Chemical and biological interactions involving arsenic (As) and phosphorus (P) appear to affect significantly As transport and distribution in Whitewood Creek, South Dakota. Data (first‐order uptake rate constants, standing crop, and accumulation factors) that can be used to predict As transport have been determined using algae collected in the creek along a transect from upstream of mine discharge down gradient through a 57‐km impacted reach. Cultures of Achnanthes minutissima (Bacillariophyceae) were isolated from four sites along a longitudinal gradient of dissolved As within the study reach and were maintained at ambient dissolved‐As concentrations. Arsenic sorption‐rate constants for cell surfaces of these isolates were estimated as a function of dissolved arsenate and orthophosphate. All isolates sorbed orthophosphate preferentially over arsenate. Initial sorption of both arsenate and orthophosphate appeared to follow a first‐order equation within media formulations but did not adequately describe other observed effects among formulations or between isolates. Although estimated sorption‐rate constants increased slightly with increased dissolved arsenate concentration, algae isolated from a site with elevated dissolved As had a significantly slower rate of As uptake compared with the same species isolated from an uncontaminated site upstream. Field and laboratory results indicate that the benthic flora represent a significant As pool, which may episodically affect water‐column concentrations.