This paper discusses the analysis of chemical substances that may be associated with the food chain. This does not mean that the chemicals are known to present significant risk due to human dietary exposure, but it is intended to illustrate the approaches that should be considered for monitoring. Benchmark confirmatory methods that are applied to persistent chemical pollutants of public health concern are robust and accurate, but their sophistication limits the extent to which they are deployed. Put simply, the cost and availability of suchmethods can constrain the number (and thus the representativity) of samples tested, thus limiting the scope of exposure assessment.