title: 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 (pH3.8) has elevated concentrations of As with an average value of about 2.9 mg L(-1). Aqueous As is highly correlated with pH (R2=0.97, p<0.001) indicating that incongruent dissolution of ferric arsenates controls dissolved As well as the pH of the percolating waste solution. Arsenic released from the dissolution of ferric arsenates into the pore water is, however, trapped by latter and lower-down precipitating jarosite and especially ferric (hydr)oxides. The efficiency of As sequestration by ferric (hydr)oxides in the waste dump and underlying soil has been found to be very effective, suggesting limited environmental impact of the mine waste dump on the surrounding soil ecosystems.
authors.affiliation: Institute of Geology, The Czech Academy of Sciences, v.v.i., Rozvojová 269, 165 00 Prague 6, Czech Republic. Electronic address: filippi@gli.cas.cz.
authors.forename: Michal
authors.initials: M
authors.lastname: Filippi
authors.affiliation: Institute of Geochemistry, Mineralogy and Mineral Resources, Faculty of Science, Charles University, Albertov 6, 128 43 Prague 2, Czech Republic.
authors.forename: Petr
authors.initials: P
authors.lastname: Drahota
authors.affiliation: Institute of Chemical Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic.
authors.forename: Vladimír
authors.initials: V
authors.lastname: Machovič
authors.affiliation: Institute of Geology, The Czech Academy of Sciences, v.v.i., Rozvojová 269, 165 00 Prague 6, Czech Republic.
authors.forename: Vlasta
authors.initials: V
authors.lastname: Böhmová
authors.affiliation: Institute of Geochemistry, Mineralogy and Mineral Resources, Faculty of Science, Charles University, Albertov 6, 128 43 Prague 2, Czech Republic.
authors.forename: Martin
authors.initials: M
authors.lastname: Mihaljevič
mesh_terms: D001151:Arsenic / Q000032:analysis*; D004784:Environmental Monitoring; D008906:Mining; D012987:Soil / Q000737:chemistry; D012989:Soil Pollutants / Q000032:analysis*; D064091:Waste Disposal Facilities
chemical_list: D012987:Soil; D012989:Soil Pollutants; D001151:Arsenic
keywords: Amorphous ferric arsenate (AFA); Arsenopyrite; Kaňkite; Pitticite; Scorodite; Sulfur