Fractionation of Fe and Cu isotopes in acid mine tailings: Modification and application of a sequential extraction method

Application of this method on two sites of porphyry copper mine tailings in the Atacama Desert in Chile (Chañaral bay) revealed several implications about the mobilization of Fe and Cu in an environmental setting. Iron contents and Fe isotope compositions are homogeneous with depth (0-61 cm; δ56Fe ~0.2-0.3‰) for the bulk and the Fe(hyr)oxide fraction and only the deepest samples at ~60 cm exhibited lower δ56Fe values (~0‰), which are likely related to the occurrence of an alluvium at this depth. The Fe silicate fraction shows higher δ56Fe values (0.6-0.9‰), most likely because of preferential leaching of the light Fe isotopes. This consequently indicates a more pronounced Fe isotope fractionation with depth, as is expected from longer weathering. The Fe sulfide fraction is isotopically lighter compared to the Fe(hydr)oxide fraction, because during sulfide oxidation the heavy Fe isotopes prefer the oxidized forms and oxidative precipitation results in an enriched Fe isotopic signature for Fe(hydr)oxides. The Cu isotope compositions of all bulk samples and individual fractions (except the Cu sulfides) of one site (Ch1) exhibited a decrease of the δ65Cu values from the depth towards the surface, which is potentially related to Cu mobilization during capillary water rise in the arid climate. A correlation of δ65Cu with pH indicates preferential adsorption of 65Cu on Fe(oxy)hydroxides at site Ch1, which is evident by a change of δ65Cu from 0.5‰ to −0.7‰ in the water-soluble fraction. At another site (Ch12), where pH at depths was potentially not high enough for the formation of Fe-minerals that could adsorb Cu, only minor Cu isotope fractionation was observed in the water-soluble fraction. The Cu sulfide fraction at site Ch1 exhibits higher δ65Cu values with an increase from the bottom (0.42‰) to the surface (0.92‰), which might be related to preferential leaching of the light isotopes, e.g. by microorganisms.