Distribution of inorganic arsenic species in mine tailings of abandoned mines from Korea

The main objective of the present study is to determine arsenic species in mine tailings by applying an ion exchange method. Three abandoned mines, Jingok, Cheonbo and Sino mines in Korea, which had produced mainly gold, were selected for the collection and analysis of the tailings. It was found that the arsenic speciation using an ion exchange method was effective to separate As(III) and As(V) in leachate of mine tailings. The concentration of As(V) was found to be 63-99% in the leachate, indicating that As(V) would be the major arsenic species in the mine tailings and the tailings were under oxic conditions. The total concentrations of arsenic and metal elements in the mine tailings were up to 62,350 mg/kg As, 40 wt.% Fe, 21,400 mg/kg Mn, and 7,850 mg/kg Al. Sulfate was the dominant anion throughout the leachate, reaching a maximum dissolved concentration of 734 mg/l. The results of XRD and SEM in the mine tailings showed that main arsenic-containing minerals were pyrite (FeS2) and arsenopyrite (FeAsS) which would be the source of arsenic contamination in the study area.     

Arsenic rich iron plaque on macrophyte roots - an ecotoxicological risk?

Arsenic is known to accumulate with iron plaque on macrophyte roots. Three to four years after the Aznalcóllar mine spill (Spain), residual arsenic contamination left in seasonal wetland habitats has been identified in this form by scanning electron microscopy. Total digestion has determined arsenic concentrations in thoroughly washed ‘root + plaque’ material in excess of 1000 mg kg⁻¹, and further analysis using X-ray absorption spectroscopy suggests arsenic exists as both arsenate and arsenite. Certain herbivorous species feed on rhizomes and bulbs of macrophytes in a wide range of global environments, and the ecotoxicological impact of consuming arsenic rich iron plaque associated with such food items remains to be quantified. Here, greylag geese which feed on Scirpus maritimus rhizome and bulb material in areas affected by the Aznalcóllar spill are shown to have elevated levels of arsenic in their feces, which may originate from arsenic rich iron plaque.     

Effects of the arbuscular mycorrhizal fungus Glomus mosseae on growth and metal uptake by four plant species in copper mine tailings

A greenhouse experiment was conducted to evaluate the potential role of arbuscular mycorrhizal fungi (AMF) in encouraging revegetation of copper (Cu) mine tailings. Two native plant species, Coreopsis drummondii and Pteris vittata, together with a turf grass, Lolium perenne and a leguminous plant Trifolium repens associated with and without AMF Glomus mosseae were grown in Cu mine tailings to assess mycorrhizal effects on plant growth, mineral nutrition and metal uptake. Results indicated that symbiotic associations were successfully established between G. mosseae and all plants tested, and mycorrhizal colonization markedly increased plant dry matter yield except for L. perenne. The beneficial impacts of mycorrhizal colonization on plant growth could be largely explained by both improved P nutrition and decreased shoot Cu, As and Cd concentrations. The experiment provided evidence for the potential use of local plant species in combination with AMF for ecological restoration of metalliferous mine tailings.     

Arsenic in the soils of Zimapán, Mexico

Arsenic concentrations of 73 soil samples collected in the semi-arid Zimapán Valley range from 4 to 14 700 mg As kg(-1). Soil arsenic concentrations decrease with distance from mines and tailings and slag heaps and exceed 400 mg kg(-1) only within 500 m of these arsenic sources. Soil arsenic concentrations correlate positively with Cu, Pb, and Zn concentrations, suggesting a strong association with ore minerals known to exist in the region. Some As was associated with Fe and Mn oxyhydroxides, this association is less for contaminated than for uncontaminated samples. Very little As was found in the mobile water-soluble or exchangeable fractions. The soils are not arsenic contaminated at depths greater than 100 cm below the surface. Although much of the arsenic in the soils is associated with relatively immobile solid phases, this represents a long-term source of arsenic to the environment.     

Influences of wetland plants on weathered acidic mine tailings

Establishment of Carex rostrata, Eriophorum angustifolium and Phragmites australis on weathered, acidic mine tailings (pH approximately 3) and their effect on pH in tailings were investigated in a field experiment. The amendments, sewage sludge and an ashes-sewage sludge mixture, were used as plant nutrition and their influence on the metal and As concentrations of plant shoots was analysed. An additional experiment was performed in greenhouse with E. angustifolium and sewage sludge as amendments in both weathered and unweathered tailings. After one year, plants grew better in amendments containing ashes in the field, also in those plants the metal and As shoot concentrations were generally lower than in other treatments. After two years, the only surviving plants were found in sewage sludge mixed with ashes. No effect on pH by plants was found in weathered acidic mine tailings in either field- or greenhouse experiment.     

Application of an integrated biomarker response index to assess ground water contamination in the vicinity of a rare earth mine tailings site

We utilized a multi-biomarker approach (Integrated Biomarker Response version 2, IBRv2) to investigate the scope and dispersion of groundwater contamination surrounding a rare earth mine tailings impoundment. Parameters of SD rat included in our IBRv2 analyses were glutathione levels, superoxide dismutase, catalase, and glutathione peroxidase activities, total anti-oxidative capacity, chromosome aberration, and micronucleus formation. The concentration of 20 pollutants including Cl^?, SO₄ ^2?, Na⁺, K⁺, Mg²⁺, Ca²⁺, TH, COD_Mn, As, Se, TDS, Be, Mn, Co, Ni, Cu, Zn, Mo, Cd, and Pb in the groundwater were also analyzed. The results of this study indicated that groundwater polluted by tailings impoundment leakage exhibited significant ecotoxicological effects. The selected biomarkers responded sensitively to groundwater pollution. Analyses showed a significant relationship between IBRv2 values and the Nemerow composite index. IBRv2 could serve as a sensitive ecotoxicological diagnosis method for assessing groundwater contamination in the vicinity of rare earth mine tailings. According to the trend of IBRv2 value and Nemerow composite index, the maximum diffusion distance of groundwater pollutants from rare earth mine tailings was approximately 5.7 km.

     

Remediation of arsenic-contaminated soils and washing effluents

Laboratory experiments were conducted to determine the distribution of various arsenic species in tailings and soils. Other specific goal of the tests were to evaluate the extraction efficiency of arsenic using alkaline or acid washing, to determine optimum operational parameters of alkaline washing, and to evaluate the arsenic precipitation of washing effluents by pH adjustment or ferric chloride addition. Alkaline washing using sodium hydroxide was found to be favorable in removing arsenic from tailings or soils having a higher portion of arsenic in the operationally defined crystalline mineral fraction of crystalline oxide and amorphous aluminosilicates. This is due to the ligand displacement reaction of hydroxyl ions with arsenic species and high pH conditions that can prevent readsorption of arsenic because predominant negatively charged crystalline oxides do not attract the negatively charged oxyanions. For tailings, sodium hydroxide had 10-20 times higher extraction efficiencies than hydrochloric- or citric acid. The optimum concentration of sodium hydroxide for soil washing was determined to be 200 mM for all samples, while the optimum ratios were 10:1 and 5:1 for tailings and field/river sedimentary soils, respectively. The washing effluent of river soil was effectively treated by adjusting pH to 5-6 with hydrochloric acid, resulting in arsenic concentrations of <50 microgl(-1). In the case of field soil effluent, an addition of ferric chloride with a minimum mass ratio of 11 (Fe/As) was needed to reduce the arsenic below 50 microgl(-1).     

Enhanced mobilization of arsenic and heavy metals from mine tailings by humic acid

Arsenic and heavy metal mobilization from mine tailings is an issue of concern as it might pose potential groundwater or ecological risks. Increasing attention recently has been focused on the effects of natural organic matter on the mobility behavior of the toxicants in the environment. Column experiments were carried out in this research study to evaluate the feasibility of using humic acid (HA) to mobilize arsenic and heavy metals (i.e., Cu, Pb and Zn) from an oxidized Pb-Zn mine tailings sample collected from Bathurst, New Brunswick, Canada. Capillary electrophoresis analyses indicated that arsenate [As(V)] was the only extractable arsenic species in the mine tailings and the addition of HA at pH 11 did not incur the oxidation-reduction or methylation reactions of arsenic. A 0.1% HA solution with an initial pH adjusted to 11 was selected as the flushing solution, while distilled water (initial pH adjusted to 11) was used as the control to account for the mobilization of arsenic and the heavy metals by physical mixing and the effect of pH. It was found that the HA could significantly enhance the mobilization of arsenic and heavy metals simultaneously from the mine tailings. After a 70-pore-volume-flushing, the mobilization of arsenic, copper, lead and zinc reached 97, 35, 838 and 224 mg kg(-1), respectively. The mobilization of arsenic and the heavy metals was found to be positively correlated with the mobilization of Fe in the presence of the HA. Moreover, the mobilization of arsenic was also correlated well with that of the heavy metals. The mobilization of co-existing metals to some extent might enhance arsenic mobilization in the presence of the HA by helping incorporate it into soluble aqueous organic complexes through metal-bridging mechanisms. Use of HA in arsenic and heavy metal remediation may be developed as an environmentally benign and possible effective remedial option to reduce and avoid further contamination.     

Water striders (family Gerridae): mercury sentinels in small freshwater ecosystems

To circumvent some of the previous limitations associated with contaminant-monitoring programs, we tested the suitability of the water strider (Hemiptera: Gerridae) as a mercury sentinel by comparing total mercury concentrations in water striders and brook trout (Salvelinus fontinalis) from a variety of stream sites in New Brunswick, Canada. There was a strong association between the two variables across sites (r(2)=0.81, P<0.001) in systems where both atmospheric deposition and a point source (an abandoned gold mine) were likely contributing to ambient mercury levels. In a small stream draining the gold mine tailings pile, water striders had mercury concentrations an order of magnitude higher than those from reference locations. Temporal variation at three southern New Brunswick stream sites was non-significant. These results suggest that water strider mercury levels accurately quantify food chain entry of the element. The use of sentinel species holds great potential for expanding contaminant-monitoring programs.     

The potential of Thai indigenous plant species for the phytoremediation of arsenic contaminated land

To assess the potential of the native plant species for phytoremediation, plant and soil samples were collected from two areas in Thailand that have histories of arsenic pollution from mine tailings. The areas were the Ron Phibun District (Nakorn Si Thammarat province) and Bannang Sata District (Yala province), and samples were taken in 1998 and 1999 and analysed for total arsenic by atomic absorption spectrophotometry. Arsenic concentrations in soil ranged from 21 to 14,000 microg g(-1) in Ron Phibun, and from 540 to 16,000 microg g(-1) in Bannang Sata. The criteria used for selecting plants for phytoremediation were: high As tolerance, high bioaccumulation factor, short life cycle, high propagation rate, wide distribution and large shoot biomass. Of 36 plant species, only two species of ferns (Pityrogramma calomelanos and Pteris vittata), a herb (Mimosa pudica), and a shrub (Melastoma malabrathricum), seemed suitable for phytoremediation. The ferns were by far the most proficient plants at accumulating arsenic from soil, attaining concentrations of up to 8350 microg g(-1) (dry mass) in the frond.     

Effects of dissolution kinetics on bioaccessible arsenic from tailings and soils

Dissolution kinetics of arsenic from soils and tailings were studied under simulated gastrointestinal conditions to determine the effects of residence time, pH and soil composition on the bioaccessibility of arsenic. The samples were sieved to four particle size fractions from bulk to <45 μm, and included arsenic minerals, soils and tailings with total arsenic concentrations ranging from 19 to 420 00 mg kg⁻¹. The bioaccessible arsenic concentrations varied from 2.8 to 10 000 mg kg⁻¹, and the highest concentrations were associated with the smallest particle size fractions. Kinetic parameters were determined for each sample extracted under gastric conditions (pH = 1.8) followed by intestinal conditions (pH = 7.0). Under gastric pH conditions, dissolution appeared to be diffusion-controlled and followed an exponential curve, whereas a logarithmic or linear model was used to describe the mixed dissolution mechanisms observed under intestinal conditions. Nine of the 13 samples tested reached a steady state bioaccessible arsenic concentration within the 5-h physiologically-based extraction test (PBET). However the bioaccessible arsenic concentrations in four tailings samples increased significantly (p = 0.034) between the 5-h and the extended 24-h extraction under intestinal conditions. Since arsenic absorption may occur along the entire digestive tract, assessments based on the standard 5-h PBET extraction may not adequately estimate the risks associated with arsenic absorption in such cases. The slow dissolution kinetics associated with secondary arsenic minerals in some tailings samples may require extending the PBET extractions to longer periods, or extrapolating using the proposed kinetic models, to reach steady state concentrations in simulated gastrointestinal fluids.     

Screening the phytoremediation potential of desert broom (Baccharis sarothroides Gray) growing on mine tailings in Arizona, USA

The metal concentrations in a copper mine tailings and desert broom (Baccharis sarothroides Gray) plants were investigated. The metal concentrations in plants, soil cover, and tailings were determined using ICP-OES. The concentration of copper, lead, molybdenum, chromium, zinc, arsenic, nickel, and cobalt in tailings was 526.4, 207.4, 89.1, 84.5, 51.7, 49.6, 39.7, and 35.6mgkg(-1), respectively. The concentration of all elements in soil cover was 10-15% higher than that of the tailings, except for molybdenum. The concentration of copper, lead, molybdenum, chromium, zinc, arsenic, nickel, and cobalt in roots was 818.3, 151.9, 73.9, 57.1, 40.1, 44.6, 96.8, and 26.7mgkg(-1) and 1214.1, 107.3, 105.8, 105.5, 55.2, 36.9, 30.9, and 10.9mgkg(-1) for shoots, respectively. Considering the translocation factor, enrichment coefficient, and the accumulation factor, desert broom could be a potential hyperaccumulator of Cu, Pb, Cr, Zn, As, and Ni.     

High levels of activity of bats at gold mining water bodies: implications for compliance with the International Cyanide Management Code

Wildlife and livestock are known to visit and interact with tailings dam and other wastewater impoundments at gold mines. When cyanide concentrations within these water bodies exceed a critical toxicity threshold, significant cyanide-related mortality events can occur in wildlife. Highly mobile taxa such as birds are particularly susceptible to cyanide toxicosis. Nocturnally active bats have similar access to uncovered wastewater impoundments as birds; however, cyanide toxicosis risks to bats remain ambiguous. This study investigated activity of bats in the airspace above two water bodies at an Australian gold mine, to assess the extent to which bats use these water bodies and hence are at potential risk of exposure to cyanide. Bat activity was present on most nights sampled during the 16-month survey period, although it was highly variable across nights and months. Therefore, despite the artificial nature of wastewater impoundments at gold mines, these structures present attractive habitats to bats. As tailings slurry and supernatant pooling within the tailings dam were consistently well below the industry protective concentration limit of 50 mg/L weak acid dissociable (WAD) cyanide, wastewater solutions stored within the tailings dam posed a minimal risk of cyanide toxicosis for wildlife, including bats. This study showed that passively recorded bat echolocation call data provides evidence of the presence and relative activity of bats above water bodies at mine sites. Furthermore, echolocation buzz calls recorded in the airspace directly above water provide indirect evidence of foraging and/or drinking. Both echolocation monitoring and systematic sampling of cyanide concentration in open wastewater impoundments can be incorporated into a gold mine risk-assessment model in order to evaluate the risk of bat exposure to cyanide. In relation to risk minimisation management practices, the most effective mechanism for preventing cyanide toxicosis to wildlife, including bats, is capping the concentration of cyanide in tailings discharged to open impoundments at 50 mg/L WAD.     

Total arsenic accumulation in edible pods and seeds of Phaseolus vulgaris.

The main objective of this study was to evaluate whether arsenic accumulated in the edible pods and seeds of Phaseolus vulgaris, cv. Helda, above the Spanish maximum recommended concentration for food crops, 1 mg kg(-1) on a fresh weight basis. Only organic arsenicals were used because they are: a) the only arsenic species allowed for agricultural applications and b) more mobile than inorganic species. Selection of French beans, a sensitive plant to arsenic, was based on the fact that arsenic upward translocation is higher in sensitive than in tolerant plants. A 2 x 3 factorial experiment was conducted with two organic arsenic species: methylarsonic acid (MAA) or dimethylarsinic acid (DMAA) and three arsenic concentrations: 0.2, 0.5, or 1.0 mg L(-1). Arsenic phytotoxicity was primarily determined by soluble arsenic concentration. Experimental results showed that the low bean plant tolerance to arsenic is possibly due to the high arsenic upward transport to shoots, which could result in profound negative metabolic consequences. Even under extremely adverse conditions, arsenic residues in edible beans were below the maximum statutory limit set by the Spanish legislation. It can be concluded that the major danger of organic arsenical herbicides is that of decreased productivity rather than high arsenic uptake by consumers.     

TOTAL ARSENIC ACCUMULATION IN EDIBLE PODS AND SEEDS OF PHASEOLUS VULGARIS

The main objective of this study was to evaluate whether arsenic accumulated in the edible pods and seeds of Phaseolus vulgaris, cv. Helda, above the Spanish maximum recommended concentration for food crops, 1 mg kg^?1 on a fresh weight basis. Only organic arsenicals were used because they are: a) the only arsenic species allowed for agricultural applications and b) more mobile than inorganic species. Selection of French beans, a sensitive plant to arsenic, was based on the fact that arsenic upward translocation is higher in sensitive than in tolerant plants. A 2 × 3 factorial experiment was conducted with two organic arsenic species: methylarsonic acid (MAA) or dimethylarsinic acid (DMAA) and three arsenic concentrations: 0.2, 0.5, or 1.0 mg L^?1. Arsenic phytotoxicity was primarily determined by soluble arsenic concentration. Experimental results showed that the low bean plant tolerance to arsenic is possibly due to the high arsenic upward transport to shoots, which could result in profound negative metabolic consequences. Even under extremely adverse conditions, arsenic residues in edible beans were below the maximum statutory limit set by the Spanish legislation. It can be concluded that the major danger of organic arsenical herbicides is that of decreased productivity rather than high arsenic uptake by consumers.     

Reuse of washing effluent containing oxalic acid by a combined precipitation–acidification process

This study aims at evaluating the reuse feasibility of effluent produced by the soil washing of mine tailings with oxalic acid. Alkaline chemicals such as NaOH, Ca(OH)₂, and Na₂CO₃ are used for the precipitation of arsenic and heavy metals in the effluent containing oxalic acid. All of the target contaminants are removed with very high efficiency (up to 100%) at high pH. The precipitation using NaOH at pH 9 is determined to be the most cost-effective method for the removal of arsenic as well as heavy metals in the effluent. The effluent decontaminated by NaOH is consecutively reused for the soil washing of raw mine tailings, resulting in considerable efficiency. Furthermore, even more arsenic and heavy metals are extracted from raw mine tailings by acidifying the decontaminated effluent under the alkaline condition, compared with direct reuse of the decontaminated effluent. Here, the oxalic acid, which is a weak complex-forming ligand as well as a weak acid, has noticeable effects on both soil washing and effluent treatment by precipitation. It extracts efficiently the contaminants from the mine tailings without adverse change of soil and also makes possible the precipitation of the contaminants in the effluent unlike strong chelating reagent. Reuse of the washing effluent containing oxalic acid would make the existing soil washing process more environment-friendly and cost-effective.     

Role of expanded clay and porous ceramic amendments on plant establishment in minespoils

Greenhouse experiments were conducted to examine the impact of expanded clay (Turface) or porous ceramic (Isolite) amendments on germination, biomass production, plant Zn concentration, and Zn accumulation by Festuca arundinacea grown in mine tailings. Because previous studies have demonstrated that fertilization is essential for plant growth in these tailings, manure was also added to the tailings. Plant growth and germination were greatest if the expanded clay was added topically to the tailings. To a lesser extent, plant growth and germination was also stimulated by topical additions of porous ceramic. However, no benefit was observed if either amendment was mixed into the top 10 cm of the mine tailings. The concentration of Zn in F. arundinacea tissues was lowest if the expanded clay was added topically to the mine tailings. Roots growing in the layer of clay or ceramic amendment appeared to be smaller, finer, and more abundant than the large, coarse roots found throughout the tailings-manure mixture. These results suggest that topical application of an expanded clay or porous ceramic product will increase seed germination and improve plant establishment and growth in contaminated minespoils.     

Electromigration of arsenic and co-existing metals in mine tailings

The aim of this study was to investigate the feasibility of enhanced electrokinetic remediation technology for controlled leaching and collection of labile arsenic fractions from mine tailings. Direct current was applied to tailings for 20 d using ammonium oxalate and sodium hydroxide as enhancement solutions. Migration of arsenic was observed, resulting in 63-71% removal near the cathode but only 6-17% overall removal in the entire tailings matrix in 20 d. However, significant migration of arsenic towards the anode and accumulation in a collection well near the anode was observed, especially under alkaline conditions. Thus, treatment time and consumption of chemicals could probably be reduced by installing specific collection or adsorption zones near the anode. A relationship between electrokinetic mobility of arsenic and other elements and their extractability in sequential extraction tests was established, indicating that dissolution or desorption of the elements and thermodynamic conditions (pH and Eh gradient) played a bigger role in the electrokinetic removal process than electromigration of soluble ions.     

Arsenic uptake and accumulation in curly endives (Cichorium endivia L.) irrigated with contaminated water

Arsenic accumulation in vegetables for direct human consumption represents a concern for food safety purposes. This potential problem can be of economic importance particularly in much appreciated, high-quality horticultural products. In this work, a greenhouse set of experiments were conducted to evaluate possible phytotoxic effects and arsenic accumulation in the production of curly endives with arsenic contaminated water.Two concentration levels (0.5 mg/L and 1.0 mg/L) and two arsenic species (As+3 and As+5) were considered. Dry mass production tended to be reduced as As+3 concentration increased in irrigation water. However, As+5 treatments did not show significant dry mass production differences with a blank (control experiment). As accumulation in plant increased with As concentration in irrigation waters, following a linear trend. Nevertheless, the increase of accumulated As was not statistically significant for As+5 at 0.5 mg/L. Calculated biological absorption coefficients resulted in higher than previous values reported in the literature, which was attributed here to the source of arsenic (irrigation water). Considering field values for As+5/As+3 ratio and averaged concentrations in water, the obtained results support that there is not a short-or medium-term risk to food safety in the curly endive crop in the region of Castilla y León (Spain).     

Changes in pH and organic acids in mucilage of Eriophorum angustifolium roots after exposure to elevated concentrations of toxic elements

The presence of Eriophorum angustifolium in mine tailings of pyrite maintains a neutral pH, despite weathering, thus lowering the release of toxic elements into acid mine drainage water. We investigated if the presence of slightly elevated levels of free toxic elements triggers the plant rhizosphere to change the pH towards neutral by increasing organic acid contents. Plants were treated with a combination of As, Pb, Cu, Cd, and Zn at different concentrations in nutrient medium and in soil in a rhizobox-like system for 48–120 h. The pH and organic acids were detected in the mucilage dissolved from root surface, reflecting the rhizospheric solution. Also the pH of root–cell apoplasm was investigated. Both apoplasmic and mucilage pH increased and the concentrations of organic acids enhanced in the mucilage with slightly elevated levels of toxic elements. When organic acids concentration was high, also the pH was high. Thus, efflux of organic acids from the roots of E. angustifolium may induce rhizosphere basification.