Chromium is a common soil contaminant and, although it has been studied widely, questions about its speciation and dissolutions kinetics remain unanswered. We combined information from an irrigation experiment performed with intact soil columns with data from batch experiments to evaluate solubility and mobilization mechanisms of Cr(III) in a historically contaminated soil (greater than 65 years). Particulate and colloidal Cr(III) forms dominated transport in this soil, but their concentrations were independent of irrigation intensity (2-20 mm h-1). Extended X-ray absorption fine structure (EXAFS) measurements indicated that Cr(III) associated with colloids and particles, and with the solid phase, mainly existed as dimeric hydrolyzed Cr(III) bound to natural organic matter. Dissolution kinetics of this species were fast (less or equal to 1 day) at low pH (less than 3) and slightly slower (less or equal to 5 days) at neutral pH. Furthermore, it proved possible to describe the solubility of the dimeric Cr(III) organic matter complex with a geochemical equilibrium model using only generic binding parameters, opening the way for use of geochemical models in risk assessments of Cr(III)-contaminated sites.