Sulphide Oxidation and Geochemical Processes in Mine Tailings
ISSN 1402-1757, ISRN LTU-LIC -03/64-SE
Licentiate thesis 2003:64, Luleå University of Technology
The generation of acid mine drainage (AMD) from oxidation of sulphide- bearing waste is a world wide problem, due to low pH levels and the release of metals to recipients. It is therefore important to understand the fundamental geochemical processes occurring in mine waste.
The geochemistry of the drainage water from the tailings at the abandoned Laver copper mine in Northern Sweden was studied in 2001 and compared with a previous study performed in 1993. All drainage water is collected in a brook, which means that Laver is a favourable site for mass balance studies.
The results show a decrease in the amount of sulphide-associated elements such as S, Cu and Zn in the drainage water, and an increase of the pH level. It has been suggested that this is due to the decrease in the sulphide oxidation rate in the tailings. Modelling the oxidation front movement using the shrinking core model gives similar results. This indicates that the sulphur transported in the drainage water could relatively well reflect the oxidation rate in the tailings. Oxygen sampling was also performed in 2001- 2002 to evaluate whether the flux of oxygen into the tailings was restricted by a vegetation cover. The results show that vegetation does not limit oxygen diffusion into the tailings. There is an atmospheric concentration throughout a profile through oxidised grass covered tailings during the whole sampling period. Oxygen concentrations at depths where sulphide oxidation occurs show seasonal variations, probably due to varying water saturation. Cemented layers were sampled at two locations in the Laver impoundment tailings, where they had been formed in spite of the low sulphide content and lack of carbonates.
The aim of the study was to determine the effects of cemented layer formation on metal mobility in the tailings. The cementing agents are jarosite and Fe-oxyhydroxides. Arsenic is strongly enriched and somewhat higher concentrations of Pb, V, Mo and Hg, compared to those in unoxidised tailings, occur in these layers. Sequential extraction shows that these metals are mostly adsorbed/co-precipitated with crystalline iron oxyhydroxides. The enriched metals will probably be remobilised if changes towards more reducing conditions occur, for instance as a result of remediation of the tailings impoundment. An attempt was made to use LA-ICP-SMS to quantify the role of pyrite surfaces as scavengers of metals in oxidising mine tailings. Pyrite grains were collected from a profile through the pyrite-rich tailings at the Kristineberg mine in Northern Sweden. At each spot hit by the laser, the surface layer was analysed in the first shot, and a second shot on the same spot indicated the chemical composition of the pyrite immediately below. The crater diameter for a laser shot is known, and by estimating the crater depth and total pyrite surface, the total enrichment on pyrite grains was calculated. Results are presented for As, Cd, Co, Cu, Ni and Zn.
The results clearly show that there is an enrichment of As, Cd, Cu and Zn on the pyrite surfaces below the oxidation front in the tailings, but not of Co and Ni. Arsenic is also enriched on the pyrite grains that survived in the oxidised zone. However, only 1.4 to 3.1% of the Cd and Zn released by sulphide oxidation in the oxidised zone had been enriched on the pyrite surfaces in the unoxidised tailings, but for As and Cu the corresponding figures are about 64 and 43%, respectively. The results should not be taken too literally but allow the conclusion that scavenging to pyrite surfaces is an important process for retention of As and Cu below the oxidation front in pyrite-rich tailings. Although only pyrite grains that appeared to be fresh, without surface coatings, were used in this study, the possibility of a thin layer of Fe-hydroxides occurring must be considered. Both adsorption to the pyrite directly, or to Fe-oxyhydroxides, may explain the enrichment of As, Cd, Cu and Zn on the pyrite surfaces, and, in the case of Cu, also replacement of Fe (II) by Cu(II) in pyrite.