Release of chromium from Cr(III)- and Ni(II)-substituted goethite in presence of organic acids: Role of pH in the formation of colloids and complexes.

High levels of Cr(III) are hosted in Fe (oxyhydr)oxides in soils derived on (ultra)mafic rocks, which can pose potential risks to the environment. Organic acids can cause the solubilization of Fe (oxyhydr)oxides and the release of Cr(III). However, the release behaviors of Cr(III) from Fe (oxyhydr)oxides by organic acids and its main factors remain unclear. This study investigates the speciation of Cr released from Cr(III)-substituted goethite in the presence of citrate and oxalate and the effects of pH (3-7). Batch experiments showed that Fe(III) and Cr(III) dissolution were significantly enhanced by citrate and oxalate, and the extent of dissolution was negatively correlated with pH. When at relatively high pH (5-7), AF4-ICP-MS results revealed that large proportions of dissolved Fe (>58 %) and Cr (18 %-73 %) were presented in the form of Cr(III)-citrate colloids in the sizes of 1-125 nm and 125-350 nm. Further, FTIR and cryogenic XPS characterization demonstrated that the formation of·Cr(III)-citrate colloids was attributed to the adsorption and complexation of citrate on the substituted goethite surface. However, Cr was mainly released as soluble Cr(III)-organic complexes when presented at pH 3. While low pH inhibited the formation of Cr(III)-organic colloids, it promoted the release of Cr by facilitating the dissociation of surface Cr(III)-organic complexes. In addition, the incorporation of Ni(II) in Cr(III)-substituted goethite weakened the adsorption of organic acid by shortening the crystal size of goethite, thus significantly inhibiting the formation of Cr(III)-organic complexes and colloids. This study confirms the formation of Cr(III)-organic acid colloids and highlights the importance of pH on Cr release behavior, which is essential for evaluating Cr transport and fate in soils with high background values.