Coprecipitation mechanisms of Zn by birnessite formation and its mineralogy under neutral pH conditions

Abstract

Birnessite (δ-Mn(IV)O₂) is a great manganese (Mn) adsorbent for dissolved divalent metals. In this study, we investigated the coprecipitation mechanism of δ-MnO₂ in the presence of Zn(II) and an oxidizing agent (sodium hypochlorite) under two neutral pH values (6.0 and 7.5). The mineralogical characteristics and Zn-Mn mixed products were compared with simple surface complexation by adsorption modeling and structural analysis. Batch coprecipitation experiments at different Zn/Mn molar ratios showed a Langmuir-type isotherm at pH 6.0, which was similar to the result of adsorption experiments at pH 6.0 and 7.5. X-ray diffraction and X-ray absorption fine structure analysis revealed triple-corner-sharing inner-sphere complexation on the vacant sites was the dominant Zn sorption mechanism on δ-MnO₂ under these experimental conditions. A coprecipitation experiment at pH 6.0 produced some hetaerolite (ZnMn(III)₂O₄) and manganite (γ-Mn(III)OOH), but only at low Zn/Mn molar ratios (< 1). These secondary precipitates disappeared because of crystal dissolution at higher Zn/Mn molar ratios because they were thermodynamically unstable. Woodruffite (ZnMn(IV)₃O₇•2H₂O) was produced in the coprecipitation experiment at pH 7.5 with a high Zn/Mn molar ratio of 5. This resulted in a Brunauer-Emmett-Teller (BET)-type sorption isotherm, in which formation was explained by transformation of the crystalline structure of δ-MnO₂ to a tunnel structure. Our experiments demonstrate that abiotic coprecipitation reactions can induce Zn-Mn compound formation on the δ-MnO₂ surface, and that the pH is an important controlling factor for the crystalline structures and thermodynamic stabilities.

Keywords: Surface complexation; X-ray absorption fine structure; Zinc removal; δ-MnO(2).