, sewage treatment, landfilling, pulpmilling, and the slaughtering of animals and meat processing. VSCs are reactive and malodorous, and they can also be detrimental to human health, therefore it is of great interest to be able to analyze these compounds.

However, the standard techniques that are now available for determination of VSCs entail detection limits that in some cases exceed the odor thresholds, and, what is more, they require the use of solvents and toxic reagents. In addition, a single standard method does not exist that can be used to analyze all the VSCs that are most often associated with bioindustrial processes.

In the present studies, a technique based on solid-phase microextraction (SPME) was developed for analysis of the VSCs that are commonly found in the bioindustry. The method could even be applied to very complex gas matrices representing point-source emissions of these compounds in amounts below their odor thresholds. Furthermore, the procedure constitutes an improvement compared to the other techniques employed to determine VSCs, because SPME is less time-consuming, it does not require the use of solvents or other chemicals, and it can extract all the compounds simultaneously. The potential of applying SPME for time-weighted average sampling of VSCs was also investigated. These experiments showed that the connnercially available fiber coating with the highest affmity for VSCs (i.e., Carboxen-polydimethylsiloxane)could achieve accurate determination of dimethyldisulfide, whereas use of thatcoating to collect the other compounds was highly influenced by externalparameters that are subject to variation. This work also included investigationsof several important aspects of SPME analysis of VSCs, such as the choice offiber coating, artifact formation, and the impact of various parameters on theextraction.

The current results demonstrate that the SPME methodology that was developed can be used to determine VSCs in different matrices and contexts within the bioindustry. More precisely, the technique was successfully employed for the following purposes: to determine background levels ofVSCs to which workers were exposed; to monitor VSC emissions during the biogas process; to supervise the quality of produced biogas; to investigate the efficiency of processes used for abatement of VSCs; and to ascertain the cause of odor problems.

Abstract [sv]

Den här avhandlingen behandlar bestämningen av en grupp föreningar som går under det gemensamma namnet flyktiga svavelföreningar. Dessa föreningar fmns naturligt i vår atmosfår, men kan även bildas genom mänsklig påverkan, till exempel under förbränning av fossila bränslen. Inom bioindustrin är dessa föreningar vanligt förekommande, därför att de kan bildas då bakterier bryter ner organiskt material under syrefria förhållanden. Bioindustrin är en gemensam benänrning för till exempel soptippar, biogasanläggningar, vattenreningsverk, pappersbruk ellerslakterier.

De flyktiga svavelföreningarna är av intresse i dessa sammanhang på gnmd av att de är illaluktande och giftiga, vilket i hög grad påverkar arbetsmiljön för personer som arbetar vid sådana industrier och för människor boende i närheten. Eftersom föreningarna är mycket reaktiva, ger de även upphov till korrosion i ledningar, tankar och motorer. Den metodik som idag finns tillgänglig för bestänrning av dessa föreningar är bristfållig, eftersom den är krånglig att använda, okänsligare än våra egna näsor och kräver användande av lösningsmedel och andra giftiga kemikalier. Dessutom kan man inte analysera alla vanligt förekommande flyktiga svavelföreningar med en och samma teknik.

Vad jag anser vara mitt främsta bidrag med denna avhandling, är att jagutvecklat en teknik, där man kan analysera de vanligast förekommandeflyktiga svavelföreningarna inom bioindustrin med en och samrna metod.Det går dessutom att använda tekniken i prover med mycket komplicerade matriser, vilket innebär att förekomsten av andra flyktiga kemiska föreningar, som i värsta fall kan störa analysen, frnns närvarande i höga koncentrationer. Känsligheten i metoden är fortfarande hög och koncentrationer lägre än vad våra näsor kan känna av kan bestänunas. Jag har använt mig av en teknik, som fi·ån början utvecklades av Dr. Janusz Pawliszyn på 90-talet, som kallas fastfasmikroextraktion och denna teknik hal" fördelen av att vara enkel att använda och dessutom fri från lösningsmedel och andra giftiga reagens.

I ett samarbete med ett franskt laboratorimn har jag även undersökt om det var möjligt att använda telmiken för exponeringsmätningar, vilket innebär att man genom ett enda prov kan ta reda på den totala exponeringen en person som arbetar vid en bioindustri utsätts för under en dag. Tyvärr var detta bara möjligt för en av de undersökta föreningarna, medan de andra visade sig vara alltfor påverkade av parametrar som kan forändras undermätningens gång såsom temperatur och luftfuktighet.

I övrigt innehåller avhandlingen gnmdliga undersökningar av analytiska aspekter på den teknik jag använt såsom val av adsorbent (det material som foreningama ska "fastna" på for att sedan kunna överfOras till ett analytiskt instrument), påverkan av experimentella parametrar och även undersökningar av reaktioner som kan ske under analysens gång som kan överfora de msprungliga foteningarna till andra molekyler. Till sist har jag visat att den teknik jag utvecklat verkligen fungerar genom att tillämpa den på en mängd olika prover. Huvuddelen av de prover som analyserats har hämtats vid en biogasanläggning i Linköping (Linköping Biogas AB). Vid denna anläggning produceras i genomsnitt ungefår sju miljoner kubikmeterbiogas per år, som används som bränsle i stadens bussar, taxibilar samt även en del andra kommunala fordon. Prover har även hämtats vid andra bioindustrier, till exempel från två olika reningsverk. Tekniken har använts bland annat för att analysera bakgrundshalter vid biogasanläggningen i Linköping for att se vilka koncentrationer av svavelforeningar personer som arbetar där utsätts for. Svavelhalter har mätts under biogasprocessen for att optimera tillsatsen av järnklorid, ett ämne som används for att minska svavelhalterna. Kvaliteten av producerad biogas med avseende på innehåll av svavelforeningar har undersökts. Effektiviteten av processer som används for att ta bort svavelforeningar har bestämts och luktproblemhar kunnat lösas genom att ta reda på vad som faktiskt orsakatluktproblemet med hjälp av den mätmetodik som utvecklats i detta arbete.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2003. , 85 p.
Series
Linköping Studies in Arts and Science, ISSN 0282-9800 ; 275
National Category
Social Sciences Interdisciplinary
Identifiers
URN: urn:nbn:se:liu:diva-29568Local ID: 14943ISBN: 91-7373-669-4 (print)OAI: oai:DiVA.org:liu-29568DiVA: diva2:250384
Public defence
2003-05-28, Sal Elysion, Hus-T, Universitetsområdet Valla, Linköping, 10:15 (Swedish)
Opponent
Supervisors
Available from: 2009-10-09 Created: 2009-10-09 Last updated: 2014-09-01Bibliographically approved
List of papers
1. Trace determination of volatile sulfur compounds by solid-phase microextraction and GC-MS
Open this publication in new window or tab >>Trace determination of volatile sulfur compounds by solid-phase microextraction and GC-MS
2002 (English)In: The Analyst, ISSN 0003-2654, E-ISSN 1364-5528, Vol. 127, no 8, 1045-1049 p.Article in journal (Refereed) Published
Abstract [en]

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.

National Category
Social Sciences Interdisciplinary
Identifiers
urn:nbn:se:liu:diva-29669 (URN)10.1039/b202985e (DOI)15051 (Local ID)15051 (Archive number)15051 (OAI)
Available from: 2009-10-09 Created: 2009-10-09 Last updated: 2017-12-13Bibliographically approved
2. Quantification of volatile sulfur compounds in complex gaseous matrices by solid-phase microextraction
Open this publication in new window or tab >>Quantification of volatile sulfur compounds in complex gaseous matrices by solid-phase microextraction
2002 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 963, no 1-2, 57-64 p.Article in journal (Refereed) Published
Abstract [en]

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.

Keyword
matrix effects, air analysis, volatile sulfur compounds, sulfur compounds
National Category
Social Sciences Interdisciplinary
Identifiers
urn:nbn:se:liu:diva-29522 (URN)10.1016/S0021-9673(02)00556-3 (DOI)14880 (Local ID)14880 (Archive number)14880 (OAI)
Available from: 2009-10-09 Created: 2009-10-09 Last updated: 2017-12-13Bibliographically approved
3. Solid-phase microextraction for determination of background levels and point-source emissions of volatile sulfur compounds in the bioindustry
Open this publication in new window or tab >>Solid-phase microextraction for determination of background levels and point-source emissions of volatile sulfur compounds in the bioindustry
(English)Manuscript (preprint) (Other academic)
Abstract [en]

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%.

Keyword
Solid-phase microexh·acUon, Volatile sulfur compounds, Air analysis, Matrix effects, Artifact formation, Competitive adsmption
National Category
Social Sciences Interdisciplinary
Identifiers
urn:nbn:se:liu:diva-79018 (URN)
Available from: 2012-06-27 Created: 2012-06-27 Last updated: 2012-06-27Bibliographically approved
4. Hydrogen production from organic waste
Open this publication in new window or tab >>Hydrogen production from organic waste
Show others...
2001 (English)In: International journal of hydrogen energy, ISSN 0360-3199, E-ISSN 1879-3487, Vol. 26, no 6, 547-550 p.Article in journal (Refereed) Published
Abstract [en]

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.

Keyword
Fermentation, Hydrogen, Membrane, Palladium, Waste
National Category
Social Sciences
Identifiers
urn:nbn:se:liu:diva-47367 (URN)10.1016/S0360-3199(00)00125-7 (DOI)
Available from: 2009-10-11 Created: 2009-10-11 Last updated: 2017-12-13Bibliographically approved
5. Evaluation of solid-phase microextraction for time-weighted average sampling of volatile sulfur compounds at ppb concentrations
Open this publication in new window or tab >>Evaluation of solid-phase microextraction for time-weighted average sampling of volatile sulfur compounds at ppb concentrations
2003 (English)In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 75, no 11, 2626-2632 p.Article in journal (Refereed) Published
Abstract [en]

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.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-46617 (URN)10.1021/ac034124g (DOI)
Available from: 2009-10-11 Created: 2009-10-11 Last updated: 2017-12-13
6. Occurrence and abatement of volatile sulfur compounds during biogas production
Open this publication in new window or tab >>Occurrence and abatement of volatile sulfur compounds during biogas production
2004 (English)In: Journal of the Air & Waste Management Association, ISSN 1047-3289, Vol. 54, no 7, 855-861 p.Article in journal (Refereed) Published
Abstract [en]

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.

National Category
Social Sciences Interdisciplinary
Identifiers
urn:nbn:se:liu:diva-32074 (URN)17929 (Local ID)17929 (Archive number)17929 (OAI)
Available from: 2009-10-09 Created: 2009-10-09 Last updated: 2017-12-13Bibliographically approved

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