The potential use of serpentinite in the passive treatment of acid mine drainage: batch experiments

The efficiency of serpentinite as an alternative alkalinity generating material for the passive treatment of acid mine drainage (AMD) was assessed in the laboratory. Three series of batch experiments were designed for the passive treatment of a low pH (1.6) AMD synthetic solution containing 2,500 ppm Fe²⁺, 6,600 ppm SO₄^2–, 10.5 ppm Al, 15 ppm Ni, and traces of Cr, Mn and Cu. The influencing factors studied were: the effect of water/rock ratio, residence time, type of the alkalinity generating material (dolomite, magnesite, marble, serpentinite), and nature of the system (open vs. closed cells). The variations in solution chemistry observed in the open cells indicate that a lower water/rock ratio (0.33 ml/g) was the most efficient for metals removal. The optimal residence time in open cells was 24 h to reach the higher pH values. In the closed cells laboratory setup, synthetic AMD was placed in contact with the various alkaline materials for three different contact times (24, 48, 72 h). The optimal pH was reached after 48 h and did not change appreciably for longer contact time, and the best results for metal removals were obtained with marble and serpentinite. Single treatment efficiency was compared with a successive treatment approach. The most promising results were obtained with a five step treatment: (1) pre-treatment in a closed cell using serpentinite, (2) aeration and settling, (3) treatment in an open cell using marble, (4) final aeration and settling, and (5) filtration with a coarse silica sand. With this configuration, the final pH was 6.5 and pronounced metals depletion was achieved (100% for Al, 99.95% for Fe, 85.7% for Ni).     

Environmental impact and remediation of acid mine drainage: a management problem

 Work carried out at the abandoned copper (Cu) and sulphur (S) mine at Avoca (south east Ireland) has shown acid mine drainage (AMD) to be a multi-factor pollutant. It affects aquatic ecosystems by a number of direct and indirect pathways. Major impact areas are rivers, lakes, estuaries and coastal waters, although AMD affects different aquatic ecosystems in different ways. Due to its complexity, the impact of AMD is difficult to quantify and predict, especially in riverine systems. Pollutional effects of AMD are complex but can be categorized as (a) metal toxicity, (b) sedimentation processes, (c) acidity, and (d) salinization. Remediation of such impacts requires a systems management approach which is outlined. A number of working procedures which have been developed to characterise AMD sites, to produce surface water quality management plans, and to remediate mine sites and AMD are all discussed. Received: 16 January 1996 · Accepted: 5 March 1996     

Field assessment of acid mine drainage contamination in surface and ground water

Both sulfate and conductivity are useful indicators of acid mine drainage (AMD) contamination. Unlike pH, they are both extremely sensitive to AMD even where large dilutions have occurred. The advantage of using sulfate to trace AMD is that unlike other ions it is not removed to any great extent by sorption or precipitation processes, being unaffected by fluctuations in pH. These two parameters are also closely associated as would be expected, as conductivity is especially sensitive to sulfate ions. Therefore, as sulfate analysis is difficult in the field, conductivity can be used to predict sulfate concentration in both AMD and contaminated surface waters using regression analysis. Most accurate predictions are achieved by using equations given for specific conductivity ranges or AMD sources. There is also potential to use conductivity to predict approximate concentrations of key metals when the pH of the water is within their respective solubility ranges.     

Pollution of Osheepcheon Creek by abandoned coal mine drainage in Dogyae area,eastern part of Samcheok coal field,Kangwon-Do,Korea

Osheepcheon Creek running through the Dogyae area is being polluted by the influx of the abandoned coal mine drainage. Generally, the more polluted water has lower pH and Eh and higher conductivity values. The concentrations of Mg, Ca, Fe, SO₄, and some trace elements, such as Cd, Co, Cr, Mo, Ni, Pb, Rb, Sr, U and Zn, are tens to hundreds of times more concentrated in the abandoned coal mine drainage than in the unpolluted streamwater. However, most immobile toxic pollutants from the mine drainage are quickly removed from the streamwater by the precipitation of amorphous Fe hydroxide and sorption on the precipitated Fe hydroxide. The fast removal of the pollutants from the streamwater maintains the water quality of the creek as acceptable at most places along the stream path, except where the abandoned coal mine drainage flows in. However, the creek has the potential of deteriorating quickly if the mine drainage is allowed to be continuously combined with the streams. A function of pH, Eh, and conductivity has been developed with discriminant function analysis for the purpose of easy, fast, and inexpensive measurement of the degrees of pollution of the streams. The estimated pollution of the streams with the discriminant function are consistent with what the chemical compositions of the water samples indicate. The pollution map of the study area was constructed from the calculated scores with the discriminant function. The pollution map suggests that the pollutants mainly come from the west side of Osheepcheon Creek. Thus, the abandoned coal mine drainage from the west side has to be appropriately treated as soon as possible to prevent Osheepcheon Creek from being further polluted. Considering the topography, climate, and the amount of the mine drainage, an active treatment method is recommended.     

Zero-valent iron and organic carbon mixtures for remediation of acid mine drainage: Batch experiments

A series of laboratory batch experiments was conducted to evaluate the potential for treatment of acid mine drainage (AMD) using organic C (OC) mixtures amended by zero-valent Fe (Fe⁰). Modest increases in SO₄ reduction rates (SRRs) of up to 15% were achieved by augmenting OC materials with 5 and 10 dry wt% Fe⁰. However, OC was essential for supporting SO₄ reducing bacteria (SRB) and therefore SO₄ reduction. This observation suggests a general absence of autotrophic SRB which can utilize H₂ as an electron donor. Sulfate reduction rates (SRRs), calculated using a mass-based approach, ranged from −12.9 to −14.9 nmol L⁻¹ d⁻¹  g⁻¹ OC. Elevated populations of SRB, iron reducing bacteria (IRB), and acid producing (fermentative) bacteria (APB) were present in all mixtures containing OC. Effective removal of Fe (91.6–97.6%), Zn (>99.9%), Cd (>99.9%), Ni (>99.9%), Co (>99.9%), and Pb (>95%) was observed in all reactive mixtures containing OC. Abiotic metal removal was achieved with Fe⁰ only, however Fe, Co and Mn removal was less effective in the absence of OC. Secondary disordered mackinawite [Fe_1+xS] was observed in field-emission scanning electron microscopy (FE-SEM) backscatter electron micrographs of mixtures that generated SO₄ reduction. Energy dispersive X-ray (EDX) spectroscopy revealed that Fe–S precipitates were Fe-rich for mixtures containing OC and Fe⁰, and S-rich in the absence of Fe⁰ amendment. Sulfur K-edges determined by synchrotron-radiation based bulk X-ray absorption near-edge structure (XANES) spectroscopy indicate solid-phase S was in a reduced form in all mixtures containing OC. Pre-edge peaks on XANES spectra suggest tetragonal S coordination, which is consistent with the presence of an Fe–S phase such as mackinawite. The addition of Fe⁰ enhanced AMD remediation over the duration of these experiments, however long-term evaluation is required to identify optimal Fe⁰ and OC mixtures.     

酸性矿山废水中石灰岩包壳作用研究

研究石灰岩包壳作用有助于深入了解酸性矿山废水(AMD)在富含石灰岩的金属硫化物尾矿中的释放机制。采用AMD滞留浸泡石灰岩颗粒试料的实验方法,研究在酸水饱和条件下石灰岩次生包壳的形成作用。研究表明,AMD的Fe含量是影响石灰岩包壳作用的主因之一。在高Fe浓度(如1 029~1 033 mg/L)的AMD中,石灰岩颗粒表面可依次沉淀富Al相、石膏、纤铁矿(吸附Zn、Cu及As等),发生石灰岩包壳/钝化作用,使溶液维持酸性;而在低Fe浓度(6.71~74.8 mg/L)的AMD中,次生包壳难以生成,石灰岩得以大量溶解释碱并充分中和溶液中的H~+,使溶液达到中性。因此,Fe硫化物含量较高(如Fe含量10.62%、S含量5.70%)的石灰岩尾矿,由于其氧化后可生成高Fe浓度的酸性水而导致石灰岩包壳作用,具有释放AMD(及重金属)的危险,应注意防控。     

Acid mine drainage and acid rock drainage processes in the environment of Herrerías Mine (Iberian Pyrite Belt, Huelva-Spain) and impact on the Andevalo Dam

The present work describes the process of acid water discharge into the Andévalo Dam (Iberian Pyrite Belt, Huelva-Spain) starting from the interpretation of rainfall data and chemical analyses regarding pH, conductivity, metal and sulphate content in water, from a time series corresponding to the sampling of two confluent channels that discharge water into the referred dam. Statistical data treatment allows us to conclude the existence of acid mine drainage processes in the Chorrito Stream, which are translated into very low pH values and high sulphate and metal concentrations in the water coming from Herrerías Mine. On the other hand, the Higuereta Stream shows, for the same parameters, much lower values that can be interpreted as the channel response to acid rock drainage processes in its drainage basin induced by the rocky outcrops of the Iberian Pyrite Belt.     

Mineralogical constraints on the determination of neutralization potential and prediction of acid mine drainage

 Acid-base accounting tests, commonly used as a screening tool in acid mine drainage (AMD) predictions, have limitations in (1) measuring with confidence the amount of neutralizers present in samples and (2) affording an interpretation of what the test results mean in terms of predicting the occurrence of acid mine drainage. Aside from the analytical difficulties inherent to the conventional methods, a potential source of error in neutralization potential (NP) measurements is the contribution from the dissolution of non-carbonate minerals. Non-carbonate alkalinity measured during static tests may or may not be available to neutralize acidity produced in the field. In order to assess the value-added of extending the NP with the knowledge of mineralogical composition and evaluate potential sources of errors in NP measurements, a suite of samples were examined and characterized in terms of their mineralogical and chemical compositions. The results indicate that although the acid-base accounting tests work well for simple compositions, the tests may result in overestimation or underestimation of NP values for field samples. Mineralogical constraint diagrams relating NP determinations to Ca, Mg and CO₂ concentrations were developed with the purpose to serve as supplementary guides to conventional static tests in identifying possible NP contributions from non-carbonate minerals and checking the quality of the chemical testing results. Mineralogical NP makes it possible to interpret the meaning of NP results and to assess the behaviour of samples over time by predicting the onset of AMD and calculating NP values for individual size fractions. Received: 1 June 1998 · Accepted: 6 October 1998     

Arsenate and arsenite adsorption onto Al-containing ferrihydrites. Implications for arsenic immobilization after neutralization of acid mine drainage

Natural ferrihydrites (Fh) often contain impurities such as aluminum, especially in acid mine drainage, and these impurities can potentially impact the chemical reactivity of Fh with respect to metal (loid) adsorption. In the present study, we have investigated the influence of aluminum on the sorption properties of ferrihydrite with respect to environmentally relevant aqueous arsenic species, arsenite and arsenate. We have conducted sorption experiments by reacting aqueous As(III) and As(V) with synthetic Al-free and Al-bearing ferrihydrite at pH 6.5. Our results reveal that, when increasing the Al:Fe molar ratio in Fh, the sorption density dramatically decreased for As(III), whereas it increased for As(V). Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy analysis at the As K-edge indicated that the As^IIIO₃ pyramid binds to FeO₆ octahedra on both Al-free Fh and Al-bearing Fh, by forming bidentate mononuclear edge-sharing (²E) and bidentate binuclear corner-sharing (²C) surface complexes characterized by As–Fe distances of 2.9 Å and 3.4 Å, respectively. The decrease in As(III) sorption density with increasing Al:Fe ratio in Fh could thus be explained by a low affinity of the As(OH)₃ molecule for Al surface sites compared to Fe ones. In contrast, on the basis of available literature on As(V) adsorption mechanisms, we suggest that, in addition to inner-sphere ²C arsenate surface complexes, outer-sphere arsenate surface complexes forming hydrogen bonds with both Al–OH and Fe–OH surface sites could explain the enhancement of As(V) sorption onto aluminous Fh relative to Al-free Fh, as observed in the present study. The presence of aluminum in Fh may thus enhance the mobility of arsenite with respect to arsenate in Acid Mine Drainage impacted systems, while mixed Al:Fe systems could present an alternative for arsenic removal from impacted waters, provided that As(III) would be oxidized to As(V).     

A pilot-scale field experiment for the microbial neutralization of a holomictic acidic pit lake

A strategy to neutralize acidic pit lakes was tested in an upscaling process using field mesocosms of 26 to ca. 4500 m³ volume in the acidic pit Mining Lake 111 in Germany. After addition of the substrates Carbokalk and straw a neutral sediment layer formed, in which microbial sulfate and iron reduction as well as sulfide precipitation occurred. The net rate of neutralization was limited by the precipitation of iron sulfides rather than by microbial reactions. Oxidation of H₂S by ferric iron in the anoxic sediment lowered the net sulfate reduction rate. Seasonal fluctuations of iron sulfides in the sediment showed that the reaction products were not necessarily stable. The long-term success of the approach depends on the net partition of the precipitated iron-(mono-/di-) sulfide that is permanently buried in the anoxic sediment. It could be shown by field experiments that the long-term success of the neutralization depends on the spatial scale and duration of the experiments. Volumes from 26 to 4500 m³, exposition times from 4 months to 5 years, and increasingly thick coverings of the sediments with straw, from zero to 40 cm, were used. Net neutralization rates decreased from 41 meq m^− 2 d^− 1 in laboratory microcosms to a mean rate of 2.3 meq m^− 2 d^− 1 in the 4500 m³ field experiment. The results show that the success of the microbial treatment of acid pit lakes lastly depends on the limnological conditions in the lake that cannot be simulated by upscaling of simple laboratory experiments.     

The status of the passive treatment systems for acid mine drainage in South Korea

This study was performed to investigate the operating status, evaluate the problems, and discuss possible improvement methods of passive treatment systems for acid mine drainage (AMD) in South Korea. Thirty-five passive treatment systems in 29 mines have been constructed from 1996 to 2002 using successive alkalinity producing systems (SAPS) as the main treatment process. We investigated 29 systems (two for metal mines), 19 of which revealed various problems. Overflows of drainage from SAPS, wetland, or oxidation ponds were caused by the flow rate exceeding the capacities of the facilities or by the reduced permeability of the organic substance layer. Leakages occurred at various parts of the systems. In some cases, clogged and broken pipes at the mouths of the mine adits made the whole system unusable. Some systems showed very low efficiencies without apparent leakage or overflow. Even though the systems showed fairly good efficiencies in metal removal ratios (mainly iron) and pH control; sulfate removal rates were very poor except in three systems, which may indicate very poor sulfate reductions with sulfate reducing bacteria (SRB) as a means.     

Experimental study of the stability of metals associated with iron oxyhydroxides precipitated in acid mine drainage

Iron oxyhydroxide precipitates associated with acid mine drainage (AMD) from the Stearns Coal Zone in southeastern Kentucky were analyzed for their metal (Al, Cu, Pb, Mn, Ni, and Zn) content. The most concentrated metals within these sediments are nickel (27–32×10³μmol/kg), manganese (16–29×10³μmol/kg), and aluminum (13–22×10³μmol/kg) as determined by HCl-HNO₃ digestion. Metal concentrations associated with the organic fraction as determined by H₂O₂ digestion were generally far lower, with the exception of aluminum. "Batch" experiments (at initial pH=2.0) were used to analyze the stability of these metals associated with a contaminated soil. Aluminum was the most mobile of the metals, presumably the result of the formation of aluminum-sulfate aqueous complexes. The solubilization rates for nickel and iron were very similar, suggesting that nickel, unlike the other metals, coprecipitated with iron in these sulfatic oxyhydroxides. Received: 9 October 1997 · Accepted: 15 December 1997     

The potential formation of acid mine drainage in pyrite-bearing hard-coal tailings under water-saturated conditions: an experimental approach

 Annually, an amount of approximately 13 million cubic meters of hard-coal tailings must be disposed of in the German Ruhr Valley. Besides the waste of land in a densily populated region, the disposal of the pyrite-bearing material under atmospheric conditions may lead to the formation of acid mine drainage (AMD). Therefore, alternative disposal opportunities are of increasing importance, one of which being the use of tailings under water-saturated conditions, such as in backfilling of abandoned gravel pits or in the construction of waterways. In this case, the oxidation of pyrite, and hence the formation of AMD, is controlled by the amount of oxygen dissolved in the pore water of tailings deposited under water. In case the advective percolation of water is suppressed by sufficient compaction of the tailings, oxygen transport can be reduced to diffusive processes, which are limited by the diffusive flux of dissolved oxygen in equilibrium with the atmospheric pO₂. Calculations of the duration of pyrite oxidation based on laboratory experiments have shown that the reduction of oxygen is mainly controlled by the content of organic substance rather than the pyrite content, a fact that is supported by results from oxidation experiments with nitrate. A "worst case" study has lead to the result that the complete oxidation of a 1.5-m layer of hard-coal tailings deposited under water-saturated conditions would take as much as several hundred thousand years. Received: 6 May 1996 · Accepted: 2 August 1996     

Interaction of acid mine drainage with waters and sediments at the Corona stream, Lousal mine (Iberian Pyrite Belt, Southern Portugal)

This study investigates the geochemical characteristics of the acid mine drainage discharged from the abandoned mine adits and tailing piles in the vicinity of the Lousal mine and evaluates the extent of pollution on water and on the stream sediments of the Corona stream. Atmospheric precipitation interacting with sulphide minerals in exposed tailings produces runoff water with pH values as low as 1.9–2.9 and high concentrations of (9,249–20,700 mg l⁻¹), Fe (959–4,830 mg l⁻¹) and Al (136–624 mg l⁻¹). The acidic effluents and mixed stream water carry elevated Cu, Pb, Zn, Cd and As concentrations that exceed the water quality standards. However, the severity of contamination generally decreases 4 km downstream of the source due to mixing with fresh waters, which causes the dilution of dissolved toxic metals and neutralization of acidity. Some natural attenuation of the contaminants also occurs due to the general reduced solubility of most trace metals, which may be removed from solution, by either co-precipitation or adsorption to the iron and aluminium precipitates.     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Effectiveness of various dispersed alkaline substrates for the pre-treatment of ferriferous acid mine drainage

Dispersed alkaline substrates (DAS) have been successfully used in passive treatment of highly contaminated acid mine drainage (AMD) to limit coating and clogging issues. However, further optimization of DAS systems is still needed, especially for their long-term efficiency during the treatment of ferriferous AMD. In the present study, three types of DAS comprised of natural alkaline materials (wood ash, calcite, dolomite), in different proportions (20%v/v, 50%v/v, 80%v/v), and a substrate with high surface area (wood chips) were tested in 9 batch reactors. The testing was carried out, in duplicate, for a period of 91 days, to evaluate the comparative performance of the mixtures for iron pre-treatment in ferriferous AMD (2500 mg/L Fe, at pH 4). Results showed increasing of pH (between 4.15 and 7.12), regardless of the proportion of alkaline materials in the DAS mixtures. Among the tested mixtures, wood ash type DAS were more effective for Fe removal (99.9%) than calcite or dolomite type DAS (up to 66%). All tested DAS had limited efficiency for sulfate removal and an additional treatment unit, such as a sulfate-reducing biochemical reactor, is needed. Moreover, due to the similar performances of the calcite and dolomite DAS, they could be potentially substituted and rather be used in a polishing treatment unit. Based on these findings, the most promising mixture was the 50% wood ash type DAS (WA50-DAS).     

Impacts of acid mine drainage on a stream in subtropical China during a major flood event

Field and laboratory work was carded out to investigate the chemistry and ecotoxicity of stream water affected by acid mine drainage in a tributary catchment of the Pearl River in subtropical China during a major flood event that corresponded to a return period of 100 years occurred in the study area. The results indicate that stream water was affected by acid mine drainage from the Dabaoshan Mine at least to a distance of 25 km downstream of the mine water discharge point. It appears that sulfide-H^＋ from the waste rock dumps was readily available for discharging and the amount of H^＋ being transported outwards depended on the volume of out-flowing waters. However, there was a lag time for the discharge of the metals. This may be attributed to the slower release of metals, relative to H^＋, because it might take more time for the dissolution of heavy metal-bearing compounds. Fe, Zn and Al were the major metals of potential toxicity contained in the AMD-affected stream water, followed by Mn, Cu, Pb, As, Cd and Ni. Acute toxicity tests show that the AMD-affected stream water at 3.5 km downstream of the discharge point was highly toxic to the test organisms.