The occurrence and distribution of contaminants in aquatic systems are major components of the National Water-Quality Assessment (NAWQA) Program. Bed-sediment samples were collected at 18 sites in the Rio Grande Valley study unit between September 1992 and March 1993 to characterize the geographic distribution of organic compounds, including chlorinated insecticides, polychlorinated biphenyls (PCB's), and other chlorinated hydrocarbons, and also trace elements. Two-millimeter-size- fraction sediment was analyzed for organic compounds and less than 63-micron-size-fraction sediment was analyzed for trace elements. Concentrations of p,p'-DDE were detected in 33 percent of the bed-sediment samples. With the exception of DDT-related compounds, no other organochlorine insecticides or polychlorinated biphenyls were detected in samples of bed sediment. Whole-body fish samples were collected at 11 of the bed- sediment sites and analyzed for organic compounds. Organic compounds were reported more frequently in samples of fish, and more types of organic compounds were found in whole-body fish samples than in bed-sediment samples. Concentrations of p,p'-DDE were detected in 91 percent of whole-body fish samples. Polychlorinated biphenyls, cis-chlordane, trans-chlordane, trans- nonachlor, and hexachlorobenzene were other organic compounds detected in whole-body samples of fish from at least one site. Because of the extent of mineralized areas in the Rio Grande Basin arsenic, cadmium, copper, lead, mercury, selenium, and zinc concentrations in bed-sediment samples could represent natural conditions at most sites. However, a combination of natural conditions and human activities appears to be associated with elevated trace-element concentrations in the bed-sediment sample from the site Rio Grande near Creede, Colorado, because this sample exceeded the background trace-element concentrations calculated for this study. Fish-liver samples were collected at 12 of the bed-sediment sites and analyzed for trace elements. Certain trace elements were detected at higher concentrations in fish-liver samples than in bed-sediment samples from the same site. Both bed-sediment and fish-tissue samples are necessary for a complete environmental assessment of the occurrence and distribution of trace elements.