title: Low molecular weight carboxylic acids in oxidizing porphyry copper tailings.
abstract: The distribution of low molecular weight carboxylic acids (LMWCA) was investigated in pore water profiles from two porphyry copper tailings impoundments in Chile (Piuquenes at La Andina and Cauquenes at El Teniente mine). The objectives of this study were (1) to determine the distribution of LMWCA, which are interpreted to be the metabolic byproducts of the autotroph microbial community in this low organic carbon system, and (2) to infer the potential role of these acids in cycling of Fe and other elements in the tailings impoundments. The speciation and mobility of iron, and potential for the release of H+ via hydrolysis of the ferric iron, are key factors in the formation of acid mine drainage in sulfidic mine wastes. In the low-pH oxidation zone of the Piuquenes tailings, Fe(III) is the dominant iron species and shows high mobility. LMWCA, which occur mainly between the oxidation front down to 300 cm below the tailings surface at both locations (e.g., max concentrations of 0.12 mmol/L formate, 0.17 mmol/L acetate, and 0.01 mmol/L pyruvate at Piuquenes and 0.14 mmol/L formate, 0.14 mmol/L acetate, and 0.006 mmol/L pyruvate at Cauquenes), are observed at the same location as high Fe concentrations (up to 71.2 mmol/L Fe(II) and 16.1 mmol/L Fe(III), respectively). In this zone, secondary Fe(III) hydroxides are depleted. Our data suggest that LMWCA may influence the mobility of iron in two ways. First, complexation of Fe(III), through formation of bidentate Fe(III)-LMWCA complexes (e.g., pyruvate, oxalate), may enhance the dissolution of Fe(III) (oxy)hydroxides or may prevent precipitation of Fe(III) (oxy)hydroxides. Soluble Fe(III) chelate complexes which may be mobilized downward and convert to Fe(II) by Fe(III) reducing bacteria. Second, monodentate LMWCA (e.g., acetate and formate) can be used by iron-reducing bacteria as electron donors (e.g., Acidophilum spp.), with ferric iron as the electron acceptor. These processes may, in part, explain the low abundances of secondary Fe(III) hydroxide precipitates below the oxidation front and the high concentrations of Fe(II) observed in the pore waters of some low-sulfide systems. The reduction of Fe(III) and the subsequent increase of iron mobility and potential acidity transfer (Fe(II) oxidation can result in the release of H+ in an oxic environment) should be taken in account in mine waste management strategies.
authors.affiliation: Institute of Mineralogy and Geochemistry (BFSH2), University of Lausanne, 1015 Lausanne, Switzerland. Bernhard.Dold@unil.ch
authors.forename: Bernhard
authors.initials: B
authors.lastname: Dold
authors.forename: David W
authors.initials: DW
authors.lastname: Blowes
authors.forename: Ralph
authors.initials: R
authors.lastname: Dickhout
authors.forename: Jorge E
authors.initials: JE
authors.lastname: Spangenberg
authors.forename: Hans-Rudolf
authors.initials: HR
authors.lastname: Pfeifer
mesh_terms: D000085:Acetates / Q000032:analysis; D002245:Carbon Dioxide / Q000032:analysis; D002264:Carboxylic Acids / Q000032:analysis*; D002412:Cations; D003300:Copper / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry; D005561:Formates / Q000032:analysis; D006863:Hydrogen-Ion Concentration; D007501:Iron / Q000032:analysis / Q000737:chemistry*; D008906:Mining; D008970:Molecular Weight; D010084:Oxidation-Reduction; D010100:Oxygen / Q000032:analysis; D016062:Porosity; D019289:Pyruvic Acid / Q000032:analysis; D013440:Sulfides / Q000737:chemistry; D014871:Water Microbiology; D018508:Water Purification / Q000379:methods*
chemical_list: D000085:Acetates; D002264:Carboxylic Acids; D002412:Cations; D005290:Ferric Compounds; D005561:Formates; D013440:Sulfides; C030544:formic acid; D002245:Carbon Dioxide; C021024:ferric hydroxide; D003300:Copper; D019289:Pyruvic Acid; D007501:Iron; D010100:Oxygen