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Chromate mobility, reactivity, and bioavailability in soil environments are affected by adsorption reactions on iron oxide minerals, but the adsorption mechanisms remain controversial. In this study, we employed in situ attenuated total reflectance Fourier transform infrared spectroscopy and theoretical frequency calculations to characterize chromate adsorption on 2-line ferrihydrite. The effects of pH, aqueous chromate concentration, ionic strength, and deuterium exchange were investigated. Results suggest the formation of monodentate and bidentate surface complexes. It was determined that monodentate complexes are dominant at low surface coverage and pH ≥ 6.5 and that bidentate complexes form at high surface coverage and pH < 6. Deuterium exchange experiments indicated that the inner-sphere complexes are not protonated. Difference spectra revealed that monodentate complexes are particularly susceptible to ionic strength effects under acidic conditions.

A pilot-scale treatment study was implemented at a deposition site of chromite ore processing residue (COPR) in New Jersey. Ferrous sulfate heptahydrate (FeSO4 x 7H2O) was employed to reduce hexavalent chromium in two dosages with three types of soil mixing equipment. XANES analyses of treated samples cured for 240 days indicated that all treatment combinations failed to meet the Cr(VI) regulatory limit of 240 mg/kg. More importantly, the discrepancy between XANES and alkaline digestion results renders the latter unreliable for regulatory purposes when applied to ferrous-treated COPR. Regardless of Cr-(VI), the introduction of reductant containing sulfate, mechanical mixing, water, acidity, and the resulting temperature increase in treated COPR promoted dissolution of brownmillerite (Ca2FeAlO5), releasing alumina and alkalinity. The pH increase caused initially precipitated gypsum (CaSO4 x 2H2O) to progressively convert to ettringite (Ca6Al2(SO4)3 x 32H2O) and its associated volume expansion under both in situ and ex situ conditions, with a maximum of 0.8 m vertical swell within 40 days of curing. While Cr-(VI) treatment remains a challenge, the intentional exhaustion of the heave potential of COPR by transforming all Al sources to ettringite emerges as a possible solution to delayed ettringite formation, which would hamper site redevelopment.

Ferrihydrite is a nanocrystalline Fe (hydr)oxide and important sink for environmental contaminants. Although Fe (hydr)oxides are rarely pure in natural systems, little is known about the effects of structural impurities such as Al on the surface properties and reactivity of ferrihydrite. In this study, we characterized the adsorption mechanisms of chromate, selenate, and sulfate on Al-substituted ferrihydrite (0, 6, 12, 18, and 24 mol % Al) using in situ attenuated total reflection Fourier transform infrared spectroscopy. Spectral data sets recorded as a function of pH were processed using a multivariate curve resolution technique to identify which types of surface species form and to generate their concentration profiles as a function of pH and Al content. Results show a significant increase in relative fraction of outer-sphere complexes for all three oxyanions with increasing Al substitution. In addition, the effect of Al substitution is found to be mechanism-specific in the case of chromate, with bidentate complexes disproportionately suppressed over monodentate complexes at higher Al contents. Overall, our findings have important implications for the fate of chromate, selenate, and sulfate in subsurface environments and offer new insight into the surface reactivity of Al-ferrihydrite.