Chromate Reduction in Highly Alkaline Groundwater by Zerovalent Iron: Implications for Its Use in a Permeable Reactive Barrier

It is not currently known if the widely used reaction of zerovalent iron (ZVI) and Cr­(VI) can be used in a permeable reactive barrier (PRB) to immobilize Cr leaching from hyperalkaline chromite ore processing residue (COPR). This study compares Cr­(VI) removal from COPR leachate and chromate solution by ZVI at high pH. Cr­(VI) removal occurs more rapidly from the chromate solution than from COPR leachate. The reaction is first order with respect to both [Cr­(VI)] and the iron surface area, but iron surface reactivity is lost to the reaction. Buffering pH downward produces little change in the removal rate or the specific capacity of iron until acidic conditions are reached. SEM and XPS analyses confirm that reaction products accumulate on the iron surface in both liquors, but that other surface precipitates also form in COPR leachate. Leachate from highly alkaline COPR contains Ca, Si, and Al that precipitate on the iron surface and significantly reduce the specific capacity of iron to reduce Cr­(VI). This study suggests that, although Cr­(VI) reduction by ZVI will occur at hyperalkaline pH, other solutes present in COPR leachate will limit the design life of a PRB

Enhanced Crystallographic Incorporation of Strontium(II) Ions into Calcite via Preferential Adsorption at Obtuse Growth Steps

Sr-containing calcium carbonates were precipitated from solutions containing Ca­(OH)₂, SrCl₂, and Na₂CO₃ in a reactor where constant solution composition was maintained. The total concentration of divalent ions was same in all experiments, but the Sr/Ca ratio was varied between 0.002 and 0.86, and the pH value was between 12.02 and 12.25. All solutions were oversaturated with respect to calcite (saturation index SI_calcite = 1.2–1.5). Calcite was the only product formed at low Sr/Ca ratios, but at Sr/Ca ≥ 0.45 strontianite was detected in some systems. Sr-rich precipitate was observed in both a surface layer on rhombic calcite seed crystals (6.9–6 μm) and as smaller calcite crystals (>3.64–1.96 μm) that were elongated along their C-axis. The degree of crystal elongation increased with the Sr/Ca ratio in those crystals. Precipitates recovered from low Sr/Ca ratio experiments exhibited an XRD spectrum identical to that of rhombic calcite; however, the peaks attributed to Sr-containing calcite shifted progressively to lower 2θ values with increasing solution Sr/Ca ratio, indicating increased lattice volume. Sr K-edge EXAFS analysis of the precipitates showed that the shift in morphology and lattice volume is accompanied by a change in the local coordination of Sr²⁺ in calcite. The Sr–O bond lengths were similar to the Ca–O bond lengths in calcite, but Sr–O coordination increased from 6-fold in crystals containing 0.21 wt% Sr, to 8-fold in crystals containing 9.47 wt% Sr, and the Sr–Ca coordination decreased from 6 and 6 (for the first and second Sr–Ca shells, respectively) to 4 and 1. It is suggested that Sr²⁺ undergoes preferential incorporation at obtuse (+) growth sites on the calcite surface due to its large ionic radius (1.13 Å), and this increases the growth rate parallel to the C-axis, resulting in the observed elongation in this direction

Sustained bauxite residue rehabilitation with gypsum and organic matter 16 years after initial treatment

Bauxite residue is a high volume byproduct of alumina manufacture which is commonly disposed of in purpose-built bauxite residue disposal areas (BRDAs). Natural waters interacting with bauxite residue are characteristically highly alkaline, and have elevated concentrations of Na, Al, and other trace metals. Rehabilitation of BRDAs is therefore often costly and resource/infrastructure intensive. Data is presented from three neighboring plots of bauxite residue that was deposited 20 years ago. One plot was amended 16 years ago with process sand, organic matter, gypsum, and seeded (fully treated), another plot was amended 16 years ago with process sand, organic matter, and seeded (partially treated), and a third plot was left untreated. These surface treatments lower alkalinity and salinity, and thus produce a substrate more suitable for biological colonisation from seeding. The reduction of pH leads to much lower Al, V, and As mobility in the actively treated residue and the beneficial effects of treatment extend passively 20–30 cm below the depth of the original amendment. These positive rehabilitation effects are maintained after 2 decades due to the presence of an active and resilient biological community. This treatment may provide a lower cost solution to BRDA end of use closure plans and orphaned BRDA rehabilitation

Behavior of Aluminum, Arsenic, and Vanadium during the Neutralization of Red Mud Leachate by HCl, Gypsum, or Seawater

Red mud leachate (pH 13) collected from Ajka, Hungary is neutralized to < pH 10 by HCl, gypsum, or seawater addition. During acid neutralization >99% Al is removed from solution during the formation of an amorphous boehmite-like precipitate and dawsonite. Minor amounts of As (24%) are also removed from solution via surface adsorption of As onto the Al oxyhydroxides. Gypsum addition to red mud leachate results in the precipitation of calcite, both in experiments and in field samples recovered from rivers treated with gypsum after the October 2010 red mud spill. Calcite precipitation results in 86% Al and 81% As removal from solution, and both are nonexchangeable with 0.1 mol L^–1 phosphate solution. Contrary to As associated with neoformed Al oxyhydroxides, EXAFS analysis of the calcite precipitates revealed only isolated arsenate tetrahedra with no evidence for surface adsorption or incorporation into the calcite structure, possibly as a result of very rapid As scavenging by the calcite precipitate. Seawater neutralization also resulted in carbonate precipitation, with >99% Al and 74% As removed from solution during the formation of a poorly ordered hydrotalcite phase and via surface adsorption to the neoformed precipitates, respectively. Half the bound As could be remobilized by phosphate addition, indicating that As was weakly bound, possibly in the hydrotalcite interlayer. Only 5–16% V was removed from solution during neutralization, demonstrating a lack of interaction with any of the neoformed precipitates. High V concentrations are therefore likely to be an intractable problem during the treatment of red mud leachates