Low-crystallinity products of trace-metal precipitation in neutralized pit-lake waters without ferric and aluminous adsorbent: Geochemical modelling and mineralogical analysis

Abstract

AbstractThe removal of dissolved trace metals during neutralization of acid mine drainage has usually been described and modelled as a progressive, pH-dependent sorption onto standard ferric or aluminous adsorbent. In the absence of adsorbent mineral surfaces, trace metals tend to form amorphous to low-crystallinity compounds which are often difficult to characterize. Here, we study the behaviour of the more soluble metals (Cu2+, Zn2+, Mn2+, Co2+, Ni2+, Cd2+) in the absence of ferric and aluminous adsorbent by neutralization experiments with waters from two acidic pit lakes. The objectives of our study were to identify the mineral products formed by trace-metal precipitation and the pH ranges at which these metals are removed from the solutions. Both geochemical modelling and detailed mineralogical and chemical analyses (XRD, SEM, TEM, XRF, ICP-AES) were undertaken to characterize the products. The schwertmannite and hydrobasaluminite colloids formed in the initial neutralization stages were removed from the waters at pH 3.5 and 5.1, respectively. These two minerals had previously adsorbed the Cr3+ and Pb2+ initially present in the solutions. The Cu precipitates were amorphous to X-rays, though chemical and modelling data suggest that Cu probably precipitated as a precursor of brochantite (Cu4(SO4)(OH)6·2H2O) at pH >6.0, together with minor quantities of other Cu hydroxysulfates (langite, antlerite) and Cu(OH)2. At higher pH, other divalent metals (Zn2+, Mn2+) precipitated as silicates, carbonates and/or (possibly) minor oxides and (oxy)hydroxides. The high concentration of aqueous SiO2 in the solutions allowed Zn to precipitate as willemite (Zn2SiO4) at pH >7.0. Similarly, the presence of inorganic carbon (originally as CO2 (aq.)) greatly influenced the nature of the corresponding precipitate of Mn. This metal was initially present as Mn2+ and experienced a partly oxidative precipitation forming, in combination with Mg2+, the hydroxyl carbonate desautelsite (Mg6Mn2(CO3)(OH)16·4H2O) at pH 9.0–10.0. The formation of Mn3+/Mn4+ oxides and hydroxides (hausmannite, manganite, birnessite) could not be demonstrated, although geochemical calculations support their subordinate formation. Other metallic cations such as Co2+, Ni2+ and Cd2+ did not form discrete mineral phases but were totally removed by sorption onto and/or incorporation into the cited Zn and Mn compounds. The discrepancies between theoretical and demonstrated mineralogy and the significance of these minerals for future pit-lake remediation initiatives are discussed.