Solubility and transport of Cr(III) in a historically contaminated soil - Evidence of a rapidly reacting dimeric Cr(III) organic matter complex

•Dimeric Cr(III) bound to natural organic matter predominates in this soil.•The dimeric Cr(III) species has fast dissolution kinetics.•Solubility of dimeric Cr(III) was accurately described using a geochemical model.•Mobilization of particle bound Cr(III) was independent of irrigation intensity.

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 (>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 (≤1 day) at low pH (<3) and slightly slower (≤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.

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