Arsenopyrite weathering in acidic water: Humic acid affection and arsenic transformation

Arsenopyrite is a common metal sulfide mineral and weathers readily in the open environment, releases As, and pollutes the surrounding environment. Humic acid (HA) is ubiquitous in soils, sediments and waters, and contains various functional groups and complex with arsenic, iron and other metal ions that affect the weathering behavior of arsenopyrite. Because As, iron, and HA are redox-active compounds, electrochemical techniques, including polarization curves, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV), were used to fundamentally investigate the weathering process and mechanism of arsenopyrite over a wide range of environmental relevant conditions. Polarization curves showed higher HA concentrations (0-1000 mg•L^-1), higher temperatures (5-35°C) or acidities (pH 1.0-7.0) promoted arsenopyrite weathering; there was a linear relationship between the corrosion current density (i_corr), temperature (T) and acidity (pH): i_corr = -3691.2/T + 13.942 and i_corr = -0.2445pH + 2.2125, respectively. Arsenopyrite weathering readily occurred in the presence of HA as confirmed by its activation energy of 24.1 kJ•mol^-1, and EIS measurements confirmed that the kinetics were controlled by surface reaction as confirmed by decreased double layer resistance. CV and surface characterization (FTIR and XPS) showed that arsenopyrite initially oxidized to S⁰, As(III) and Fe²⁺, then S⁰ and Fe²⁺ were ultimately converted into SO₄^2- and Fe³⁺, while As(III) oxidized to As(V). Furthermore, the carboxyl (-COOH) and phenolic (-OH) of HA could bind with As(III)/(V) and Fe³⁺ via a ligand exchange mechanism forming As(III)/(V)-HA and As(III)/(V)-Fe-HA complexes that hinders the formation of FeAsO₄ and decreases the bioavailability of As. Findings gained from this study are valuable for the understanding of the fate and transport of As in acidic conditions, and have powerful implications for the remediation and management of As-bearing sites affected by mining activities.