Abstract: A continuous emission monitoring system is disclosed for detecting toxic substances of various types in either stack gas or ambient air. Particular systems are illustrated for monitoring lewisite and chromium(VI). Each system employs a gas sampler that utilizes a high-volume, wet cyclone concentrator unit which scrubs the contaminants from the gas into water or another suitable scrubbing solution. In-line chemical processing of the contaminated sample thus obtained is accomplished either within the sampling unit or by an external chemistry processing module. After processing to provide an analyte in the sample indicative of the presence of a predetermined contaminant, the sample stream is delivered to an ion chromatograph or other analyzer to determine the presence and quantity of the analyte and indicate whether a danger level has been reached. This provides monitoring on an essentially real-time or near real-time basis.