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Detection of sulfur compounds is difficult in complex samples such as soil and food. The volatility of these compounds can be an advantage if a trapping method is used. This method must be inert for the highly reactive compounds to avoid artifacts resulting from sample preparation and analysis procedures. This chapter describes the use headspace analysis with cryofocusing to detect low levels (ppb) of volatile sulfur compounds produced via fermentation of milk. This method is relatively simple compared to the use of sophisticated instrumentation for the unique identification tools available. It is also useful for other sample types. Milk is a good sample of a difficult substrate that reacts with volatile compounds and is reflective of the level of difficulty for this analysis.