Arsenic mineralogy and mobility in the arsenic-rich historical mine waste dump.

Abstract A more than 250 year-old mine dump was studied to document the products of long-term arsenopyrite oxidation under natural conditions in a coarse-grained mine waste dump and to evaluate the environmental hazards associated with this material. Using complementary mineralogical and chemical approaches (SEM/EDS/WDS, XRD, micro-Raman spectroscopy, pore water analysis, chemical extraction techniques and thermodynamic PHREEQC-2 modeling), we documented the mineralogical/geochemical characteristics of the dumped arsenopyrite-rich material and environmental stability of the newly formed secondary minerals. A distinct mineralogical zonation was found (listed based on the distance from the decomposed arsenopyrite): scorodite (locally associated with native sulfur pseudomorphs) plus amorphous ferric arsenate (AFA/pitticite), kaňkite, As-bearing ferric (hydr)oxides and jarosite. Ferric arsenates and ferric (hydr)oxides were found to dissolve and again precipitate from downward migrating As-rich solutions cementing rock fragments. Acidic pore water (pH 3.8) has elevated concentrations of As with an average value of about 2.9 mg L − 1 . Aqueous As is highly correlated with pH ( R 2  = 0.97, p