RESUMO
The analysis of volatile sulfur compounds using headspace solid-phase microextraction (HS-SPME) is heavily influenced by matrix effects. The effects of a wine matrix, both non-volatile and volatile components (other than ethanol) were studied on the analysis of several common sulfur volatiles found in wine, including hydrogen sulfide (H2S), methanethiol (MeSH), dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), diethyl disulfide (DEDS), methyl thioacetate (MeSOAc), and ethyl thioacetate (EtSOAc). Varying levels of devolatilized wine and common wine volatiles (acids, esters, alcohols) were added to synthetic wine samples to act as matrices. Sulfur standards were added and analyzed using gas chromatography with pulsed-flame photometric detection (GC-PFPD). Five internal standards were used to find best representatives of each compound despite matrix effects. Sensitivity remained stable with the addition of devolatilized wine, while addition of volatile components decreased sensitivity. DMS was found to be best measured against EMS; DMDS and the thioacetates were best measured against DES; H2S, MeSH, DEDS, and DMTS were best measured against DIDS. The method was used to quantitate the volatile sulfur compounds in 21 wines with various ethanol contents and volatile profiles.
Assuntos
Microextração em Fase Sólida/métodos , Compostos de Enxofre/análise , Compostos Orgânicos Voláteis/análise , Vinho/análise , Cromatografia Gasosa/métodos , Dissulfetos/análise , Análise de Alimentos/métodos , Sulfeto de Hidrogênio/análise , Fotometria/métodos , Sensibilidade e Especificidade , Compostos de Sulfidrila/análise , Sulfetos/análise , Compostos de Enxofre/química , Compostos Orgânicos Voláteis/químicaRESUMO
Complications in the analysis of volatile sulfur compounds (VSC) in wine using solid-phase microextraction (SPME) arise from sample variability. Constituents of the wine matrix, including ethanol, affect the volatility and adsorption of sulfur volatiles on SPME fiber coatings (Carboxen- polydimethylsiloxane(PDMS); DVB-Carboxen-PDMS and DVB-PDMS), which can impact sensitivity and accuracy. Here, several common wine sulfur volatiles, including hydrogen sulfide (H2S), methanethiol (MeSH), dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), diethyl disulfide (DEDS), methyl thioacetate (MeSOAc), and ethyl thioacetate (EtSOAc) are analyzed, using SPME followed by gas chromatography (GC), using a system equipped with a pulsed-flame photometric detection (PFPD) system, at various ethanol concentrations in a synthetic wine matrix. Ethyl methyl sulfide (EMS), diethyl sulfide (DES), methyl isopropyl sulfide (MIS), ethyl isopropyl sulfide (EIS), and diisopropyl disulfide (DIDS) are evaluated as internal standards. The absorption of volatile compounds on the SPME fiber is greatly affected by ethanol. All compounds exhibit a stark decrease in detectability with the addition of ethanol, especially between 0.0 and 0.5% v/v. However, the ratio of interested sulfur compounds to the internal standard becomes more stable when the total alcohol concentration exceeds 2%. EMS was found to best resemble DMS. EIS and DES were found to best resemble DMDS, MeSOAc, and EtSOAc. DIDS was found to best resemble DEDS, DMTS, H2S, and MeSH.