A deactivated glass capillary, wall-coated open tubular (WCOT) column is the heart of a novel gas chromatographic procedure for measuring reduced sulfur-containing gases in air samples. These deactivated, high resolution WCOT columns provide optimal chromatographic separation of compounds such as H/sub 2/S, COS, CH/sub 3/SH, CH/sub 3/SCH/sub 3/, CS/sub 2/, CH/sub 3/SSCH/sub 3/, and other organosulfur species. In addition, the combination of WCOT columns, a deactivated GC, and the flame photometric detector (FPD) increases the sensitivity of the GC/FPD method for sulfur compounds. The GC/WCOT/FPD instrumentation is also designed for complete compatibility with a cryogenic sampling procedure. This surface-deactivated, cryogenic enrichment system has been shown to provide known sampling efficiencies between 40% to approximately 100% for the important inorganic and organosulfur compounds at the low and sub-ppB concentrations. The methodology described has been successfully applied to field analyses of sulfur compound emissions from biogenic sources.