An improvement in the procedure for investigation of organic acids and a new derivatization method, amenable to gas chromatographic-mass spectrometric detection of alcohols, are presented. The latter is based on the formation of phenacetyl esters. The simultaneous application of the two methods also allows data to be obtained on some volatile neutrals present in complex natural aqueous fluids. Application to wine and cider vinegars allowed detection of a number of previously unreported components, among which are interesting partially esterified polycarboxylic esters.