Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in sediments and flood-plain soils collected along the Tittabawassee River in Michigan ranged from 102 to 53,600 pg/g, dry wt. Mean PCDD/PCDF concentrations in downstream sediment and soil were from 10- to 20-fold greater than those found at locations upstream of Midland, Michigan. Concentrations of PCDD/PCDF in sediments and flood-plain soils from the Tittabawassee watershed were comparable to those found in industrialized areas such as the Housatonic and lower Passaic Rivers in the U.S. Concentrations of PCDDs/PCDFs in soil and sediment were not correlated with total organic carbon (TOC) in sediments or soils. OCDD and 2,3,7,8-TeCDF were the predominant congeners in sediment/soil collected from locations downstream of Midland, Michigan. Principal component analysis of the PCDD/PCDF congener profile suggested the presence of sources originating from a mixture of chlorophenol and other chlorinated compound production. Mass balance analysis of TCDD equivalents (TCDD-EQs) derived from H4IIE-luc bioassay of sediment extracts and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) estimated from instrumental analysis suggested that PCDDs/PCDFs were the major dioxin-like compounds present in sediments. A significant correlation existed between bioassay-derived TCDD-EQs and instrumentally measured TEQs (r2 = 0.94).