Field measurements and bioassay experiments were done to investigate the effects of arsenic and phosphorus interactions on sorption of these solutes by the benthic flora (periphyton and submerged macrophytes) in Whitewood Creek, a stream in western South Dakota. Short-term (24-hour) sorption experiments were used to determine arsenic transport characteristics for algae (first-order rate constants for solute sorption, biomass, and accumulation factors) collected in the creek along a transect beginning upstream from a mine discharge point and downgradient through a 57-kilometer reach. Temporal changes in biomass differed significantly between and within sampling sites. Arsenic concentrations in plant tissue increased with distance downstream, but temporal changes in concentrations in tissues differed considerably from site to site. Cultures of Achnanthes minutissima(Bacillariophyceae) and Stichococcus sp. (Chlorophyceae) were isolated from four sites along a longitudinal concentration gradient of dissolved arsenic within the study reach and were maintained at ambient solute concentrations. Arsenic accumulation factors and sorption-rate constants for these isolates were determined as a function of dissolved arsenate and orthophosphate. Cell surfaces of algal isolates exhibited preferential orthophosphate sorption over arsenate. Initial sorption of both arsenate and orthophosphate followed first-order mass transfer for each culturing condition. Although sorption-rate constants increased slightly with increased dissolved-arsenate concentration, algae, isolated from a site with elevated dissolved arsenic in the stream channel, had a significantly slower rate of arsenic sorption compared with the same species isolated from an uncontaminated site upstream. In diel studies, amplitudes of the pH cycles increased with measured biomass except at a site immediately downstream from water-treatment-plant discharge. Inorganic pentavalent arsenic dominated arsenic speciation at all sites—not a surprising result for the well-oxygenated water column along this reach. Concentration fluctuations in dissolved-arsenic species lagged pH fluctuations by approximately 3 hours at the most downstream site, but no discernible lag was observed at an artificially pooled area with an order of magnitude higher biomass. Furthermore, the amplitudes of diel fluctuations in arsenic species were greater at the pooled area than at the most downstream site. Lack of correspondence between changes in dissolved-orthophosphate concentrations and arsenic species may have resulted from preferential sorption of orthophosphate over arsenate by the biomass. Based on carbon-fixation estimates, the phosphorus demand from photosynthetic activity required water-column concentrations to be supplemented by another source such as phosphate regeneration within the benthic community or desorption of particle-bound phosphate.