Geochemistry of arsenic in uranium mine mill tailings,Saskatchewan, Canada

The Rabbit Lake U mine in-pit tailings management facility (TMF) (425 m long×300 m wide×91 m deep) is located in northern Saskatchewan, Canada. The objectives of this study were to quantify the distribution of As phases in the tailings and evaluate the present-day geochemical controls on dissolved As. These objectives were met by analyzing pore fluid samples collected from the tailings body for dissolved constituents, measuring Eh, pH, and temperature of tailings core and pore fluid samples, conducting sequential extractions on solid samples, conducting geochemical modeling of pore fluid chemistry using available thermodynamic data, and by reviewing historical chemical mill process records. Dissolved As concentrations in 5 monitoring wells installed within the tailings body ranged from 9.6 to 71 mg/l. Pore fluid in the wells had a pH between 9.3 and 10.3 and Eh between +58 and +213 mV. Sequential extraction analyses of tailings samples showed that the composition of the solid phase As changed at a depth of 34 m. The As above 34 m was primarily associated with amorphous Fe and metal hydroxides while the As below 34 m was associated with Ca, likely as amorphous poorly ordered calcium arsenate precipitates. The change in the dominant As solid phases at this depth was attributed to the differences in the molar ratio of Fe to As in the mill tailings. Below 34 m it was <2 whereas above 34 m it was >4. The high Ca/As ratio during tailings neutralization would likely precipitate Ca₄(OH)₂(AsO₄)₂:4H₂O type Ca arsenate minerals. Geochemical modeling suggested that if the pore fluids were brought to equilibrium with this Ca-arsenate, the long-term dissolved As concentrations would range between 13 and 126 mg/l.     

Distribution of arsenic and nickel in uranium mill tailings,Rabbit Lake,Saskatchewan, Canada

The Rabbit Lake U mine in-pit tailings management facility (TMF) is located in northern Saskatchewan, Canada. The tailings body is approximately 425 m long×300 m wide and 91 m thick at its centre. An investigation of the TMF was performed to collect tailings samples from depth to quantify the distribution of As and Ni in the tailings with respect to ore type and assess the distribution of As and Ni with respect to tailings mineralogy. The tailings body consists of alternating layers of ice, frozen tailings and unfrozen tailings which varied in texture from a slurry to a firm silty sand. The tailings solids are predominately composed of quartz (16–36%), calcium sulphate (0.3–54%) and illite (3 and 14%). Arsenic and Ni concentrations in the tailings show similar patterns with depth which were strongly related to historical changes in As and Ni concentrations in the mill feed. Mineralogy of the ore bodies indicated that As and Ni in the mill feed occurred primarily as 1:1 molar ratio arsenides such as niccolite and gersdorffite. Arsenic and Ni concentrations in the tailings were also measured at a near 1:1 molar ratio. Mill process records showed that an average of 71% of the As in the mill feed was solubilized during leaching. SEM analysis suggested that solubilized As is precipitated as Ca²⁺, Fe³⁺ and Ni²⁺ arsenates during the neutralization process. Mill records indicated that 17,000 tonnes of As were discharged to the TMF of which approximately 88% was as arsenates and 12% as primary arsenides.     

Geochemical constraints on underground disposal of uranium mill tailings

A three phase investigation has been conducted on groundwater quality impacts of the underground disposal of tailings from acid-leach milling of uranium ores. These phases included field collection and analysis of samples obtained during backfilling of mill tailings in empty underground mine stopes, collection of soil samples from mill tailings piles and previously backfilled stopes, and evaluation of thermodynamic constraints on possible geochemical transformations. Contaminants of principal concern include As, Mo, Se, U, V and Ra-226.The investigation has shown that short-term degradation of groundwater due to backfill disposal of the sand fraction of uranium tailings is negligible. Long-term effects, defined as those occurring after mining operations cease and the mine fills with water, are predicted to also be very small. This is attributed to immobilization of pollutants through chemical reduction and precipitation, as well as adsorption onto aquifer materials. This conclusion is substantiated, in part, by observation of high concentrations of most of the contaminants on the silt and clay fraction of the soil samples collected, in contrast to the concentrations found on the sand fraction.     

Arsenic readily released to pore waters from buried mill tailings

At the McClean Lake Operation in the Athabasca Basin of northern Saskatchewan, the untreated acid raffinate solutions associated with U mill tailings contain up to 700 mg/L dissolved As. To reduce the concentration of As and other contaminants in acid tailing slurries at the JEB mill at McClean Lake, ferric sulfate may be added to the acid raffinates to assure that their molar Fe/As ratio equals or exceeds 3. Tailings slurries are then neutralized with lime to pH 4, and subsequently to pH 7–8. The neutralized tailings contain minerals from the original ore, which are chiefly quartz, illite, kaolinite and chlorite, and precipitated (secondary) minerals that include gypsum, scorodite, annabergite, hydrobasaluminite and ferrihydrite. Most of the As is associated with the secondary arsenate minerals, scorodite and annabergite. However, a few percent is adsorbed and/or co-precipitated, mainly by ferrihydrite. Of major concern to provincial and federal regulators is the risk that significant amounts of As might be released from the tailings to pore waters after their subaqueous disposal in the tailings management facility. A laboratory study was performed to address this issue, measuring readily desorbed As using a method known as equilibrium partitioning in closed systems (EPICS). The EPICS method was selected because it employs a leaching solution that, except for its As concentration, is identical in composition to the neutralized raffinate in contact with the tailings. Laboratory experiments and modeling results demonstrated that the As that could be readily released to pore waters is about 0.2% of the total As in the tailings. Long-term, such releases may contribute no more than a few mg/L of dissolved As to tailings pore waters.     

The mobility of radium-226 and trace metals in pre-oxidized subaqueous uranium mill tailings

The exchange of ²²⁶Ra and trace metals across the tailings-water interface and the mechanisms governing their mobility were assessed via sub-centimetre resolution profiling of dissolved constituents across the tailings–water interface in Cell 14 of the Quirke Waste Management Area at Rio Algom's Quirke Mine, near Elliot Lake, Ontario, Canada. Shallow zones (<1.5 m water depth) are characterized by sparse filamentous vegetation, well-mixed water columns and fully oxygenated bottom waters. Profiles of dissolved O₂, Fe and Mn indicate that the tailings deposits in these areas are sub-oxic below tailings depths of ∼3 cm. These zones exhibit minor remobilization of Ra in the upper 5 cm of the tailings deposit; ²²⁶Ra fluxes at these sites are relatively small, and contribute negligibly to the water column activity of ²²⁶Ra. The shallow areas also exhibit minor remobilization of Ni, As, Mo and U. The release of these elements to the water cover is, however, limited by scavenging mechanisms in the interfacial oxic horizons. The presence of thick vegetation (Chara sp.) in the deeper areas (>2 m water depth) fosters stagnant bottom waters and permits the development of anoxia above the benthic boundary. These anoxic tailings are characterized by substantial remobilization of ²²⁶Ra, resulting in a relatively large flux of ²²⁶Ra from the tailings to the water column. The strong correlation between the porewater profiles of ²²⁶Ra and Ba (r²=0.99), as well as solubility calculations, indicate that the mobility of Ra is controlled by saturation with respect to a poorly ordered and/or impure barite phase [(Ra,Ba)SO₄]. In the anoxic zones, severe undersaturation with respect to barite is sustained by microbial SO₄ reduction. Flux calculations suggest that the increase in ²²⁶Ra activity in the water cover since 1995 (from <0.5 to 2.5 Bq l⁻¹) can be attributed to an increase in the spatial distribution of anoxic bottom waters caused by increased density of benthic flora. The anoxic, vegetated areas also exhibit minor remobilization with respect to dissolved As, Ni and Zn. The removal of trace metals in the anoxic bottom waters appears to be limited by the availability of free sulphide. Collectively, the data demonstrate that while the water cover over the U mill tailings minimizes sulphide oxidation and metal mobility, anoxic conditions which have developed in deeper areas have led to increased mobility of ²²⁶Ra.     

Release ofRa from uranium mill tailings by microbial Fe(III) reduction

Uranium mill tailings were anaerobically incubated in the presence of H₂ with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H₂ and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved²²⁶Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of²²⁶Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved²²⁶Ra from uranium mill tailings.     

The mineralogy of arsenic in uranium mine tailings at the Rabbit Lake In-pit Facility, northern Saskatchewan, Canada

 A detailed investigation of the mineralogy of As in the tailings of the Rabbit Lake uranium ore processing facility was conducted. The milling/ore extraction process was sampled at three different locations to obtain information about when, where and under what condition secondary As phases form. These samples were compared with four samples of varying As content from the Rabbit Lake in-pit tailings management facility (TMF). Up to 20% As in the tailings are present in primary minerals that reach the tailings directly because they are not dissolved during the uranium extraction. The remaining 80% constitute As that was dissolved during ore extraction and then re-precipitated before being discharged into the tailings pond. It was not possible to conclusively identify any individual re-precipitated (secondary) As minerals in the Rabbit Lake TMF. Indirect evidence from sequential extraction analyses suggests the presence of an amorphous Ca-As phase and a possible, but unlikely, minor amount of an amorphous Fe-As phase. However, the close association between hydrous ferric oxide (HFO) and As could be clearly demonstrated. HFO was identified to be 2-line ferrihydrite and its XRD pattern geometry indicates a substantial amount of adsorbed As. This is in good agreement with SEM, TEM and sequential extraction analyses that all showed the close association of HFO and As. Received: 14 February 2000 · Accepted: 9 May 2000     

The arsenic source term for an in-pit uranium mine tailings facility and its long-term impact on the regional groundwater

Detailed field sampling and analyses and laboratory-based diffusion-cell experiments were used in conjunction with 3-D reactive transport modeling (MODFLOW and MT3D99) to quantify the fate and long-term (10 ka) transport of As in the Rabbit Lake In-pit Tailings Management Facility (RLITMF), northern Saskatchewan, Canada. The RLITMF (300 m × 425 m × 90 m thick) was engineered to ensure solute transport within the RLITMF is dominated by diffusion. Concentrations of As in the tailings pore fluids ranged from 0.24 to 140 mg/L (n = 43). Arsenic speciation analyses indicate 90% of this arsenic exists as As⁵⁺. This observation is supported by pH–Eh measurements of pore fluids (n = 135). Geochemical analyses yielded a strong inverse correlation between the Fe/As molar ratio in the tailings solids and the corresponding concentration of dissolved As, which is attributed to the adsorption of As to secondary 2-line ferrihydrite present in the tailings. Diffusion-cell testing yielded values for the effective diffusion coefficient, sorption coefficient, and effective porosity of As in the tailings of 4.5 × 10⁻¹⁰ m²/s, 2–4 cm³/g and 0.36, respectively. Reactive transport simulations using the field and laboratory data show adsorption of As to the tailings and diffusive transport of dissolved As in the tailings should reduce the source term concentration of As to between 40% and 70% of the initial concentrations over the 10 ka simulation period. Based on these simulations, the As concentrations in the regional groundwater, 50 m down gradient of the tailings facility, should be maintained at background concentrations of 0.001 mg/L over the 10 ka period. These findings suggest the engineered in-pit disposal of U mine tailings can provide long-term protection for the local groundwater regime from As contamination.     

铀尾矿库退役后的污染源项调查方法

从源项调查的目的、意义、基本内容和主要方法等方面进行了研究,分析了国内该方面研究工作的主要动态,指出了目前源项调查工作存在的主要问题,并对退役治理工作提出了合理的建议。     

Geochemical processes in mill tailings deposits: modelling of groundwater composition

A general model is presented for geochemical processes occurring in the unsaturated zone of a carbonate-depleted, pyritic tailings deposit. Quantification of slow geochemical reactions, using published, empirical rate laws from small-scale experiments on monomineralic samples, and geochemical equilibrium reactions successfully reproduced the relative rates of field processes in the case study, Impoundment 1 in Kristineberg. Reproduction of absolute rates was achieved by scaling down all laboratory-derived mineral weathering rates by two orders of magnitude. The sensitivity of the modelled groundwater composition and pH to rates of pH-buffering processes and redox reactions indicated that inclusion and accurate quantification of all dominant geochemical processes on the field scale is necessary for reliable prediction of groundwater composition and pH.     

Depositional characteristics of uranium tailings from Saskatchewan,Canada

The management of uranium tailings, generated as a by-product of ore processing, is particularly important to minimize the environmental footprint of the industry. A clear understanding of tailings slurry behavior is required at the time of deposition to help evaluate the storage capacity and life span of the containment facilities. The main purpose of this study was to investigate the segregation and self-weight settling properties of uranium tailings. Detailed laboratory investigations were conducted on tailings from 4, 5, and 6 % nominal mill feeds (high-grade McArthur River ores blended with special wastes on site) from the Cameco Key Lake operation. The results indicate that the three uranium tailings can be characterized as a sandy silt material with a negligible amount of clay. Their depositional behavior is governed by the initial solids content of the slurry. The investigated tailings showed insignificant segregation between 25 and 40 % initial solids content. The initial hydraulic conductivity during settling was about 10^?4 m/s at a void ratio of 4 and was increased by half an order of magnitude for the 4 % mill feed, and by almost two orders of magnitude for the 5 and 6 % mill feeds at a void ratio of 8. Over the same range of initial void ratio, the settling potential increased threefold: from 8 to 24 % for the 4 % mill feed and from 12 to 36 % for the 5 and 6 % mill feeds. The better rate and amount of dewatering of future high mill feed tailings as compared to the current low mill feed tailings means that the onsite containment facility can store more tailings thereby supporting a longer life span of the mill.     

Speciation and colloid transport of arsenic from mine tailings

In addition to affecting biogeochemical transformations, the speciation of As also influences its transport from tailings at inoperative mines. The speciation of As in tailings from the Sulfur Bank Mercury Mine site in Clear Lake, California (USA) (a hot-spring Hg deposit) and particles mobilized from these tailings have been examined during laboratory-column experiments. Solutions containing two common, plant-derived organic acids (oxalic and citric acid) were pumped at 13 pore volumes d⁻¹ through 25 by 500 mm columns of calcined Hg ore, analogous to the pedogenesis of tailings. Chemical analysis of column effluent indicated that all of the As mobilized was particulate (1.5 mg, or 6% of the total As in the column through 255 pore volumes of leaching). Arsenic speciation was evaluated using X-ray absorption spectroscopy (XAS), indicating the dominance of arsenate [As(V)] sorbed to poorly crystalline Fe(III)-(hydr)oxides and coprecipitated with jarosite [KFe₃(SO₄, AsO₄)₂(OH)₆] with no detectable primary or secondary minerals in the tailings and mobilized particles. Sequential chemical extractions (SCE) of <45 μm mine tailings fractions also suggest that As occurs adsorbed to Fe (hydr)oxides (35%) and coprecipitated within poorly crystalline phases (45%). In addition, SCEs suggest that As is associated with 1 N acid-soluble phases such as carbonate minerals (20%) and within crystalline Fe-(hydr)oxides (10%). The finding that As is transported from these mine tailings dominantly as As(V) adsorbed to Fe (hydr)oxides or coprecipitated within hydroxysulfates such as jarosite suggests that As release from soils and sediments contaminated with tailings will be controlled by either organic acid-promoted dissolution or reductive dissolution of host phases.     

某铀尾矿库区地下水238^U迁移模拟

将铀尾矿库核素迁移问题概括为均质多孔介质中稳定的二维水流条件下的三维溶质迁移问题,利用Visual Modflow软件（MT3D）采用全隐式差分法对某铀尾矿库放射性核素迁移进行了模拟研究,模拟值结果与浓度实测值较吻合,揭示了尾矿库放射性核素时空迁移规律。     

Influence of hardpan layers on arsenic mobility in historical gold mine tailings

Hardpans, or cemented layers, form by precipitation and cementation of secondary minerals in mine tailings and may act as both physical and chemical barriers. Precipitation of secondary minerals during weathering of tailings can sequester metal(loid)s, thereby limiting their release to the environment. At Montague Gold Mines in Nova Scotia, tailings are partially cemented by the Fe arsenate mineral scorodite (FeAsO₄·2H₂O). Previous studies have shown that the formation of scorodite can effectively limit aqueous As concentrations due to its relatively low solubility (<1 mg/L at pH 3–4) and high As content (43–52 wt.% As₂O₅, this study). Co-existing waters and solids were sampled at Montague Gold Mines to identify present-day field conditions influencing scorodite precipitation and dissolution, and to better understand the mineralogical and chemical relationship between hardpan and tailings. In addition to scorodite, hardpan cements were found to include amorphous Fe arsenate and Fe oxyhydroxide. Nearly all hardpan is associated with historical arsenopyrite-bearing concentrate which provides a source of acidity, As⁵⁺ and Fe³⁺ for secondary mineral precipitation. Pore waters sampled from the hardpan have pH values ranging from 2.43 to 7.06. Waters with the lowest pH values also have the highest As concentrations (up to 35.8 mg/L) and are associated with the most extensive hardpan and greatest amount of weathered sulfide. Samples from areas with discontinuous hardpan and less sulfide have near-neutral pH and lower As concentrations. Detailed petrographic observations indicate that the identity and stability of As-bearing secondary minerals depends on the continued availability of sulfide concentrate. The results of this study are being used to develop remediation strategies for highly weathered, hardpan-bearing tailings that consider the stability of both primary and secondary minerals under various cover scenarios.     

Mobility of arsenic and environmentally significant elements in mine tailings following liming

Remediation of a legacy tin-tailings site in northeast Tasmania, Australia was carried out by statutory authorities. This study evaluated the fate of As and other deleterious trace metals Cd, Cu, Fe and Zn (among others) following the application of lime and fertiliser. Arsenic concentrations in the tailings ranged from 86 mg/kg to 0.26 wt%. Surface application of lime resulted in a 100-fold reduction in dissolved As concentrations in on-site surface waters; from an average of 196 µg/L prior to lime addition, to between 2.0 and 7.4 µg/L post-amendment. The concentration of other deleterious elements, however, varied between dry and wet cycles. The concentrations of Cd, Cu and Zn in surface waters were high and similar to pre-remediation levels during dry conditions (0.4, 13.5 and 6.1 mg/L, respectively), and only below freshwater ecosystem protection values during wet conditions. Bioaccumulation of Cd was observed in the naturally occurring coloniser, Juncus pallidus, with 4–5 times more Cd in the above-ground biomass relative to the tailings. Ferric arsenate (scorodite) was the dominant source of As identified in the tailings mineralogy. Hydrous ferric oxides and Fe-bearing cassiterite were also identified as hosting As. The pH increase in the surface lime-amended tailings was inferred to result in precipitation of observed hydrous ferric oxides, hematite and goethite, providing high-surface area for adsorption of arsenate onto positively charged surfaces. Jarosite was observed in both the surface lime-amended and subsurface non-amended tailings and suggests a continued supply of acidity to the pore waters despite the application of lime. Leaching experiments showed that As was more mobile in the lime-dosed tailings than in subsurface non-amended tailings, likely owing to desorption in alkaline pH conditions. By contrast, the mobility of Cd, Cu and Zn in the surface lime-amended tailings was reduced by at least two orders of magnitude compared with subsurface non-amended tailings. Evaluation of the applied rehabilitation strategy highlights the limits of a single chemical remediation approach to a polymetallic (including metalloids) waste with complex mineralogy and large seasonal fluctuations. Rehabilitation of metalliferous mine sites requires a complete understanding of all environmentally significant elements and their pathways into local receptors.     

The biogeochemical expression of deeply buried uranium mineralization in Saskatchewan, Canada

Ten kilometres from the eastern edge of the Athabasca Sandstone, near McClean Lake, uranium mineralization (locally up to 27% U₃O₈) lies 150 m beneath the surface at the unconformity between the Athabasca and crystalline basement.A biogeochemical survey of the area sampled A_H and B_F soil horizons, peat moss, and plant organs from the dominant species, viz. black spruce (Picea mariana), jack pine (Pinus banksiana), labrador tea (Ledum groenlandicum), and leather leaf (Chamaedaphne calyculata). Uranium concentrations in the ash of various media are surprisingly high: spruce twigs up to 154 ppm U; labrador tea and leather leaf stems around 100 ppm U. Conversely, labrador tea roots yield < 5 ppm U and spruce trunk wood usually < 1 ppm U. Soils give values of 1–3 ppm U. Contoured U values reveal that highest concentrations occur in plants growing above, but laterally displaced from the mineralization. Track-Etch data show a similar pattern. Upward migration of ions along steeply inclined fractures is invoked to explain the phenomenon. Other elements are present in varying concentrations, depending upon the plant species and the plant organ. High concentrations of several elements are recorded, most notably Cd and Ag in the conifers.     

Control of As and Ni releases from a uranium mill tailings neutralization circuit: Solution chemistry, mineralogy and geochemical modeling of laboratory study results

Processing U ores in the JEB Mill of the McClean Lake Operation in northern Saskatchewan produces spent leaching solutions (raffinates) with pH  1.5, and As and Ni concentrations up to 6800 and 5200 mg L⁻¹, respectively. Bench-scale neutralization experiments (pH 2–8) were performed to help optimize the design of mill processes for reducing As and Ni concentrations in tailings and raffinates to 1 mg L⁻¹ prior to their disposal. Precipitate mineralogy determined by chemical analysis, XRD, SEM, EM, XM and EXAFS methods, included gypsum (the dominant precipitate), poorly crystalline scorodite (precipitated esp. from pH 2–4), annabergite, hydrobasaluminite, ferrihydrite, green rust II and theophrastite. The As was mostly in scorodite with smaller amounts in annabergite and trace As adsorbed and/or co-precipitated, probably by ferrihydrite. Geochemical modeling indicated that above pH 2, the ion activity product (IAP) of scorodite lies between the solubility products of amorphous and crystalline phases (log K_sp = −23.0 and −25.83, respectively). The IAP decreases with increasing pH, suggesting that the crystallinity of the scorodite increases with pH. Forward geochemical models support the assumption that during neutralization, particles of added base produce sharp local pH gradients and disequilibrium with bulk solutions, facilitating annabergite and theophrastite precipitation.     

Arsenic and iron speciation in uranium mine tailings using X-ray absorption spectroscopy

In northern Saskatchewan, Canada, high-grade U ores and the resulting tailings can contain high levels of As. An environmental concern in the U mining industry is the long-term stability of As within tailings management facilities (TMFs) and its potential transfer to the surrounding groundwater. To mitigate this problem, U mill effluents are neutralized with lime to reduce the aqueous concentration of As. This results in the formation of predominantly Fe³⁺–As⁵⁺ secondary mineral phases, which act as solubility controls on the As in the tailings discharged to the TMF. Because the speciation of As in natural systems is critical for determining its long-term environmental fate, characterization of As-bearing mineral phases and complexes within the deposited tailings is required to evaluate its potential transformation, solubility, and long-term stability within the tailings mass. In this study, synchrotron-based bulk X-ray absorption spectroscopy (XAS) was used to study the speciation of As and Fe in mine tailings samples obtained from the Deilmann TMF at Key Lake, Saskatchewan. Comparisons of K-edge X-ray absorption spectra of tailings samples and reference compounds indicate the dominant oxidation states of As and Fe in the mine tailings samples are +5 and +3, respectively, largely reflecting their generation in a highly oxic mill process, deposition in an oxidized environment, and complexation within stable oxic phases. Linear combination fit analyses of the K-edges for the Fe X-ray absorption near edge spectra (XANES) to reference compounds suggest Fe is predominantly present as ferrihydrite with some amount of the primary minerals pyrite (8–15% in some samples) and chalcopyrite (5–15% in some samples). Extended X-ray absorption fine structure (EXAFS) analysis of As K-edge spectra indicates that As⁵⁺ (arsenate) present in tailings samples is adsorbed to the ferrihydrite though an inner-sphere bidentate linkage.