Weathering of sulphide minerals and trace element speciation in tailings of various ages in the Guanajuato mining district, Mexico

We studied the behavior of the trace elements (TE) As, Cu, Pb and Zn associated with sulphide minerals in tailings of different age at the Guanajuato mining district, Mexico. The objective was to determine the dominant fractions into which the TE move as tailings age and to identify how much time is needed until the dominant metal fractions approach equilibrium. We collected 21 samples from the surface of mine waste deposits of different ages (0, 2 , 4, 16, 70, 75, and 100 years), and measured their aqua regia extractable contents of As, Cu, Pb and Zn. We also applied a sequential extraction procedure to quantify water soluble TE as well as TE associated with carbonates, iron oxides, sulphides and the residual fraction. The mineralogy was analysed by X-ray diffraction, and selected samples were studied on polished specimens through a stereoscopic microscope. The TE in samples extracted with aqua regia ranged between 10 and 168 mg kg− 1 for As, 12 to 194 mg kg− 1 for Cu, 31 to 308 mg kg− 1 for Pb, and 122 to 1129 mg kg− 1 for Zn, and varied in a wide range within each age group of tailings. Water soluble Cu, Pb and Zn contents were below detection limits in almost all samples, which was attributed to the alkaline pH (7.17 to 8.61) in the tailings. Water extractable As was detected only in tailings older than 16 years, and concentrations ranged between 0.06 and 7.58 mg kg− 1. The proportion of TE associated with sulphides decreased in the tailings as they age, while the proportion of TE associated with iron oxides increased with time of exposure to the atmosphere, approximating equilibrium after 60 years for As, Cu and Zn, and after 40 years for Pb. Observations of polished specimens suggests that oxidation proceeds until coatings of secondary minerals cover and protect sulphide mineral grains from further weathering. First order rate equations were adjusted to the proportions of TE associated with either sulphides or iron oxides. Assuming that the TE in sulphide fractions correspond to arsenopyrite (FeAsS), chalcopyrite (CuFeS2), galena (PbS) and sphalerite (ZnS), the relative oxidation rate of sulphides followed the order: PbS > ZnS > FeAsS ≈ CuFeS2, while the relative affinity of the elements with iron oxides followed the sequence Cu ≈ Zn > As > Pb.