Climatic and compositional controls on secondary arsenic mineral formation in high-arsenic mine wastes, South Island, New Zealand

Recent and historic gold mines and mine wastes in the South Island of New Zealand have been exposed under a wide range of climatic conditions for up to 100 yr. The studied sites are in rain shadow areas east of the Southern Alps, and in wet areas west of the mountains. Arsenic concentrations in mine wastes are up to 20 wt% locally. The arsenic is primarily derived from arsenopyrite in gold-bearing ore, although roasting and oxidation of ore occurred at some mines. Arsenolite was a byproduct of roasting at two sites, and this was also discharged into mine wastes. Five secondary As minerals, scorodite, kankite, pharmacosiderite, zykaite, and bukovskyite, have formed in different mines and mine wastes during surficial oxidation and remobilisation. The minerals formed under different chemical and climatic conditions. Ferrihydrite with combined arsenate (up to 20 wt% As) occurs at all localities. Scorodite is the most common secondary As mineral, replacing arsenopyrite and/or arsenolite, and forming cement in mine wastes. Dissolution and precipitation of scorodite, which is strongly pH dependent, controls maximum dissolved As concentrations on a regional scale. Kankite has formed instead of scorodite in a persistently moist microclimate east of the mountains. Pharmacosiderite formed instead of scorodite on the 50 yr time-scale in mine tunnels at pH 7-8. Pharmacosiderite is distinctly less soluble than scorodite in this groundwater setting at pH 7-8, and apparently restricts dissolved As to 25 mg/L locally. Bukovskyite and zykaite form where dissolved sulfate concentrations are elevated and the host mine wastes are perennially damp.