The quantitative determination of wine volatile sulfur compounds by automated headspace solid-phase microextraction (HS-SPME) with a carboxen-polydimethylsiloxane (CAR-PDMS) fiber and subsequent gas chromatography-pulsed flame photometric detection (GC-PFPD) has been evaluated. The direct extraction of the sulfur compounds in 5 ml of wine has been found to suffer from matrix effects and short linear ranges, problems which could not be solved by the use of different internal standards or by multiple headspace SPME. These problems were attributed to saturation of the fiber and to competitive effects between analytes, internal standards and other wine volatiles. Another problem was the oxidation of analytes during the procedure. The reduction in sample volume by a factor 50 (0.1 ml diluted with water or brine) brought about a reduction in the amount of sulfur compounds taken in the fiber by a factor just 3.3. Consequently, a new procedure has been proposed. In a sealed vial containing 4.9 ml of saturated NaCl brine, the air is thoroughly displaced with nitrogen, and the wine (0.1 ml) and the internal standards (0.02 ml) are further introduced with a syringe through the vial septum. This sample is extracted at 35 degrees C for 20 min. This procedure makes a satisfactory determination possible of hydrogen sulfide, methanethiol, ethanethiol, dimethyl sulfide, diethyl sulfide and dimethyl disulfide. The linear dynamic ranges cover the normal ranges of occurrence of these analytes in wine with typical r2 between 0.9823 and 0.9980. Reproducibility in real samples ranges from 10 to 20% and repeatability is better than 10% in most cases. The method accuracy is satisfactory, with errors below 20% for hydrogen sulfide and mostly below 10% for the other compounds. The proposed method has been applied to the analysis of 34 Spanish wines.