Passive treatment of acid rock drainage (ARD) is a sustainable approach to control ARD, with sulfide inhibition by silica being a promising alternative. In a small-scale column leaching, a total of four cells loaded with pyritic waste rock (11 wt% S) from an operating Cu mine in Sweden were kept in a climatic chamber at a controlled temperature and humidity. The waste rock was leached for 11 weeks before treatment using alkaline silicate solution was applied, without pH buffer and adjuster. One cell was left untreated, whereas the others were treated with silicate solution as a source of dissolved silica, with and without H2O2 pre-oxidation. The pH in silica-treated cells generated leachate with circumneutral pH until the end of the leaching cycle, whereas sulfide oxidation accelerated in the absence of treatment. Leachate quality in all Si-treated cells improved, as evidenced by the suppressed release of sulfur and other metals (e.g., Al, Fe, Cu, Co, Mn, and Ni). Upon treatment with a longer contact time, silica (SiO2) layer developed on waste rock and inhibited pyrite. The layer remained stable upon extended exposure to air and water for up to 10 weeks after treatment. Despite forming a siliceous Fe–O phase, H2O2 pre-oxidation resulted in indirect oxidation of sulfides and other phases. With an excess of silicate solution and at alkaline pH, pyrite surfaces are devoid of coating and metal ions were mobilized. Finally, this study suggested that treatment of pyritic waste rock using silica can attenuate ARD formation and prevent metal leaching by pyrite inhibition and maintaining a circumneutral pH environment or both.

Geothermal waters often are enriched in trace metal(loid)s, such as arsenic, antimony, molybdenum, and tungsten. The presence of sulfide can lead to the formation of thiolated anions; however, their contributions to total element concentrations typically remain unknown because nonsuitable sample stabilization and chromatographic separation methods convert them to oxyanions. Here, the concurrent widespread occurrence of thioarsenates, thiomolybdates, thiotungstates, and thioantimonates, in sulfide-rich hot springs from Yellowstone National Park and Iceland is shown. More thiolation was generally observed at higher molar sulfide to metal(loid) excess (Iceland > Yellowstone). Thioarsenates were the most prominent and ubiquitous thiolated species, with trithioarsenate typically dominating arsenic speciation. In some Icelandic hot springs, arsenic was nearly quantitatively thiolated. Also, for molybdenum, thioanions dominated over oxyanions in many Icelandic hot springs. For tungsten and antimony, oxyanions typically dominated and thioanions were observed less frequently, but still contributed up to a few tens of percent in some springs. This order of relative abundance (thioarsenates > thiomolybdates > thiotungstates ≈ thioantimonates) was also observed when looking at processes triggering transformation of thioanions such as mixing with non-geothermal waters or H2S degassing and oxidation with increasing distance from a discharge. Even though to different extents, thiolation contributed substantially to speciation of all four elements studied, indicating that their analysis is required when studying geothermal systems.

The best available technology for preventing the formation of acid drainage water from the sulfidic waste rock at mine closure aims to limit the oxygen access to the waste. There is, however, a concern that contaminants associated with secondary minerals become remobilized due to changing environmental conditions. Metal(loid) mobility from partially oxidized sulfidic waste rock under declining and limited oxygen conditions was studied in unsaturated column experiments. The concentrations of sulfate and metal(loid)s peaked coincidently with declining oxygen conditions from 100 to < 5 sat-% and to a lesser extent following a further decrease in the oxygen level during the experiment. However, the peak concentrations only lasted for a short time and were lower or in the similar concentration range as in the leachate from a reference column leached under atmospheric conditions. Despite the acid pH (~ 3), the overall quality of the leachate formed under limited oxygen conditions clearly improved compared with atmospheric conditions. In particular, the release of As was two orders of magnitude lower, while cationic metals such as Fe, Cu, Mn, and Zn also decreased, although to a lesser extent. Decreased sulfide oxidation is considered the primary reason for the improved water quality under limited oxygen conditions. Another reason may be the immobility of Fe with the incorporation of metal(loid)s in Fe(III) minerals, in contrast to the expected mobilization of Fe. The peaking metal(loid) concentrations are probably due to remobilization from solid Fe(III)-sulfate phases, while the relatively high concentrations of Al, Mn, and Zn under limited oxygen conditions were due to release from the adsorbed/exchangeable fraction. Despite the peaking metal(loid) concentrations during declining oxygen conditions, it is clear that the primary remediation goal is to prevent further sulfide oxidation.

During the operation of a mine, waste rock is often deposited in heaps and usually left under ambient conditions allowing sulfides to oxidize. To focus on waste rock management for preventing acid rock drainage (ARD) formation rather than ARD treatment could avoid its generation and reduce lime consumption, costs, and sludge treatment. Leachates from 10 L laboratory test cells containing sulfide-rich (> 60% pyrite) waste rock with and without the addition of lime kiln dust (LKD) (5 wt.%) were compared to each other to evaluate the LKD’s ability to maintain near neutral pH and reduce the sulfide oxidation. Leaching of solely waste rock generated an acidic leachate (pH < 1.3) with high concentrations of As (21 mg/L), Cu (20 mg/L), Fe (18 g/L), Mn (45 mg/L), Pb (856 μg/L), Sb (967 μg/L), S (17 g/L), and Zn (23 mg/L). Conversely, the addition of 5 wt.% LKD generated and maintained a near neutral pH along with decreasing of metal and metalloid concentrations by more than 99.9%. Decreased concentrations were most pronounced for As, Cu, Pb, and Zn while S was relatively high (100 mg/L) but decreasing throughout the time of leaching. The results from sequential extraction combined with element release, geochemical calculations, and Raman analysis suggest that S concentrations decreased due to decreasing sulfide oxidation rate, which led to gypsum dissolution. The result from this study shows that a limited amount of LKD, corresponding to 4% of the net neutralizing potential of the waste rock, can prevent the acceleration of sulfide oxidation and subsequent release of sulfate, metals, and metalloids but the quantity and long-term stability of secondary minerals formed needs to be evaluated and understood before this method can be applied at a larger scale.

This report is the outcome of the SIP STRIM project

StopOx-Utilization of industrial residuals for prevention of sulfide oxidation in mine waste implemented at Applied geochemistry, Luleå University of Technology running from 2015 to 2018. Boliden Mineral has been partner and co-funder of the project. Other partners in the project were Cementa, Dragon Mining, MEROX, Nordkalk, and SP Processum. The overall aim of the project was to develop prevention technologies to reduce the sulfide oxidation in mine waste, during and after operation, and thereby reduce the generation of acid mine drainage. The StopOx project has been focusing on sulfidic mine waste from the Boliden area which were disposed of and are causing acid mine drainage or have the potential. Industrial residues/products were supplied by BillerudKorsnäs, Cementa, MEROX, and Nordkalk. The report consists of chapters based on three subprojects.

Chapter 1. Introduction

Chapter 2. Inhibition technology with aim to minimize waste rock oxidation during operations by using residues from other industries (passivation of sulfidic surfaces by the formation of secondary minerals)

Chapter 3. The suitability of green liquor dregs as substitutes for or additives to till in a sealing layer as part of a cover system

Chapter 4. Weathering of waste rock under changing chemical conditions

The research described in chapters 2 and 3 was performed by Ph.D. students and will continue until 2021, while the subproject in chapter 2 ended in 2018.

Prevention and mitigation of acid rock drainage (ARD) from mine wastes are crucial for limiting environmental impact. However, preventive measures are often too expensive, potentially harmful to the environment or not applied early enough. This study aimed to test the potential of different secondary raw materials for maintaining a circumneutral pH (6–7) in a sulfide oxidation environment, allowing secondary minerals to form on reactive sulfide surfaces to prevent release of acid, metals and metalloids, and thereby ARD generation. Five materials (blast furnace slag, granulated blast furnace slag, cement kiln dust, bark ash, lime kiln dust) were selected based on their alkaline properties, availability and yearly yield. High sulfidic (>50 wt%, sulfide) waste rock from an active Cu–Zn–Au–Ag open pit mine in northern Sweden was leached in small-scale laboratory test cells under ambient condition for 4–8 weeks before adding secondary raw materials on the surface in an attempt to prevent ARD generation. During 52 subsequent weeks of leaching, the pH and electrical conductivity in the leachate from the waste rock varied between 1.7-4.6 and 2.1–22.8 mS/cm, respectively. All secondary raw materials were able to increase the pH to circumneutral. However, blast furnace slag, granulated blast furnace slag and cement kiln dust were not able to maintain a circumneutral pH for an extended time due to self-cementation or carbonation, whereas bark ash (1 wt%) and lime kiln dust (5 wt%) prevented acidity, metal and metalloid leaching. Materials such as cement kiln dust and bark ash contained elevated concentrations of, e.g., Cd and Zn, but the release of metals and metalloids was generally low for most elements, except for Cl, K and Na, most likely due to salt dissolution.

The geochemistry of Fe(II) and Fe(III) was studied in natural geothermal waters in Iceland. Samples of surface and spring water and sub-boiling geothermal well water were collected and analyzed for Fe(II), Fe(III) and Fe_total concentrations. The samples had discharge temperatures in the range 27–99 °C, pH between 2.46 and 9.77 and total dissolved solids 155–1090 mg/L. The concentrations of Fe(II) and Fe(III) were determined in the <0.2 μm filtered and acidified fraction using a field-deployed ion chromatography spectrophotometry (IC-Vis) method within minutes to a few hours of sampling in order to prevent post-sampling changes. The concentrations of Fe(II) and Fe(III) were <0.1–130 μmoL/L and <0.2–42 μmoL/L, respectively. In-situ dialysis coupled with Fe(II) and Fe(III) determinations suggest that in some cases a significant fraction of Fe passing the standard <0.2 μm filtration method may be present in colloidal/particulate form. Therefore, such filter size may not truly represent the dissolved fraction of Fe but also nano-sized particles. The Fe(II) and Fe(III) speciation and Fe_total concentrations are largely influenced by the water pH, which in turn reflects the water type formed through various processes. In water having pH of ∼7–9, the total Fe concentrations were <2 μmoL/L with Fe(III) predominating. With decreasing pH, the total Fe concentrations increased with Fe(II) becoming increasingly important and predominating at pH < 3. In particular in waters having pH ∼6 and above, iron redox equilibrium may be approached with Fe(II) and Fe(III) possibly being controlled by equilibrium with respect to Fe minerals. In many acid waters, the Fe(II) and Fe(III) distribution may not have reached equilibrium and be controlled by the source(s), reaction kinetics or microbial reactions

Prevention and mitigation of acid rock drainage from mining are decisive for limiting environmental impact. Five by-products and industrial remnants (lime kiln dust, blast furnace slag, granulated blast furnace slag, cement kiln dust and fly ash) were investigated for their suitability to prevent acidity and metal(loid)s during leaching from highly sulfidic (50wt%, sulfide) waste rock in small scale laboratory test cells. Variations in pH and electrical conductivity in leachate allowed differentiation between the different materials. Lime kiln dust (5wt%) and fly ash (1 and 2.5wt%) were observed to be the most suitable materials to prevent acidity and metal(loid)s leaching.

The chemical composition of geothermal fluids may be altered upon ascent from the reservoir to surface by processes including boiling, degassing, mixing, oxidation and water-rock interaction. In an attempt to quantify these processes, a three step model was developed that includes: (1) defining the composition of the end-member fluid types present in the system, (2) quantifying mixing between the end-members using non-reactive elemental concentrations and enthalpy and (3) quantifying the changes of reactive elements including degassing, oxidation and water-rock interaction. The model was applied to geothermal water at Vonarskard, Iceland, for demonstration having temperatures of 3-98°C, pH of 2.15-9.95 and TDS of 323-2250ppm, and was thought to be produced from boiled reservoir water, condensed steam and non-thermal water. Most geothermal water represented mixture of non-thermal water and condensed steam whereas the boiled reservoir water was insignificantly mixed. CO2 and H2S degassing was found to be quantitative in steam-heated water, with oxidation of H2S to SO4 also occurred. In contrast, major rock forming elements are enriched in steam-heated water relative to their mixing ratios, suggesting water-rock interaction in the surface zone. Boiled reservoir water observed in alkaline hot springs have, however, undergone less geochemical changes upon ascent to surface and within the surface zone.