The general methods used to complete measurements of human exposures are identified and illustrations are provided for the cases of indirect and direct methods used for exposure analysis. The application of the techniques for external measurements of exposure, microenvironmental and personal monitors, are placed in the context of the need to test hypotheses concerning the biological effects of concern. The linkage of external measurements to measurements made in biological fluids is explored for a suite of contaminants. This information is placed in the context of the scientific framework used to conduct exposure assessment. Examples are taken from research on volatile organics and for a large scale problem: hazardous waste sites.