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The supergene alteration of cobalt arsenides produces various characteristic mineral assemblages including erythrite, pharmacolite, and other Ca±Mg±Co-bearing arsenates, which upon precipitation remove Co and As from natural waters. Their paragenetic relationships and stability conditions have not been investigated in detail. We present a detailed study on these assemblages, their successions and coexisting fluid compositions from the mining area of Wittichen, southwest Germany, where primary skutterudite and safflorite in granite-hosted barite-calcite veins are undergoing oxidation. Water analyses from the old mines, a semi-quantitative stability diagram and quantitative reaction path modeling are used to constrain their conditions of formation.

Weathering of cobalt arsenides: Natural assemblages and calculated stability relations among secondary Ca-Mg-Co arsenates and carbonates