Project: Kolarctic ENBI EnviMIne

The objectives of the project are to develop a methodology for environmentally safe mine closure under specific conditions in the Barents region by cross border cooperation, exchange experiences and scientific knowledge.</p

Sulphide oxidation, oxygen diffusion and metal mobility in sulphide-bearing mine tailings in Northern Sweden

Large quantities of sulphide-bearing mining wastes produced from ore processing are deposited throughout the world. Sulphide oxidation in the wastes may release acidic water with high concentrations of metals to the environment. Remediation strategies are usually site specific, since the physical and chemical properties of the wastes vary. Therefore, sulphide oxidation, oxygen diffusion and metal mobility in unoxidised and oxidised, remediated and unremediated wastes have been studied in the present work. The efficiency of different cover systems on unoxidised tailings from Kristineberg, were studied in pilot-scale test cells (5*5*3 m3)under field conditions. Clayey till, sewage sludge, apatite and Trisoplast were used as sealing layers and unspecified till as a protective cover. In one cell tailings were left uncovered. Unoxidised tailings in the test-cells in the initial stage after deposition showed relatively low sulphur release (600- 800 mg/l)in leachate waters, which probably was an effect of high moisture content in the tailings prior to deposition. Near-neutral pH found in the leachates was an effect of neutralisation by carbonate minerals present and lime (Ca(OH)2) added prior to deposition. Similar sulphur concentrations were found also in the uncovered tailings. The sulphide oxidation rate increased with time in the uncovered tailings, and decreased in the covered. The lowest oxygen concentrations were observed below the cover system with sewage sludge, which was the most effective barriar against oxygen in a short-term perspective. The oxygen fluxes through the clayey till and apatite layers were within the same magnitude and varied between 0.5 and 4 mole/year,m2. The Trisoplast layer seemed to have failed as a barrier against oxygen. Tailings studied at field scale at Laver and Kristineberg had oxidised for more than 50 years. The tailings at Kristineberg have high pyrite content (c.25% and 50%) and those at Laver have low grade of pyrrhotite (2-3%). The Laver tailings are unremediated, while at Kristineberg the tailings were remediated in 1996. The transport of metals in the drainage water at Laver decreased during a study period of 8 years. The transport of dissolved sulphur indicated a declining trend of sulphide oxidation rate in the tailings, which was confirmed by oxygen measurements in the tailings and weathering rate estimations. The decline was considered to be natural as a result of the increased distance that oxygen has to travel to reach unoxidised sulphide grains. The major part of the amounts of metals released by sulphide oxidation were secondarily retained in the tailings, and to a small extent in layers cemented by jarosite and Fe-(oxy)hydroxides. Sequential extraction of these layers showed that metals such as Cu and Pb were mostly associated with crystalline Fe-(oxy)hydroxides. Most important retention mechanism was, however, sorption onto minerals surfaces below the oxidation front. The studied Impoundment 1 at Kristineberg was remediated by two different methods; on one part a dry cover consisting of a sealing layer and a protective cover were applied, and the groundwater table was raised and a single dry cover applied on the other part. When the groundwater table was raised in oxidised tailings, secondarily retained metals such as Fe, Mg, Mn, S and Zn were remobilised resulting in increased concentrations in the groundwater. The concentrations declined with time, due to dilution by inflowing uncontaminated water. Decreased concentrations of Fe, Mg, Mn, S and Zn were observed also in the groundwater below the dry cover as the amount of percolating water decreased. The concentrations of trace elements such as Cd, Co, Cr, Cu, Ni and Pb were almost depleted in the groundwater, since these metals were retained within the tailings by mechanisms such as co-precipitation, precipitation and sorption. Analysis of pyrite grains by LA-ICP-SMS showed that pyrite surfaces were important for retention of As and Cu, in particular, but also for Cd and Zn. This study shows that the physico-chemical conditions expressed by pH and redox potential have a large impact on element mobility’s. For example, As was mobilised as a result of remediation, while the concentrations of most metals decreased in the drainage waters.Godkänd; 2006; 20061116 (pafi

Sulphide oxidation and geochemical processes in mine tailings

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.</p

The effect of vegetation on mine tailings

One of the major aims with passive remediation of sulfide-bearing mine tailings is to minimize or exclude oxygen diffusion through the tailings and decrease the oxidation of sulfides. A vegetation cover could potentially decrease the oxygen flux by oxygen consumption during decay of organic matter. The abandoned Cu mine at Laver in northern Sweden has not been remediated except for establishment of vegetation, and this offers the opportunity to investigate the effect of a vegetation cover on tailings.Whole-year sampling of surface drainage water from the tailings impoundment was performed during 1993 and 2001. The release of metals was only 5-10 % of the estimated weathering rate in the tailings during 1993 because of secondary retainment within the tailings. Results from 2001 show decreasing concentrations of several elements and increasing pH, indicating decreasing oxidation rate.Pore-gas measurement in two vertical profiles shows that vegetation on the tailings has no effect as a barrier for oxygen diffusion in comparison with barren parts.Cemented layers, which have formed at various depths in the tailings, have decreased the flux of oxygen to deeper parts; this could be an explanation of the decreased oxidation rate. The different cemented layers in the tailings differ in chemical composition and physical characteristics. There are two major types, both of which both contain iron oxides and carbon. The origin of the carbon is possibly the vegetation cover. None of the cemented layers acts as a trap for heavy metals, but As is enriched.The effect of vegetation as a oxygen barrier is negligible, but vegetation could act as a source for organic matter that could increase aggregation of iron oxides and clay minerals, thereby enhancing the formation of cemented layers or increasing metal-organic complexes which decrease the mobility of metals.</p

The occurrence of As, Hg, Sb and Tl in pyritic waste rock and the ability to prevent their release

Pyrite contains varying content of trace elements. Upon oxidation, these elements can be released having a great impact on water quality. Therefore, it is crucial to identify trace elements occurrence in minerals, and their overall leachability to ensure that suitable measures are taken to protect the environment. Sulfide-rich waste rock was mineralogically investigated, screened and quantified using QEMSCAN and LA-ICP-MS. The water quality was determined by leaching the waste rock in small scale test cells for more than two years. Arsenic, Hg, Sb, and Tl were elevated and the dominating trace elements in the waste rock with a content of 217, 17, 38, and 26 ppm respectively. Results show that pyrite was the most abundant mineral (66%) with traces of other sulfides such as arsenopyrite, chalcopyrite, and sphalerite. The abundance of pyrite along with the scarcity of any buffering minerals resulted in high concentrations of Fe3+ which subsequently generated acidic leachate pH (&lt;1.3) with extremely high concentrations of As (21 mg/L), Hg (13 µg/L), Sb (967 µg/L), and Tl (317 µg/L). The leachability of elements varied substantially. The highest leachability was observed for As (18%) due to the presence in pyrite preferentially to arsenopyrite or as a sulfosalt. Conversely, Sb was primarily identified in various sulfosalts such as Bournonite, found in cracks between pyrite grains, which can explain the lower leachability (5%). Results from LA-ICP-MS show that Hg was distributed in the more porous parts of the pyrite and displayed a partial correlation with Tl. However, Hg had low leachability compared to Tl implying at least two sources of Hg in the pyrite.Additional leaching tests with pyritic waste rock treated with lime kiln dust (5wt.%) to inhibit the sulfide oxidation are ongoing. The treatment has limited oxidation and leaching of As and Tl but has not prevented the release of Hg and Sb indicating restricted ability to prevent the oxidation of sulfide minerals such as sulfosalts. The overall results from LA-ICPMS and leaching of the waste rock indicate that mineral association of trace elements profoundly influences the possibility to prevent their release during sulfide oxidation and the overall effectiveness of inhibition. Moreover, this suggests that the ability to prevent sulfide oxidation in more complex mine wastes could prove difficult.</p

Prevention of sulfide oxidation in sulfide-rich waste rock

The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.</p

Projekt: Användning av restprodukter för förhindrande sulfid oxidation i reaktivt gruvavfall- en förstudie

En inventering av lämpliga restmaterial för efterbehandling och behandling av gruvavfall har genomförts och resulterat i en rapport</p