The role of counter ions in nano-hematite synthesis: Implications for surface area and selenium adsorption capacity.

Nano metal oxides are of interest for aqueous selenium (Se) remediation, and as such, nano-hematite (nα-Fe2O3) was examined for use as a Se adsorbent. The effect of surface area on adsorption was also studied. nα-Fe2O3 particles were synthesized from Fe(NO3)3 and FeCl3 via forced hydrolysis. The resulting particles have similar sizes, morphologies, aggregate size, pore size, and PZC. The nα-Fe2O3 from FeCl3 (nα-Fe2O3-C) differs from the nα-Fe2O3 from Fe(NO3)3 (nα-Fe2O3-N) with a ∼25±2m(2)/g greater surface area. Selenite Se(IV) adsorption capacity on nα-Fe2O3 has a qmax ∼17mg/g for the freeze-dried and re-suspended nα-Fe2O3. The Δqmax for nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension was 4.6mg/g. For selenate Se(VI), the freeze-dried and re-suspended particles realize a Δqmax= 1.5mg/g for nα-Fe2O3 from Fe(NO3)3 and FeCl3. The nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension demonstrated Se(VI) Δqmax=5.4mg/g. In situ ATR-FTIR isotherm measurements completed for Se(VI) at a pH 6 suggest that Se(VI) forms primarily outer-sphere complexes with nα-Fe2O3 synthesized from both salts.

Mechanisms of Chromate, Selenate, and Sulfate Adsorption on Al-Substituted Ferrihydrite: Implications for Ferrihydrite Surface Structure and Reactivity.

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.

Polysulfide speciation and reactivity in chromate-contaminated soil.

Calcium polysulfide (CPS) has been observed to maintain a reducing capacity for prolonged time periods when used to treat Cr(VI)-contaminated soils. This study utilized bulk and micro-X-ray absorption near edge structure (XANES) spectroscopy to investigate sulfur speciation in soil samples treated with CPS in batch and column studies and to determine the source of the reducing potential. Bulk XANES spectra indicated the presence of two dominant sulfur species: elemental sulfur, which is the product of the sulfide-chromate redox reaction, and thiosulfate (S2O3(2-)). Micro-XANES analyses confirmed these findings and showed that elemental sulfur precipitated as large particles, while thiosulfate was diffused within the soil grains and thus available to react with chromate that leached from slowly dissolving PbCrO4. Micro-X-ray fluorescence (µXRF) analyses indicated a close association of Pb and thiosulfate, so that PbS2O3 is a likely sink for thiosulfate, accounting for up to 20% of the total S added. Sorption of thiosulfate on iron oxides below pH 8 is a second retention mechanism for thiosulfate in the solid. Given that thiosulfate cannot reduce chromate but can reduce solid-bound Fe(III) under neutral pH conditions, it is hypothesized that ferrous iron production is an additional mechanism to maintain reductive conditions in CPS-treated soils.

Mechanisms of chromate adsorption on boehmite.

Adsorption reactions play an important role in the transport behavior of groundwater contaminants. Molecular-scale information is needed to elucidate the mechanisms by which ions coordinate to soil mineral surfaces. In this study, we characterized the mechanisms of chromate adsorption on boehmite (γ-AlOOH) using a combination of extended X-ray absorption fine structure (EXAFS) measurements, in situ attenuated total reflectance Fourier transform infrared spectroscopy, and quantum chemical calculations. The effects of pH, ionic strength, and aqueous chromate concentration were investigated. Our overall findings were that chromate primarily forms outer-sphere complexes on boehmite over a broad range of pH and aqueous concentrations. Additionally, a small fraction of monodentate and bidentate inner-sphere complexes are present under acidic conditions, as evidenced by two sets of chromate stretching vibrations at approximately 915, 870, and 780cm(-1), and 940, 890, 850, and 780cm(-1), respectively. The bidentate complex is supported by a best-fit CrAl distance in the EXAFS of 3.2Å. Results from DFT also support the formation of monodentate and bidentate complexes, which are predicted to results in Gibbs energy changes of -140.4 and -62.5kJmol(-1), respectively. These findings are consistent with the intermediate binding strength of chromate with respect to similar oxyanions such as sulfate and selenite. Overall, the surface species identified in this work can be used to develop a more accurate stoichiometric framework in mechanistic adsorption models.

Investigation of chromate coordination on ferrihydrite by in situ ATR-FTIR spectroscopy and theoretical frequency calculations.

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 comparative evaluation of hexavalent chromium treatment in contaminated soil by calcium polysulfide and green-tea nanoscale zero-valent iron.

A column study for hexavalent chromium (Cr(VI)) removal from contaminated soil was performed using calcium polysulfide (CPS) and nanoscale zero-valent iron stabilized with green tea extract (GT-nZVI). Injection of CPS at 12 times the stoichiometric requirement (12×) resulted in quantitative Cr(VI) removal for up to 195 days of equivalent groundwater flow. Solid-bound Cr(VI) was reduced up to >99% (<2mg/kg). Treatment with CPS resulted in a short-term release of high sulfur concentrations. Injections of 12× and 24× stoichiometric GT-nZVI resulted in decrease in leachate pH from 6 to 2.5, which rebounded to 4.5 after the equivalent of 45 days and remained stable for the next equivalent 3 years. Metals concentrations in the effluent (Pb, Cr and Fe) increased following injection and quickly decreased, such that the mass flux was low with respect to the total amounts in the solid. Aqueous Cr(VI) was non-detect for the majority of the monitoring time, but concentrations eventually increased with respect to the control sample. Solid-bound Cr(VI) concentrations decreased by 30% and 66% in the 12× and 24× treatments, respectively. The low efficiency was attributed to increased sorption to iron surfaces at pH 2.5 and slow dissolution of PbCrO4, both of which were identified by micro-X-ray fluorescence and absorption analyses.

Calcium polysulfide treatment of Cr(VI)-contaminated soil.

Batch treatability studies for a Cr(VI)-contaminated glacial soil from a Cr plating facility were conducted using 1X and 2X the stoichiometric ratio of calcium polysulfide (CPS). The pH of the treated soil increased from 6 to 11 upon CPS addition, but progressively returned to 8-8.5 over the course of 1 year. The 1X dosage maintained a highly reducing environment up to 21 days of monitoring with the samples exposed to atmospheric oxygen, while 2X was reducing up to 180 days of curing. The EPA regulatory method for solid Cr(VI) could not reliably predict Cr(VI) in the treated solid due to ongoing reduction during the test. SPLP results showed that the CPS created an apparent Cr(VI) mobilization during the first 60 days of treatment, with subsequent decrease in soluble Cr(VI) up to 1 year of monitoring. Synchrotron micro-X-ray analyses at 60 days curing showed that Cr(VI) was predominantly bound as highly insoluble PbCrO(4) that precipitated in the interstitial pores of the soil, with very little to no Cr(VI) associated with the abundant iron oxyhydroxides. Despite its spatial accessibility and due to its low solubility, PbCrO(4) was recalcitrant to treatment, which proceeded only very slowly as judged by the SPLP data. It is concluded that, while CPS has a long residence time in the environment and is a promising reductant, in situ reduction is not an efficient treatment method for soils with highly insoluble Cr(VI) compounds, especially in surficial layers such as the one studied.