Preliminary studies on potential remediation of acid mine drainage‐impacted soils by amendment with drinking‐water treatment residuals

Mining operations result in a wide range of environmental impacts: acid mine drainage (AMD) and acid sulfate soils being among the most common. Due to their acidic pH and high soluble metal concentrations, both AMD and acid sulfate soils can severely damage the local ecosystems. Proper post‐mining management practices are necessary to control AMD‐related environmental issues. Current AMD‐impacted soil treatment technologies are rather expensive and typically not environmentally sustainable. We conducted a 60‐day bench‐scale study to evaluate the potential of a cost‐effective and environment‐friendly technology in treating AMD‐impacted soils. The metal binding and acid‐neutralizing capacity of an industrial by‐product, drinking water treatment residuals (WTRs) were used for AMD remediation. Two types of locally generated WTRs, an aluminum‐based WTR (Al‐WTR) and a lime‐based WTR (Ca‐WTR) were used. Highly acidic AMD‐impacted soil containing very high concentrations of metals and metalloids, such as iron, nickel, and arsenic, was collected from the Tab‐Simco coal mine in Carbondale, Illinois. Soil amendment using a 1:1 Al‐ and Ca‐WTR mix, applied at 5 and 10 percent rates significantly lowered the soluble and exchangeable fractions of metals in the AMD‐impacted soil, thus lowering potential metal toxicity. Soil pH increased from an extremely acidic 2.69 to a near‐neutral 6.86 standard units over the 60‐day study period. Results from this preliminary study suggest the possibility of a successful scale‐up of this innovative, cost‐effective, and environmentally sustainable technology for remediating AMD‐impacted acid sulfate soils.     

Neutralization of an extremely acidic sludge and stabilization of heavy metals in flyash aggregates

An extremely acidic, heavy metal-rich sludge (pH=-1.2) was scrubbed with a Class-F fly ash in order to simultaneously neutralize the acidity and stabilize the heavy metals contained in both wastes. This paper outlines the leaching behavior of the aggregate material generated by scrubbing. For proper fly ash/sludge ratios, the fly ash acted as an outstanding neutralizer for the acidic waste. Leaching of heavy metals from the aggregate samples was below the environmental limits within a pH range between 3 and 9. Subsequent washing of the leached aggregate with acidic CALWET solutions did not result in an additional release of heavy metals. It is proposed that coordinative bonding of the metal cations onto neutral surface sites and electrostatic adsorption led to stabilization of the heavy metals within the aggregate structure below hydrolysis pHs.     

Re-cycling of remediated soil - Evaluation of leaching tests as tools for characterization

In Sweden, leaching tests with deionized water (D.W.) are utilized in risk assessment of materials entering landfills, but implementation of these results to evaluate the risk of spreading of pollutants in the environment is difficult. One problem is that most leaching procedures only consider heavy metals release, whereas organic pollutants are left out. The aim of the present study was to assess the possible pollutant mitigation in four remediated soils, three with heavy metals and one with polycyclic aromatic hydrocarbons (PAH) contamination. The mitigation was evaluated by standardized batch and column leaching tests utilizing three different leaching solutions: D.W., a weak ionic solution (0.001 M CaCl₂) and an artificially made soil water (ASW). In general, batch leaching tests implied larger contaminant removal than column leaching test, possibly due to the more rough treatment of the soil particles, and guidelines would at times be exceeded by the batch leaching test but not by column leaching tests. Utilization of CaCl₂ was found to release less heavy metal than D.W., whereas the metals mobilized by ASW were removed from solution by the filtration of soil leachates. Low molecular weight PAH was most efficiently mobilized by CaCl₂, while D.W. worked better for high molecular weight PAH. Despite very low initial PAH-concentrations, tap- and groundwater criteria were exceeded by all leaching solutions.     

Treatment of acid lignite mine flooding water by means of microbial sulfate reduction

During and after mining activities acidic waters containing high amounts of heavy metals and sulfate often occur. In addition to precipitation processes, water purification is also possible with the help of sulfate-reducing bacteria (SRB). A mixed culture of SRB was adapted to methanol as a cheap carbon source. In order to receive high sulfate-reduction rates immobilization on porous materials proved to be advantageous. Continuous laboratory experiments based on immobilized SRB were carried out with original water from a lignite mining site reaching sulfate-reducing rates up to 132 mg SO4(2-)/(1 h). Based on these results a process for the treatment of such waters was designed. Heavy metals are removed by recycling sulfide containing effluent, excess sulfide can be oxidized to elemental sulfur by addition of hydrogen peroxide. The plant with a 3.9 m3 bioreactor with immobilized SRB was constructed at the mine site. This pilot plant was operated successfully for some months. The removal of heavy metals was close to 100%, the pH of the acidic water increased from 3.0 to 6.9. The sulfate-reducing rate again reached 134 mg SO4(2-)/(1 h). The production of sulfur from the excess sulfide is possible.     

Heavy metal leaching from hydroxide, sulphide and silicate stabilised/solidified wastes

A synthetic, mixed-metal solution has been stabilised by treatment with sodium hydroxide, sodium sulphide, and sodium silicate, respectively. The three stabilised filter cakes have subsequently been solidified using additions of ordinary Portland cement and pulverised fuel ash (PFA) which are typically used in UK solidification operations. Both the stabilised filter cakes and the solidified wastes have been subjected to an equilibrium extraction test, a modified TCLP test, and a series of single-extraction, batch leach tests using an increasingly acidic leachant. Metal release was found to be primarily dependent on the pH of the leachate. Under mildly acidic conditions, the percentages leached from the stabilised and the stabilised/solidified wastes were comparable for most metals. A high-volume fraction of these solidified wastes is occupied by the stabilised filter cake. When they are broken up and tested in single-extraction leach tests, the primary effect of the cementitious additives is to increase the pH of the leachate so that most heavy metals remain insoluble. When tested under acidic leachate conditions, copper, lead, and mercury were found to be particularly well retained within sodium sulphide stabilised wastes. Under similar test conditions, cadmium was leached at very low levels from the sodium silicate stabilised waste.     

Remediation of acid mine drainage leachate by a physicochemical and biological treatment‐train approach

Biological and physicochemical approaches were utilized in a treatment train for acid mine dis charge (AMD) waters. Anaerobic bioreactors, chemical precipitation reactors, and biopolymer chelation reactors, operated in static, semicontinuous, and continuous flow modes, removed significant quantities of metals and sulfates associated with AMD water. Static tests indicated accept able copper removal via precipitation by generation of hydrogen sulfide in anaerobic reactors. However, low pH affected the biopolymer coating in the chelation reactor, resulting in loss of bed surface. Corrections of AMD to pH > 7 resulted in some metal precipitationprior to biopolymer treatment. A series of static semicontinuous tests at pH 5.0 provided improved metal and sulfate removal. Copper (Cu⁺) was reduced to trace concentrations, while manganese (Mn⁺), although reduced, proved to be the most recalcitrant of the metals. © 2006 Wiley Periodicals, Inc.     

Relocation of net-acid-generating waste to improve post-mining water chemistry

Acidic drainage and metal leaching are long-term environmental liabilities that can persist for many decades to millennia. One technique to improve the water chemistry and ecology of post-mining landscapes is to relocate and submerge net-acid-generating mine materials in a lake or water-retaining impoundment. One example of a carefully executed relocation of waste rock took place at the Eskay Creek Mine in Canada. Pre-relocation studies included an empirical relationship that related (1) the amount of acidity retained by the waste rock during past oxidation to (2) the amount of lime needed in each truckload for neutralization of the acidity and for suppression of metal release. During relocation, thousands of rinse pH measurements indicated net acidity varied significantly over short distances within the waste rock and that acidic rock could not be reliably segregated from near-netural rock. After relocation, water from the watershed continued to be acidic for a few years, then returned to near-neutral pH and near-background concentrations of metals. The chemistry of the lake where the waste rock was submerged remains near background conditions. Therefore, with careful planning and implementation, the relocation and submergence of net-acid-generating materials can greatly improve post-mining water chemistry.     

Effects of Mine Drainage on Breakdown of Aspen Litter in Mountain Streams

Rates of aspen litter breakdown were measured at 40 sites in streams of the Rocky Mountains of Colorado, U.S.A. The sites encompassed a range of effects of mine drainage, from pristine (no effects) to highly stressed. The pH, concentrations of dissolved zinc, and deposition rates of metal oxides (the three main stresses from mine drainage) were measured in each stream. Rates of litter breakdown were estimated from changes in mass of aspen leaves in litterbags. The biological communities associated with litter breakdown also were evaluated by measuring the biomass of shredding invertebrates in litterbags and the rate of microbial respiration on litter. Of the stresses from mine drainage, concentration of zinc and deposition rate of metal oxides were most closely related (negatively) to rate of litter breakdown. Biomass of shredding invertebrates was also negatively related to concentration of dissolved zinc and deposition of metal oxides. Microbial respiration was negatively related to deposition rate of metal oxides and positively related to concentration of nutrients. Both shredder biomass and microbial respiration were positively related to litter breakdown rate and, together, accounted for 79% of its variation. Recovery of litter breakdown in streams affected by mine drainage requires remediation that limits both dissolved and deposited metals.     

Evaluation of heavy metal leaching from spent household batteries disposed in municipal solid waste

Batch leaching tests and simulated landfill lysimeter tests were performed to evaluate the contents of heavy metals leached from spent batteries in the municipal solid waste. The toxicity characteristic leaching procedure was utilized to perform the batch leaching tests of 36 spent batteries. Four lysimeters were prepared with battery contents ranging from 0% to 100% by weight for column tests, and the experiments were performed at ambient temperature. The age of all the batteries used in the study ranged from freshly disposed up to approximately 3 years old. The results from the batch tests showed that the type of battery influenced the heavy metal concentrations in the leached solutions. The lysimeter experiment results illustrated that at lower pH levels more metals are leached than at higher pH levels. The increasing amount of batteries disposed in landfills can contribute to the leaching of more metals, especially Mn and Zn, into the environment. These results indicate that the direct disposal of spent household batteries into a MSW landfill can increase the heavy metal contents in the landfill leachate.     

Microbial Activity in Relation to Small Scale Patterns of Heavy Metals and Substrate Quality in Spruce Mor Layers (Of) in Southern Sweden

The within-site correlations between soil respiration rates,lead (Pb), mercury (Hg) and cadmium (Cd) concentrations andorganic matter quality variables were investigated at four sites in southern Sweden. The aim was to study whether the within-site variation in heavy metal concentrations could beused to monitor biological effects of regional deposition of heavy metals. Two sites in the south-west, one in the mid-southof the country, and one in south-east were investigated. At the south-eastern, least contaminated, site there were no correlations between soil respiration rate, and either organicmatter quality variables or heavy metal concentrations. At the remaining sites, negative correlations were found between Pb andsoil respiration rate. However, at two of these three sites there was a covariation with cellulose that could account for these correlations. The within-site variation of pH and total nitrogen (N) was low, and did not show any correlative general trends with either respiration rate or heavy metals. Meta analysis showed that negative correlations between Pb or Hg, on the one hand, and cellulose or hemicellulose on the other weregenerally found in within-site investigations. However, this does not necessarily explain the correlation between Pb and soil respiration, as was shown for the southernmost site. A PLS model of soil respiration rates at this site, using allmeasured variables, including heavy metals, explained more variation than a model developed using only mor layer thickness,pH, carbohydrate, ash and nitrogen concentrations, as independent variables. Thus there is a risk of toxic effects from Pb even at the levels found in south-western Sweden today(>120 g Pb * g dw^-1). However, since the correlationsbetween heavy metals and cellulose were not significantly different at the different sites, random sampling variation could not be ruled out as an explanation of the different results for the different sites. The causes of the correlationbetween organic matter quality and heavy metals have not yet been clarified. Analysis of mor samples incubated in thelaboratory for 2 yr with 1200 g Pb * g dw^-1 or 5 gHg * g dw^-1 did not show any differences in carbohydrate composition, compared to control samples. This shows that within-site studies of correlations between respiration rate and heavy metals have to be combined with studies of metal additions to soils and analysis of organic matter quality beforeany valid conclusions can be made.     

Leachability of automotive shredder residues burned in a fluidized bed system

This paper presents the results of the study of a combustible fraction of automotive shredder residues (CASRs) and the corresponding ashes generated by combustion on a fluidized bed pilot with the aim to understand the influence of thermal treatment regarding properties for final disposal, such as landfilling. The chemical composition was evaluated and the leachability behaviour of ashes and CASR was investigated using the three more commonly used tests: the European Standard EN 12457, the US TCLP-EPA 1311 and the Dutch availability test EA NEN 7371. Different results were obtained depending on the specific conditions of the methods employed. It was found that both the CASR and the ashes contained large amounts of toxic metals and other undesirable elements, such as Cl and S. For the CASR, in addition to the leachability of organic matter above the limit set for hazardous materials, the release of heavy metals, either under alkaline and acidic conditions was significant, revealing the serious risks associated to the landfilling practices still being undertaken worldwide. Release of organic matter from ashes was insignificant, but solubility of sulphates increased and chlorides exceed the hazardous limits in the case of fly ashes. Toxic metals were found to leach from the ashes only under acidic conditions, except Pb and Cu which also leached from finer ashes at alkaline pH. Cr also leached from ashes at alkaline pH values. Both the Dutch availability and TCLP revealed much higher leaching intensities than the European Standard due to the acidity of leachants. However, it was found that ashes may be more resistant to acidification because they exhibit much higher acid neutralization capacity (ANC) than the untreated CASR. The study undertaken shows that thermal valorisation of the combustible fraction of ASR may avoid the risks associated with their landfilling; however, care has to be taken with the ashes because they also behave as hazardous residues. Although, the mass reduction provided by thermal treatment may make landfilling less expensive, a more profitable reutilization of the ashes should be developed.     

Potential use of lignite fly ash for the control of acid generation from sulphidic wastes

In the present paper, the potential use of lignite fly ash in the control of acid generation from sulphidic tailings disposed of at Lavrion, Greece was studied. Long-term laboratory column kinetic tests were performed on tailings containing 27% S, which were homogeneously mixed with various amounts of fly ash, ranging from 10 to 63% w/w. The drainage quality of the columns was monitored over a test period of 600 days. Chemical and mineralogical characterisation of column solid residues was performed after a 270-day test period. The hydraulic conductivity of the mixtures was also measured to evaluate the potential of fly ash to form a low permeability layer. Based on the results, the addition of fly ash to sulphidic tailings, even at the lower amount, increased the pH of the drainage at values of 8.6-10.0 and decreased the dissolved concentrations of contaminants, mainly Zn and Mn, to values that meet the European regulatory limits for potable water. Higher fly ash addition to tailings, at amounts of 31 and 63% w/w also reduced the water permeability of material from 1.2 x 10(-5) cm/sec to 3 x 10(-7) and 2.5 x 10(-8) m/s, respectively.     

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.     

分步沉淀法处理酸性矿山废水

采用分步沉淀工艺处理酸性矿山废水,考察了工艺条件对废水中有价金属元素回收效果的影响。实验结果表明:Ca(OH)_2为适宜的废水pH调节剂;调节废水pH至4.00左右并投加0.05 mL/L的H_2O_2,可首先去除Fe~(2+)及Fe~(3+),得到富Fe渣(w(Fe)=51.00%);调节废水pH至6.00~6.50,先投加50 mg/L的Na_2S,去除废水中的Cu~(2+),获得富Cu渣(w(Cu)=10.89%),再将Na_2S的投加量增至100 mg/L,去除废水中的Zn与Mn,获得富Zn-Mn渣(w(Cu)=2.37%,w(Mn)=6.79%,w(Pb)=1.61%);进一步调节废水pH至8.40,可去除剩余的Zn、Mn及其他重金属。分步沉淀工艺处理后的废水可达标排放,产生的富Fe渣、富Cu渣及富Zn-Mn渣可直接出售或具有利用价值。分步沉淀工艺可实现有价金属元素的高效回收,大幅度降低废水处理的实际成本,值得工程应用与推广。     

Evaluation of leaching and extraction procedures for soil and waste

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.     

交联阳离子淀粉的合成及其对重金属离子的吸附

通过正交实验合成了取代度为0．568的交联阳离子淀粉。考察了溶液pH、螯合剂用量、重金属离子初始浓度对交联阳离子淀粉去除重金属离子效果的影响。当重金属离子初始质量浓度为50mg／L、螯合剂投加量为0．5g／U时,Pb^2 ,Cu^2 ,Cr^3 在溶液pH为6时的去除率达到最高,分别为97．94％,99．46％,84．30％,而Cd^ 在溶液pH为7时的去除率达到最高,为99．36％。实验结果表明,交联阳离子淀粉是一种有效去除废水中重金属的处理剂。     

Passive Treatment Alternatives for Remediating Abandoned‐Mine Drainage

Abandoned‐mine drainage (AMD) is drainage flowing from or caused by surface mining, deep mining, or coal refuse piles that is typically highly acidic with elevated levels of dissolved metals. AMD results from the interactions of certain sulfide minerals with oxygen, water, and bacteria. Passive treatment systems have been used to remediate AMD at numerous sites throughout the United States. The theory behind passive treatment is to allow naturally occurring chemical, biological, and physical reactions that aid in AMD treatment to occur in the controlled environment of the system, not in the receiving water body. The advantages of passive treatment over active treatment include lower operation and maintenance costs, virtually no use of chemicals, and minimal energy consumption. The disadvantages are that smaller volumes of water are treated than with active systems, and discharges with high concentrations of dissolved metals and extremes of pH may have to be treated several times within one system to treat the discharge. AMD passive treatment systems include aerobic treatment systems and anaerobic treatment systems. It is estimated that it will take 50 years and between $5 billion and $15 billion to remediate all AMD problems in Pennsylvania. © 2001 John Wiley & Sons, Inc.     

Application of risk management techniques for the remediation of an old mining site in Greece

This article summarizes the project and risk management of a remediation/reclamation project in Lavrion, Greece. In Thoricos the disposal of mining and metallurgical wastes in the past resulted in the contamination with heavy metals and acid mine drainage. The objective of this reclamation project was to transform this coastal zone from a contaminated site to an area suitable for recreation purposes. A separate risk assessment study was performed to provide the basis of determining the relevant environmental contamination and to rate the alternative remedial schemes involved. The study used both existing data available from comprehensive studies, as well as newly collected field data. For considering environmental risk, the isolation and minimization of risk option was selected, and a reclamation scheme, based on environmental criteria, was applied which was comprised of in situ neutralization, stabilization and cover of the potentially acid generating wastes and contaminated soils with a low permeability geochemical barrier. Additional measures were specifically applied in the areas where highly sulphidic wastes existed constituting active acid generation sources, which included the encapsulation of wastes in HDPE liners installed on clay layers.     

复合重金属污染高岭土的电动修复

根据电子废弃物拆解场地的污染特征,以复合重金属(Cu,Cd,Pb)污染高岭土为研究对象,考察了电动技术对污染土壤的修复效果。实验结果表明:在电压梯度为1 V/cm、阳极液为自来水、阴极液为柠檬酸-柠檬酸钠缓冲液(pH=5)、靠近阴极设置活性炭渗透反应墙(PRB)的条件下电动修复96 h后,Cu,Cd,Pb的平均去除率分别可达79.93%,99.43%,39.36%;土壤的酸碱性对电动修复效果影响显著,通过在阴极添加缓冲液维持土壤偏酸性条件,有利于重金属污染物的电动去除;在靠近阴极设置活性炭PRB可富集重金属,减少阴极液的污染;迁移率大的酸可提取态重金属较易去除,残渣态重金属稳定性强,去除率较低。     

Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 °C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.