Selective preconcentration of volatile mercaptans in small SPE cartridges: quantitative determination of trace...

A general procedure for the selective preconcentration and purification of mercaptans has been developed. Mercaptans are strongly retained in a small (20 mg) SPE cartridge containing p-hydroxymercurybenzoate. The cartridge can then be rinsed with relatively high volumes of polar (water/methanol mixtures) and non-polar (pentane or pentane/ether mixtures) rinsing solutions to remove nearly all volatile compounds lacking a thiol functionality. Retained analytes are further eluted with a small volume of an organic solvent containing 1,4-dithioerythritol. Some basic aspects of the strategy, such as the retention of p-hydroxymercurybenzoate in the sorbent and its stability versus different rinsing and eluting systems, have been studied in depth. Light sulfur compounds contained in water or wine, including mercaptans such as methanethiol or thioethers, such as diethyl sulfide, can be quantitatively extracted, although only mercaptans can be quantitatively recovered if a polar rinsing is applied. The strategy has been applied to the GC-MS quantitative determination of some trace polyfunctional mercaptans that are key aromas in wine, such as 2-methyl-3-furanthiol, 2-furfurylthiol, 4-mercapto-4-methyl-2-pentanone, 3-mercaptohexyl acetate or 3-mercaptohexanol. The developed method reaches detection limits in the ng/L range and has a satisfactory analytical behavior, being quite simple and fast.