Ultramafic Mine Tailings Research Articles

Comparison between Co(II) and Ni(II) cycling at goethite-water interfaces: Interplay with Fe(II)-catalyzed recrystallization

Cobalt (Co) and nickel (Ni) are critical metals for modern renewable energy technologies as well as essential micronutrients for terrestrial plant health and marine primary production. Both metals are commonly surface-adsorbed onto and/or structurally-incorporated into iron (oxyhydr)oxide minerals, such as goethite (α-FeOOH), that are ubiquitously present in soils and sediments at the Earth’s surface. In sub- and anoxic environments, aqueous ferrous iron (Fe(II)) generated from dissimilatory Fe(III) reduction can induce the recrystallization of goethite and subsequently influences the speciation and mobilization of associated metals, e.g., Co(III) being reduced to Co(II). While it is generally considered that divalent Co and Ni behave similarly at goethite-water interfaces, there lacks a direct comparison of their cycling through goethite in response to Fe(II)-catalyzed recrystallization. Here, under circumneutral anoxic conditions with and without addition of aqueous Fe(II), we performed batch reaction experiments on Co(II)-substituted goethite and Co(II) and Ni(II) sorption experiments on pure goethite. The redox state and coordination environment of Co associated with goethite were determined using high energy resolution fluorescence detected X-ray absorption spectroscopy at the Co K-edge, and the distribution of solid-bound Co and Ni in goethite following sorption was revealed by sequential dissolution. Our results show that substitution of Co(II) for Fe(III) in goethite has less negative feedback on Fe(II)-catalyzed recrystallization than Ni(II), which may be related to their differing structural distortions as evidenced by EXAFS. In the absence of Fe(II), aqueous Co(II) is more favourably adsorbed onto and incorporated deeper into goethite than Ni(II), suggesting that Co(II) is more structurally compatible with goethite. The presence of Fe(II) markedly enhances the structural incorporation of both Co(II) and Ni(II) as a result of goethite recrystallization, which in turn can be inhibited by the accumulation of metals at the mineral surface. Furthermore, structurally-incorporated Co(II) is more difficult to be released back into solution (i.e. sum of aqueous and extract fractions) than Ni(II) during Fe(II)-catalyzed goethite recrystallization. Overall, our work highlights the significant differences between Co(II) and Ni(II) in their cycling at goethite-water interfaces and intricate interplay with Fe(II)-catalyzed recrystallization. This improves our understanding of their mobilization and distribution in anoxic goethite-rich systems and can provide useful insights for their enrichment and extraction from natural and artificial laterites generated from the enhanced weathering of ultramafic mine tailings.

Influence of Iron Substitution and Solution Composition on Brucite Carbonation.

Carbon neutral or negative mining can potentially be achieved by integrating carbon mineralization processes into the mine design, operations, and closure plans. Brucite [Mg(OH)2] is a highly reactive mineral present in some ultramafic mine tailings with the potential to be rapidly carbonated and can contain significant amounts of ferrous iron [Fe(II)] substituted for Mg; however, the influence of this substitution on carbon mineralization reaction products and efficiency has not been thoroughly constrained. To better assess the efficiency of carbon storage in brucite-bearing tailings, we performed carbonation experiments using synthetic Fe(II)-substituted brucite (0, 6, 23, and 44 mol % Fe) slurries in oxic and anoxic conditions with 10% CO2. Additionally, the carbonation process was evaluated using different background electrolytes (NaCl, Na2SO4, and Na4SiO4). Our results indicate that carbonation efficiency decreases with increasing Fe(II) substitution. In oxic conditions, precipitation of ferrihydrite [Fe10IIIO14(OH)2] and layered double hydroxides {e.g., pyroaurite [Mg6Fe2III(OH)16CO3·4H2O]} limited carbonation efficiency. Carbonation in anoxic environments led to the formation of Fe(II)-substituted nesquehonite (MgCO3·3H2O) and dypingite [Mg5(CO3)4(OH)2·∼5H2O], as well as chukanovite [Fe2IICO3(OH)2] in the case of 23 and 44 mol % Fe(II)-brucite carbonation. Carbonation efficiencies were consistent between chloride- and sulfate-rich solutions but declined in the presence of dissolved Si due to the formation of amorphous SiO2·nH2O and Fe-Mg silicates. Overall, our results indicate that carbonation efficiency and the long-term fate of stored CO2 may depend on the amount of substituted Fe(II) in both feedstock minerals and carbonate products.

A new method for rapid brucite quantification using thermogravimetric analysis

Brucite [Mg(OH)2] is a trace mineral found in ultramafic deposits that readily reacts to trap atmospheric CO2. Identifying and quantifying brucite content is an essential first step in determining the carbon sequestration capacity of many ultramafic mine tailings. Quantification via X-ray diffraction (XRD) has proven problematic in the past due to peak overlap issues between brucite and chlorite. Quantitative thermogravimetric analysis (TGA) methods have been used previously; however, they typically require multiple long (>10 h) analyses. Here, we demonstrate a method for rapid quantification of brucite content via TGA. Using an exponential model to fit and ignore mass loss from other minerals, brucite can be consistently detected and quantified at abundances of as low as 0.3 wt.%, a detection limit that is superior to XRD. Relative errors are as low as 3.4% for brucite abundances greater than 2 wt.%.

Mineral carbonation of ultramafic tailings: A review of reaction mechanisms and kinetics, industry case studies, and modelling

Reduction of greenhouse gas emissions is becoming a greater priority in the mining industry due to increasing social pressures, government incentives, and its consideration in companies stock evaluation. Carbon capture and sequestration in ultramafic tailings (mineral carbonation) is one technology companies can use to offset their carbon emissions. Mineral carbonation refers to the spontaneous reaction of carbon dioxide with divalent metal minerals, which safely and permanently stores carbon dioxide as a carbonate sediment. Carbon sequestration can occur passively in ultramafic mine tailings storage facilities or under optimized conditions in process designs. This review discusses the literature on mineral carbonation reaction mechanisms, candidate minerals, kinetic parameters, potential methods to accelerate mineral carbonation, examples of industry mineral carbonation, and mine-scale mineral carbonation modelling. • Mineral carbonation reaction rate limiting mechanisms and thermoynamics. • Effect of water saturation, temperature, mineralogy, depth, pH, CO 2 and grain size. • Technologies to improve CO 2 sequestration in ultramafic tailings. • Reactive transport modelling of mineral carbonation in ultramafic tailings.

Rate and capacity of cation release from ultramafic mine tailings for carbon capture and storage

Solid wastes produced during hard-rock mining have capacity to capture and store atmospheric CO2 via dissolution and precipitation of Mg-bearing carbonate minerals. However, there is a discrepancy in our understanding of weathering and dissolution in these wastes, with dissolution and reaction rates in field studies exceeding those predicted by experiments under far-from-equilibrium conditions. To reconcile these differences, a series of flow-through dissolution experiments at 25 °C and 1atm were performed to investigate the short-term dissolution kinetics of ultramafic tailings and minerals. Results show that mineral and tailings samples have two stages of dissolution: a fast, transient (or labile) stage, and a slow, stoichiometric stage. Fast releasing labile cations (i.e. labile Mg2+) are sourced from trace minerals with a high reaction rate (e.g. brucite) and from non-stoichiometric surface reaction processes of major minerals (e.g. serpentine). These cations are missing from most geochemical models for mineral weathering. The implication of these results is that the initial transient dissolution of minerals, which is typically ignored during geochemical investigations into bulk dissolution rates, is the missing ingredient for understanding dissolution of mine tailings. Labile cations released during the initial transient dissolution process have value for rapid and low-cost carbon capture and storage techniques as they represent reactivity, capacity, and the best opportunities to deploy low-cost carbon sequestration techniques using mine tailings and other industrial wastes. The presence of labile cations and changing reaction rates over time may also suggest that short-term reactivity examined during field tests may overestimate long-term carbon capture potential of some sites.

Carbonation, Cementation, and Stabilization of Ultramafic Mine Tailings.

Tailings dam failures can cause devastation to the environment, loss of human life, and require expensive remediation. A promising approach for de-risking brucite-bearing ultramafic tailings is in situ cementation via carbon dioxide (CO2) mineralization, which also sequesters this greenhouse gas within carbonate minerals. In cylindrical test experiments, brucite [Mg(OH)2] carbonation was accelerated by coupling organic and inorganic carbon cycling. Waste organics generated CO2 concentrations similar to that of flue gas (up to 19%). The abundance of brucite (2-10 wt %) had the greatest influence on tailings cementation as evidenced by the increase in total inorganic carbon (TIC; +0.17-0.84%). Brucite consumption ranged from 64-84% of its initial abundance and was mainly influenced by water availability. Higher moisture contents (e.g., 80% saturation) and finer grain sizes (e.g., clay-silt) that allowed for a better distribution of water resulted in greater brucite carbonation. Furthermore, pore clogging and surface passivation by Mg-carbonates may have slowed brucite carbonation over the 10 weeks. Unconfined compressive strengths ranged from 0.4-6.9 MPa and would be sufficient in most scenarios to adequately stabilize tailings. Our study demonstrates the potential for stabilizing brucite-bearing mine tailings through in situ cementation while sequestering CO2.

Mineralisation of atmospheric CO2 in hydromagnesite in ultramafic mine tailings – Insights from Mg isotopes

In this study we present the first Mg isotope data that record the fate of Mg during mineralisation of atmospheric CO2 in ultramafic mine tailings. At the Woodsreef Asbestos Mine, New South Wales, Australia, weathering of ultramafic mine waste sequesters significant amounts of CO2 in hydromagnesite [Mg5(CO3)4(OH)2·4H2O]. Mineralisation of CO2 in above-ground, sub-aerially stored tailings is driven by the infiltration of rainwater dissolving Mg from bedrock minerals present in the tailings. Hydromagnesite, forming on the surface of the tailings, has lower δ26Mg (δ26MgHmgs = −1.48 ± 0.02‰) than the serpentinised harzburgite bedrock (δ26MgSerpentinite = −0.10 ± 0.06‰), the bulk tailings (δ26MgBulk tailings = −0.29 ± 0.03‰) and weathered tailings containing authigenic clay minerals (δ26MgWeathered tailings = +0.28 ± 0.06‰). Dripwater (δ26MgDripwater = −1.79 ± 0.02‰) and co-existing hydromagnesite (δ26MgHmgs = −2.01 ± 0.09‰), forming in a tunnel within the tailings, and nodular bedrock magnesite [MgCO3] (δ26MgMgs = −3.26 ± 0.10‰) have lower δ26Mg than surficial fluid (δ26Mg = −0.36‰) and hydromagnesite.Complete dissolution of source minerals, or formation of Mg-poor products during weathering, is expected to transfer Mg into solution without significant alteration of the Mg isotopic composition. Aqueous geochemical data and modelling of saturation indices, along with Rayleigh distillation and mixing calculations, indicate that the 26Mg-depletion in the drip water, relative to surficial water, is the result of brucite dissolution and/or precipitation of secondary Mg-bearing silicates and cannot be assigned to bedrock magnesite dissolution. Our results show that the main mineral sources of Mg in the tailings (silicate, oxide/hydroxide and carbonate minerals) are isotopically distinct and that the Mg isotopic composition of fluids and thus of the precipitating hydromagnesite reflects both isotopic composition of source minerals and precipitation of Mg-rich secondary phases. The consistent enrichment and depletion of 26Mg in secondary silicates and carbonates, respectively, underpins the use of the presented hydromagnesite and fluid Mg isotopic compositions as a tracer of Mg sources and pathways during CO2 mineralisation in ultramafic rocks.

Carbon accounting of mined landscapes, and deployment of a geochemical treatment system for enhanced weathering at Woodsreef Chrysotile Mine, NSW, Australia

Carbonation of ultramafic mine tailings has the potential to offset greenhouse gas emissions from mining by trapping CO2 within the crystal structures of Mg-carbonate minerals and hydrotalcite supergroup minerals, which form as weathering products in tailings storage facilities. Here, we present a detailed geochemical and mineralogical assessment of tailings from the Woodsreef Chrysotile Mine, New South Wales, Australia, demonstrating that coupling mineralogical and elemental datasets improves the accuracy of carbon accounting in mined landscapes. Detailed analysis of tailings mineralogy using quantitative X-ray diffraction (XRD) and total carbon analyses reveals that previous assessments of passive mineral carbonation at Woodsreef have been underestimated. Maximum values for the abundance of total carbon (up to 0.4 wt%), as well as the abundances of secondary carbonate minerals (i.e., up to 1.9 wt% hydromagnesite and up to 2.6 wt% pyroaurite, measured with XRD) are observed between approximately 2 cm and 30 cm depth in profiles collected within experimental plots. However, an amorphous Mg-carbonate phase, that cannot be detected using XRD, is also present at comparably high abundances to depths of at least 1 m. This phase is readily observed using scanning electron microscopy, it contributes a measured carbon content of approximately 0.2 wt% at up to 1 m depth, and it has a predominantly atmospheric carbon isotopic signature (F14C > 0.80). We find that using only XRD data results in the sequestered CO2 being underestimated by nearly four times compared to estimates incorporating total carbon measurements, highlighting the important role of amorphous Mg-carbonates in the carbon cycles of mines. Combining XRD and total carbon data, we provide an estimate for passive carbon sequestration by both crystalline and amorphous carbonates in the Woodsreef tailings (11.7 kg CO2/m2, considering the upper 1 m3) and suggest that future studies should employ both XRD and total carbon measurements for carbon accounting.The Woodsreef Chrysotile Mine was also the test site for a field-based geochemical treatment system designed to promote mineral carbonation. A solar powered, independently operating geochemical treatment system is designed and deployed to deliver controlled acid (0.08 M H2SO4) or water leaching treatments, and maintain soil pore saturation within optimal levels (approximately 18–36%) to enhance the weathering rate of mine tailings. While the applied treatment did not accelerate capture and mineralisation of CO2 from air, it could be coupled to technologies that enhance the supply of CO2 for mineral carbonation. We apply our new strategy for carbon accounting to this experimental site in order to assess changes in mineralogy and the spatial scale on which carbon accounting must be done to accurately measure carbon sequestered during weathering of ultramafic rock. Our work provides important lessons and context for future trials of accelerated tailings dissolution and mineral carbonation, which will benefit the next stage of development in the scale-up of this technology.

Accelerating Mineral Carbonation in Ultramafic Mine Tailings via Direct CO2 Reaction and Heap Leaching with Potential for Base Metal Enrichment and Recovery

Abstract Accelerated carbonation of ultramafic mine tailings has the potential to offset CO2 emissions produced by mining ores from Cu-Ni-platinum group element, podiform chromite, diamondiferous kimberlite, and historical chrysotile deposits. Treatments such as acid leaching, reaction of tailings with elevated concentrations of gaseous CO2, and optimization of tailings pore water saturation have been shown to enhance CO2 sequestration rates in laboratory settings. The next challenge is to deploy treatment technologies on the pilot and field scale while minimizing cost, energy input, and adverse environmental impacts. Implementation of accelerated tailings carbonation at field scale will ideally make use of in situ treatments or modified ore-processing routes that employ conventional technology and expertise and operate at close to ambient temperatures and pressures. Here, we describe column experiments designed to trial two geochemical treatments that address these criteria: (1) direct reaction of partially saturated ultramafic tailings with synthetic flue gas from power generation (10% CO2 in N2) and (2) repeated heap leaching of ultramafic tailings with dilute sulfuric acid. In the first experiment, we report rapid carbonation of brucite [Mg(OH)2] in the presence of 10% CO2 gas within tailings sampled from the Woodsreef chrysotile mine, New South Wales, Australia. Within four weeks, we observe a doubling of the amount of CO2 stored within minerals relative to what is achieved after three decades of passive mineral carbonation via air capture in the field. Our simulated heap leaching experiments, treated daily with 0.08 M H2SO4, produce high-Mg leachates that have the potential to sequester 21.2 kg CO2 m–2 y–1, which is approximately one to two orders of magnitude higher than the rate of passive carbonation of the Woodsreef mine tailings. Although some nesquehonite (MgCO3 · 3H2O) forms from these leachates, most of the Mg is precipitated as Mg sulfate minerals instead. Therefore, an acid other than H2SO4 could be used; otherwise, sulfate removal would be required to maximize CO2 sequestration potential from acid heap leaching treatments. Reactive transport modeling (MIN3P) is employed to simulate acid leaching experiments and predict the effects of heap leaching for up to five years. Finally, our synchrotron X-ray fluorescence microscopy results for leached tailings material reveal that valuable trace metals (Fe, Ni, Mn, Co, Cr) become highly concentrated within secondary Fe (hydr)oxide minerals at the pH neutralization horizon within our column experiments. This discrete horizon migrates downward, and our reactive transport models indicate it will become increasingly enriched in first-row transition metals in response to continued acid leaching. Acid-leaching treatments for accelerated mineral carbonation could therefore be useful for ore processing and recovery of base metals from tailings, waste rock, or low-grade ores.

Prospects for CO2 mineralization and enhanced weathering of ultramafic mine tailings from the Baptiste nickel deposit in British Columbia, Canada

The Baptiste deposit is located within the Decar nickel district in British Columbia, Canada and is a promising candidate for a CO2 sequestration demonstration project. The deposit contains awaruite (nickel-iron alloy) hosted in an ultramafic complex, which is dominated by serpentine [Mg3Si2O5(OH)4; ∼80 wt.%] and contains reactive brucite [Mg(OH)2; 0.6–12.6 wt.%]. Experiments were conducted using metallurgical test samples and pulps from cores with the aim of determining the potential for this deposit to sequester CO2 via direct air capture of atmospheric CO2 and carbonation using CO2-rich gas. The experimental direct capture rate was 3.5 kg CO2/m2/yr and would sequester 17 kt CO2/yr based on year-round reaction and when extrapolated to the scale of the proposed tailings facility (5 km2). This rate can be increased by ∼5 times (19 kg CO2/m2/yr) when aerating the tailings and would offset CO2 emissions by 95 kt CO2/yr (19–25% offset of projected CO2 emissions). Experimental carbonation rates with 10% CO2 gas could achieve offsets of up to 210 kt CO2/year (42–53% CO2 offset) based on 1 h reaction times and consumption of 0.8 wt% brucite if present. Targeting brucite-rich ore zones and optimizing CO2 delivery would likely lead to greater CO2 offsets.

Opportunities for Mineral Carbonation in Australia’s Mining Industry

Carbon capture, utilisation and storage (CCUS) via mineral carbonation is an effective method for long-term storage of carbon dioxide and combating climate change. Implemented at a large-scale, it provides a viable solution to harvesting and storing the modern crisis of GHGs emissions. To date, technological and economic barriers have inhibited broad-scale utilisation of mineral carbonation at industrial scales. This paper outlines the mineral carbonation process; discusses drivers and barriers of mineral carbonation deployment in Australian mining; and, finally, proposes a unique approach to commercially viable CCUS within the Australian mining industry by integrating mine waste management with mine site rehabilitation, and leveraging relationships with local coal-fired power station. This paper discusses using alkaline mine and coal-fired power station waste (fly ash, red mud, and ultramafic mine tailings, i.e., nickel, diamond, PGE (platinum group elements), and legacy asbestos mine tailings) as the feedstock for CCUS to produce environmentally benign materials, which can be used in mine reclamation. Geographical proximity of mining operations, mining waste storage facilities and coal-fired power stations in Australia are identified; and possible synergies between them are discussed. This paper demonstrates that large-scale alkaline waste production and mine site reclamation can become integrated to mechanise CCUS. Furthermore, financial liabilities associated with such waste management and site reclamation could overcome many of the current economic setbacks of retrofitting CCUS in the mining industry. An improved approach to commercially viable climate change mitigation strategies available to the mining industry is reviewed in this paper.

Carbon Sequestration in Biogenic Magnesite and Other Magnesium Carbonate Minerals.

The stability and longevity of carbonate minerals make them an ideal sink for surplus atmospheric carbon dioxide. Biogenic magnesium carbonate mineral precipitation from the magnesium-rich tailings generated by many mining operations could offset net mining greenhouse gas emissions, while simultaneously giving value to mine waste products. In this investigation, cyanobacteria in a wetland bioreactor enabled the precipitation of magnesite (MgCO3), hydromagnesite [Mg5(CO3)4(OH)2·4H2O], and dypingite [Mg5(CO3)4(OH)2·5H2O] from a synthetic wastewater comparable in chemistry to what is produced by acid leaching of ultramafic mine tailings. These precipitates occurred as micrometer-scale mineral grains and microcrystalline carbonate coatings that entombed filamentous cyanobacteria. This provides the first laboratory demonstration of low temperature, biogenic magnesite precipitation for carbon sequestration purposes. These findings demonstrate the importance of extracellular polymeric substances in microbially enabled carbonate mineral nucleation. Fluid composition was monitored to determine carbon sequestration rates. The results demonstrate that up to 238 t of CO2 could be stored per hectare of wetland/year if this method of carbon dioxide sequestration was implemented at an ultramafic mine tailing storage facility. The abundance of tailings available for carbonation and the anticipated global implementation of carbon pricing make this method of mineral carbonation worth further investigation.

Hydrotalcites and hydrated Mg-carbonates as carbon sinks in serpentinite mineral wastes from the Woodsreef chrysotile mine, New South Wales, Australia: Controls on carbonate mineralogy and efficiency of CO2 air capture in mine tailings

Carbon mineralisation of ultramafic mine tailings can reduce net emissions of anthropogenic carbon dioxide by reacting Mg-silicate and hydroxide minerals with atmospheric CO2 to produce carbonate minerals. We investigate the controls on carbonate mineral formation at the derelict Woodsreef chrysotile mine (New South Wales, Australia). Quantitative XRD was used to understand how mineralogy changes with depth into the tailings pile, and shows that hydromagnesite [Mg5(CO3)4(OH)2·4H2O], is present in shallow tailings material (<40 cm), while coalingite [Mg10Fe3+2(CO3)(OH)24·2H2O] and pyroaurite [Mg6Fe3+2(CO3)(OH)16·4H2O] are forming deeper in the tailings material. This indicates that there may be two geochemical environments within the upper ∼1 m of the tailings, with hydromagnesite forming within the shallow tailings via carbonation of brucite in CO2-rich conditions, and pyroaurite and coalingite forming under more carbon limited conditions at depth. Radiogenic isotope results indicate hydromagnesite and pyroaurite have a modern (F14C > 0.8) atmospheric CO2 source. Laboratory-based anion exchange experiments, conducted to explore stable C isotope fractionation in pyroaurite, shows that pyroaurite δ13C values change with carbon availability, and 13C-depleted signatures are typical of hydrotalcites in C-limited environments, such as the deep tailings at Woodsreef. Quantitative XRD and elemental C data estimates that Woodsreef absorbs between of 229.0–405.1 g CO2 m−2 y−1.

Comparison of Rietveld-compatible structureless fitting analysis methods for accurate quantification of carbon dioxide fixation in ultramafic mine tailings

The carbonation of ultramafic rocks, including tailings from ultramafic-hosted ore deposits, can be used to remove CO2 from the atmosphere and store it safely within minerals over geologic timescales. Quantitative X-ray diffraction (XRD) using Rietveld refinements can be employed to estimate the amount of carbon sequestered by carbonate minerals that form as a result of weathering of ultramafic rocks. However, the presence of structurally disordered phases such as serpentine minerals, which are common in ultramafic ore bodies such as at the Woodsreef chrysotile mine (New South Wales, Australia), results in samples that cannot be analyzed using typical Rietveld refinement strategies. Previous investigations of carbon sequestration at Woodsreef and other ultramafic mine sites typically used modified Rietveld refinement methods that apply structureless pattern fitting for disordered phases; however, no detailed comparison of the accuracy (or precision) of these methods for carbon accounting has yet been attempted, making it difficult to determine the most appropriate analysis method. Such an analysis would need to test whether some methods more accurately quantify the abundances of certain minerals, such as pyroaurite [Mg6Fe23+(CO3)(OH)(16)center dot 4H(2)O] and other hydrotalcite group minerals, which suffer from severe preferred orientation and may play an important role in carbon sequestration at some mines. Here, we assess and compare the accuracy, and to a lesser extent the precision, of three different non-traditional Rietveld refinement methods for carbon accounting: (1) the PONKCS method, (2) the combined use of a Pawley fit for serpentine minerals and an internal standard (Pawley/internal standard method), and (3) the combined use of PONKCS and Pawley/internal standard methods. We examine which of these approaches represents the most accurate way to quantify the abundances of serpentine, pyroaurite, and other carbonate-bearing phases in a given sample. We demonstrate that by combining the PONKCS and Pawley/internal standard methods it is possible to quantify the abundances of disordered phases in a sample and to obtain an estimate of the amorphous content and any unaccounted intensity in an XRD pattern. Eight artificial tailings samples with known mineralogical compositions were prepared to reflect the natural variation found within the tailings at the Woodsreef chrysotile mine. Rietveld refinement results for the three methods were compared with the known compositions of each sample to calculate absolute and relative error values and to evaluate the accuracy of the three methods, including whether they produce systematic under- or overestimates of mineral abundance. Estimated standard deviations were also calculated during refinements; these values, which are a measure of precision, were not strongly affected by the choice of refinement method. The abundance of serpentine minerals is, however, systematically overestimated when using the PONKCS and Pawley/internal standard methods, and the abundances of minor phases (<10 wt%) are systematically underestimated using all three methods. Refined abundances for pyroaurite were found to be increasingly susceptible to error with increasing abundance, with an underestimation of 6.6 wt% absolute (60.6% relative) for a sample containing 10 9 wt% pyroaurite.These significant errors are due to difficulties in mitigating preferred orientation of hydrotalcite minerals during sample preparation as well as modeling its effects on XRD patterns. The abundances of hydromagnesite [Mg,(CO3)(4)(OH)(2)center dot 4H(2)O], another important host for atmospheric CO2 during weathering of ultramafic rocks, was consistently underestimated by all three methods, with the highest underestimation being 3.7 wt% absolute (or 25.0% relative) for a sample containing 15.0 wt% hydromagnesite. Overall, the Pawley/internal standard method produced more accurate results than the PONKCS method, with an average bias per refinement of 6.7 wt%, compared with 10.3 wt% using PONKCS and 12.9 wt% for the combined PONKCS-Pawley/internal standard method. Furthermore, the values for the refined abundance of hydromagnesite obtained from refinements using the Pawley/internal standard method were significantly more accurate than those for refinements done with the PONKCS method, with relative errors typically <25% for hydromagnesite abundances between 5 and 15 wt%. The simpler and faster sample preparation makes the PONKCS method well-suited for rapid carbon accounting, for instance in the field using a portable XRD; however, the superior accuracy gained when using an internal standard make the Pawley/internal standard method the preferable means of undertaking a detailed laboratory-based study. As all three methods displayed an underestimation of carbonate phases, applying these methods to natural samples will likely produce an underestimate of hydromagnesite and hydrotalcite group mineral abundances. As such, crystallographic accounting strategies that use modified Rietveld refinement methods produce a conservative estimate of the carbon sequestered in minerals.

Fate of transition metals during passive carbonation of ultramafic mine tailings via air capture with potential for metal resource recovery

Mineral carbonation in ultramafic mine tailings is generally accepted to be a safe and long term means of trapping and storing CO2 within the structures of minerals, but it poses the risk of releasing potentially hazardous metal contaminants from mineral wastes into the environment. Stockpiles of reactive, finely pulverised ultramafic mine tailings are ideal natural laboratories for the observation and promotion of the carbonation of Mg-silicate and Mg-hydroxide waste minerals via reaction with atmospheric or industrial CO2. However, ultramafic mine tailings commonly contain first-row transition metals (e.g., Cr, Co, Cu, Ni) in potentially toxic concentrations within the crystal structures of Mg-silicates, sulphides, and oxides. These transition metals are likely to be mobilised by mineral carbonation reactions, which require mineral dissolution to supply cations for reaction with carbon. At Woodsreef Chrysotile Mine, New South Wales, Australia, transition metals (i.e., Fe, Cr, Ni, Mn, Co, Cu) are most concentrated within minor oxides (magnetite and chromite) and trace alloys (awaruite, Ni2-3Fe and wairauite, CoFe) in serpentine tailings, however, mobilisation of transition metals appears to occur predominantly during dissolution of serpentine and brucite, which are more abundant and reactive phases, respectively. Here, we present new synchrotron X-ray fluorescence mapping data that provide insights into the mobility of first-row transition metals (Fe, Cr, Ni, Mn, Co, Cu) during weathering and carbonation of ultramafic mine tailings collected from the Woodsreef Chrysotile Mine. These data indicate that the recently precipitated carbonate minerals, hydromagnesite [Mg5(CO3)4(OH)2·4H2O] and pyroaurite [Mg6Fe2(CO3)(OH)16·4H2O] sequester trace metals from the tailings at concentrations of 10 s–100 s of ppm, most likely via substitution for Mg or Fe within their crystal structures, or by the physical trapping of small (μm-scale) transition-metal-rich grains (i.e., magnetite, chromite, awaruite), which are stabilised within alkaline carbonate cements. Trace transition metals are present at relatively high concentrations in the bulk tailings (i.e., ∼0.3 wt.% NiO and Cr2O3) and they are largely retained within the unaltered mineral assemblage. The weathering products that occur at the surface of the tailings and form a cement between grains of partially dissolved gangue minerals immobilise transition metals on spatial scales of micrometres and at comparable concentrations to those observed in the unaltered tailings. The end result is that trace metals are not present at detectable levels within mine pit waters. Our observations of metal mobility during passive carbonation suggest that mineral products of accelerated carbonation treatments are likely to sequester trace metals. Thus, accelerated carbonation is unlikely to pose an environmental risk in the form of metalliferous drainage so long as the neutralisation potential of the tailings is not exceeded.Understanding both trace transition metal geochemistry and mineralogy within materials targeted for mineral carbonation could allow optimisation of treatment processes and design for recovery of valuable metals. In ex situ reactors employing acid pre-treatments, trace metals mobilised from reactive phases such as serpentine and brucite could potentially be recovered using pH-swing methods, while recalcitrant metal-rich accessory minerals, including magnetite, awaruite and chromite, could be recovered from treated residue material by conventional mineral separation processes. Recovery of valuable metals (i.e., Ni, Cr and Co) as by-products of accelerated mineral carbonation technologies could also provide an important economic incentive to support broader adoption of this technology.

Kinetic testing to evaluate the mineral carbonation and metal leaching potential of ultramafic tailings: Case study of the Dumont Nickel Project, Amos, Québec

Ultramafic mine wastes are known to react passively with CO2 to form stable hydrated magnesium carbonates. This study uses kinetic tests to evaluate the carbonation potential of ultramafic mine tailings from the Dumont project (RNC Minerals, Québec, Canada) during their weathering, and to determine the impact of carbonation on the long-term quality of drainage waters. The weathering of awaruite [(Ni2.5Fe)], pentlandite [(Fe,Ni)9S8], and heazlewoodite [(Ni3S2)], which are the main sources of Ni in the studied materials, were also investigated due to their potential to generate contamination. A column test and small-scale weathering cell tests were used to simulate the passive weathering of ultramafic mine wastes, as well as concentrates of awaruite and Ni sulfides. Results from the kinetics tests confirmed that the Dumont tailings have a significant carbon sequestration potential which ranged from 8.5 to 33.6 kgCO2/t. The surface-normalized carbonation rates varied from 600 to 2200 g of CO2/m2/year. Results demonstrated that brucite [Mg(OH)2] content is the main parameter controlling CO2 uptake by the Dumont wastes. Weathering of brucite and serpentine [Mg3Si2O5(OH)4] are driven by CO2 dissolution in pore water and by sulfide oxidation. The rapid dissolution of brucite results in leachates with alkaline pH values, thus preventing metal mobility. Metals such as Ni, Zn, Fe, and Cu are suggested to precipitate as hydroxide or carbonate species within the wastes immediately upon being released through sulfide oxidation. The Ni-Fe alloy awaruite is stable and does not release metals in kinetic tests. The Dumont tailings are found to be non-acid generating and CO2 sequestration is shown to play a significant role in drainage water quality which allow generation of significant alkalinity and the rise of pH.

Multivariate study of the dynamics of CO2 reaction with brucite-rich ultramafic mine tailings

Mineral carbonation of a nickel mine tailing (NiMT) was studied using a dual-compartment carbonation cell employing moderate CO2 partial pressures for accelerating carbon uptake and to simulate outdoor temperature conditions prevailing in mining waste disposal sites. Time-dependent X-ray powder diffraction analysis and scanning electron microscopy reveal formation of transitional, metastable porous, flaky magnesium carbonates which subsequently evolved into less porous nesquehonite layers, which are shown to be responsible for surface passivation despite availability of unreacted brucite. However, the reactive cores could be turned into easily accessible regions following ex-foliation of carbonated materials. Moreover, it was demonstrated that slow carbonate nucleation events such as during carbonation of as-received ores may be significantly accelerated by means of carbonate pre-seeding strategies.

Chemical and isotopic signatures of waters associated with the carbonation of ultramafic mine tailings, Woodsreef Asbestos Mine, Australia

Extensive carbonate crusts have formed on the tailings of the Woodsreef Asbestos Mine, sequestering significant amounts of CO2 directly from the atmosphere. The physico-chemical (pH, T, conductivity), chemical (cations, dissolved inorganic carbon (DIC)) and isotopic (δ2H, δ18O, δ13CDIC, F14C) signatures of waters interacting with the tailings and associated carbonate precipitates provide insight into the processes controlling carbonation. We observe two distinct evolutionary pathways for a set of stream and meteoric-derived water samples, respectively, with both groups generally being characterised as moderately alkaline, bicarbonate-dominated and Mg-rich waters. Stream water samples are supersaturated with CO2 and therefore prone to degassing, which, in combination with evaporation, drives carbonate supersaturation and precipitation. Isotopic signatures indicate soil CO2 as the main carbon source in the stream waters entering the tailings pile, whereas water emerging downstream of the tailings pile may also contain carbon from the dissolution of isotopically light bedrock magnesite in an open system with respect to soil CO2. The evolution of meteoric-derived waters on the other hand, partly occurs under CO2-limited conditions, which results from reduced CO2 ingress at depth and/or a temporal lag between fluid alkalisation and kinetically hindered uptake of CO2 into alkaline solution. A high pH, Mg-rich meteoric water absorbs atmospheric CO2 after discharging into a tunnel within the tailings pile, resulting in high DIC concentrations with atmospheric carbon isotope signature. Evaporation of the water at the discharge point in the tunnel drives precipitation of hydromagnesite (Mg5(CO3)4(OH)2·4H2O), displaying a clear atmospheric isotope signature, broadly consistent with previous estimates of carbon and oxygen isotope fractionation during precipitation of hydrated Mg-carbonate.

A greenhouse-scale photosynthetic microbial bioreactor for carbon sequestration in magnesium carbonate minerals.

A cyanobacteria dominated consortium collected from an alkaline wetland located near Atlin, British Columbia, Canada accelerated the precipitation of platy hydromagnesite [Mg5(CO3)4(OH)2·4H2O] in a linear flow-through experimental model wetland. The concentration of magnesium decreased rapidly within 2 m of the inflow point of the 10-m-long (∼1.5 m(2)) bioreactor. The change in water chemistry was monitored over two months along the length of the channel. Carbonate mineralization was associated with extra-cellular polymeric substances in the nutrient-rich upstream portion of the bioreactor, while the lower part of the system, which lacked essential nutrients, did not exhibit any hydromagnesite precipitation. A mass balance calculation using the water chemistry data produced a carbon sequestration rate of 33.34 t of C/ha per year. Amendment of the nutrient deficiency would intuitively allow for increased carbonation activity. Optimization of this process will have application as a sustainable mining practice by mediating magnesium carbonate precipitation in ultramafic mine tailings storage facilities.

Accelerated Carbonation of Brucite in Mine Tailings for Carbon Sequestration

Atmospheric CO(2) is sequestered within ultramafic mine tailings via carbonation of Mg-bearing minerals. The rate of carbon sequestration at some mine sites appears to be limited by the rate of CO(2) supply. If carbonation of bulk tailings were accelerated, large mines may have the capacity to sequester millions of tonnes of CO(2) annually, offsetting mine emissions. The effect of supplying elevated partial pressures of CO(2) (pCO(2)) at 1 atm total pressure, on the carbonation rate of brucite [Mg(OH)(2)], a tailings mineral, was investigated experimentally with conditions emulating those at Mount Keith Nickel Mine (MKM), Western Australia. Brucite was carbonated to form nesquehonite [MgCO(3) · 3H(2)O] at a rate that increased linearly with pCO(2). Geochemical modeling indicated that HCO(3)(-) promoted dissolution accelerated brucite carbonation. Isotopic and aqueous chemistry data indicated that equilibrium between CO(2) in the gas and aqueous phases was not attained during carbonation, yet nesquehonite precipitation occurred at equilibrium. This implies CO(2) uptake into solution remains rate-limiting for brucite carbonation at elevated pCO(2), providing potential for further acceleration. Accelerated brucite carbonation at MKM offers the potential to offset annual mine emissions by ~22-57%. Recognition of mechanisms for brucite carbonation will guide ongoing work to accelerate Mg-silicate carbonation in tailings.