Mining-contaminated waters may contain high levels of arsenic (As) and iron (Fe), among various metals and metalloids. The complex behavior of As makes its contamination difficult to remediate. This study aimed to determine the sources, possible association of As and Fe with colloids and their speciation and mobility in the Jiehe River, a stream impacted by gold mining. Particulate (>450 nm), colloidal (7 e450 nm), and truely dissolved (<7 nm) forms of As and Fe were determined, and the species of As [As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid] and Fe [Fe(II) and Fe(III)] were both analyzed and modelled using geochemical program Visual MinteQ 3.0. High concentrations of As and Fe were observed in both filtered and particulate forms in most of the water samples. Total As was in the range of 1.0e719 mg L À1 with a median of 140 mg L À1. Total Fe was 0.4e68.2 mg L À1 with a median of 15.0 mg L À1. Arsenic was mainly adsorbed on ferrihydrite, goethite, and hematite in the upstream water samples. In contrast, it was mostly in truely dissolved forms in the water samples at downstream. Visual MinteQ 3.0 modelling results revealed that As adsorbed on, or co-precipitated with, stream sediment can be easily released under the environmental conditions of the downstream reach (11.4e37.5 km). These findings would benefit the environmental management of gold mining impacted Jiehe River, and indicate the need for further quantitative research on As migration facilitated by Fe (hydr)oxide colloids and the release of As from contaminated stream sediments.