Influence of Iron Substitution and Solution Composition on Brucite Carbonation.

Carbon neutral or negative mining can potentially be achieved by integrating carbon mineralization processes into the mine design, operations, and closure plans. Brucite [Mg(OH)2] is a highly reactive mineral present in some ultramafic mine tailings with the potential to be rapidly carbonated and can contain significant amounts of ferrous iron [Fe(II)] substituted for Mg; however, the influence of this substitution on carbon mineralization reaction products and efficiency has not been thoroughly constrained. To better assess the efficiency of carbon storage in brucite-bearing tailings, we performed carbonation experiments using synthetic Fe(II)-substituted brucite (0, 6, 23, and 44 mol % Fe) slurries in oxic and anoxic conditions with 10% CO2. Additionally, the carbonation process was evaluated using different background electrolytes (NaCl, Na2SO4, and Na4SiO4). Our results indicate that carbonation efficiency decreases with increasing Fe(II) substitution. In oxic conditions, precipitation of ferrihydrite [Fe10IIIO14(OH)2] and layered double hydroxides {e.g., pyroaurite [Mg6Fe2III(OH)16CO3·4H2O]} limited carbonation efficiency. Carbonation in anoxic environments led to the formation of Fe(II)-substituted nesquehonite (MgCO3·3H2O) and dypingite [Mg5(CO3)4(OH)2·âˆ¼5H2O], as well as chukanovite [Fe2IICO3(OH)2] in the case of 23 and 44 mol % Fe(II)-brucite carbonation. Carbonation efficiencies were consistent between chloride- and sulfate-rich solutions but declined in the presence of dissolved Si due to the formation of amorphous SiO2·nH2O and Fe-Mg silicates. Overall, our results indicate that carbonation efficiency and the long-term fate of stored CO2 may depend on the amount of substituted Fe(II) in both feedstock minerals and carbonate products.

Oxidation of V(IV) by Birnessite: Kinetics and Surface Complexation.

Vanadium is a redox-active metal that has been added to the EPA's Contaminant Candidate List with a notification level of 50 µg L-1 due to mounting evidence that VV exposure can lead to adverse health outcomes. Groundwater V concentration exceeds the notification level in many locations, yet geochemical controls on its mobility are poorly understood. Here, we examined the redox interaction between VIV and birnessite (MnO2), a well-characterized oxidant and a scavenger of many trace metals. In our findings, birnessite quickly oxidized sparingly soluble VIV species such as häggite [V2O3(OH)2] into highly mobile and toxic vanadate (HnVO4(3-n)-) in continuously stirred batch reactors under neutral pH conditions. Synchrotron X-ray absorption spectroscopic (XAS) analysis of in situ and ex situ experiments showed that oxidation of VIV occurs in two stages, which are both rapid relative to the measured dissolution rate of the VIV solid. Concomitantly, the reduction of birnessite during VIV oxidation generated soluble MnII, which led to the formation of the MnIII oxyhydroxide feitknechtite (ß-MnOOH) upon back-reaction with birnessite. XAS analysis confirmed a bidentate-mononuclear edge-sharing complex formed between VV and birnessite, although retention of VV was minimal relative to the aqueous quantities generated. In summary, we demonstrate that Mn oxides are effective oxidants of VIV in the environment with the potential to increase dissolved V concentrations in aquifers subject to redox oscillations.

Aqueous Vanadate Removal by Iron(II)-Bearing Phases under Anoxic Conditions.

Vanadium contamination is a growing environmental hazard worldwide. Aqueous vanadate (HxVVO4(3-x)-(aq)) concentrations are often controlled by surface complexation with metal (oxyhydr)oxides in oxic environments. However, the geochemical behavior of this toxic redox-sensitive oxyanion in anoxic environments is poorly constrained. Here, we describe results of batch experiments to determine kinetics and mechanisms of aqueous H2VVO4- (100 µM) removal under anoxic conditions in suspensions (2.0 g L-1) of magnetite, siderite, pyrite, and mackinawite. We present results of parallel experiments using ferrihydrite (2.0 g L-1) and Fe2+(aq) (200 µM) for comparison. Siderite and mackinawite reached near complete removal (46 µmol g-1) of aqueous vanadate after 3 h and rates were generally consistent with ferrihydrite, whereas magnetite removed 18 µmol g-1 of aqueous vanadate after 48 h and uptake by pyrite was limited. Removal during reaction with Fe2+(aq) was observed after 8 h, concomitant with precipitation of secondary Fe phases. X-ray absorption spectroscopy revealed V(V) reduction to V(IV) and formation of bidentate corner-sharing surface complexes on magnetite and siderite, and with Fe2+(aq) reaction products. These data also suggest that V(IV) is incorporated into the mackinawite structure. Overall, we demonstrate that Fe(II)-bearing phases can promote aqueous vanadate attenuation and, therefore, limit dissolved V concentrations in anoxic environments.