Arsenic and iron speciation in the dispersible colloid fraction (DCF; 10-1000 nm) from an As-rich mine waste pile, sediments of a streambed that collects runoff from waste pile, the streambed subsoil, and the sediments of a downstream pond were investigated by combining asymmetrical-flow field-flow fractionation (AsFIFFF)/inductively-coupled plasma mass spectrometry (ICP MS), transmission electron microscopy (TEM) and X-ray absorption (XAS) spectroscopy. Calcium, Fe and As (Fe/As molar ratio similar to 1) were the main components of the DCF from waste pile. TEM/EDS and As and Fe XAS analysis revealed the presence of nanoparticle scorodite in this same DCF, as well as Fe nanoparticles in all samples downstream of the waste pile. Arsenic and Fe XAS showed As(V) adsorbed onto nanoparticulate ferrihydrite in the DCF of downstream samples. Micro-X-ray fluorescence indicated a strong correlation between Fe and As in phyllosilicate/Fe3+ (oxi) hydroxide aggregates from the sediment pond. Fractionation analysis showed the mean particle size of the DCF from the streambed sample to be smaller than that of the streambed subsoil and sediment ponds samples. These results show that an important and variable fraction of As may be bound to dispersible colloids that can be released from contaminated soils and transported downstream in natural systems. (C) 2014 Elsevier B.V. All rights reserved.