The Hydrogeochemistry of Arsenic in the Clara Mine, Germany

Abstract.

The oxidative dissolution of primary arsenic-bearing sulfide minerals in barite-fluorite veins is a potential source of arsenic in the Clara Mine. Geological structures, especially the mineral veins, provide potential pathways for the water. The highest arsenic concentrations are found in ground water within the eastern part of the mine. Arsenic and major ions are positively correlated and provide evidence that arsenic is likely derived locally from the water-vein/water-rock interaction. Geochemical modeling with PHREEQC shows all the arsenate mineral phases to be significantly undersaturated, although secondary arsenate minerals are common in the oxidized part of the deposit. The mine waters plot near the boundary of Fe(OH)₃ and Fe²⁺ in the pH-Eh diagram for the As-Fe-S-H₂O-system. Arsenic occurs as the 5-valent species ${\text{H}}_{{\text{2}}} {\text{AsO}}^{ - }_{{\text{4}}}$ and ${\text{HAsO}}^{{{\text{2}} - }}_{{\text{4}}}$. Statistical analysis illustrates a strong association between As, Fe, pH, and HCO₃. Oxidation of the primary As-bearing minerals, such as pyrite and arsenopyrite, and the subsequent behavior of the oxyanion, arsenate, generally controls the distribution and speciation of arsenic. The low concentrations of dissolved As is due to co-precipitation and adsorption of arsenate by Fe, Al, and Mn (oxy)hydroxides.