Remediation of acid mine drainage

Environmental Chemistry Letters - Acid mine drainage induced by the mining industry causes environmental and economic issues. Acid mine drainage contains mainly metals such as Fe, Al, Cu, Ca, Mg,...     

Extraction of Co,Ni, Cu,Zn and Cd ions using 2-aminophenylaminopropylpolysiloxane

Insoluble porous solid functionalized ligand system bearing 2-aminophenylaminopropyl chelating ligand of the general formula P–(CH₂)₃NH–(C₆H₄)–NH₂ was prepared via the sol–gel process, where P represents [Si–O] _n polysiloxane network. First, the 2-aminophenylaminopropylsilane agent was prepared by substitution reaction between 3-chloropropyltrimethoxysilane and 1,2-phenylenediamine, followed by hydrolytic polycondensation between 2-aminophenylaminopropylsilane agent and tetraethylorthosilicate(TEOS). The immobilized 2-aminophenylaminopropylpolysiloxane P–(CH₂)₃NH–(C₆H₄)–NH₂(P–AphA) was characterized by ¹³C NMR, XPS, and FTIR. The results showed that 1,2-phenylenediamine groups were introduced onto polysiloxane network. The functionalized ligand system exhibits 90–100% metal uptake capacity for all metal ions except Cd²⁺. The elemental analysis data and the metal uptake capacities of the immobilized ligand system suggest that over than 90% ligand sites were involved in coordination with metal ions except that of cadmium forming 1:1 metal to ligand ratio complexes.     

Electro-remediation of tailings from a multi-metal sulphide mine: comparing removal efficiencies of Pb,Zn, Cu and Cd

Sulphidic mine tailings characterised by high concentrations of heavy metals (Pb 3532?±?97?mg/kg, Zn 8450?±?154?mg/kg, Cu 239?±?18?mg/kg and Cd 14.1?±?0.3?mg/kg) and abundant carbonate (17%) were subjected to eight lab-scale electrodialytic remediation (EDR) experiments to investigate the influence of current density, treatment time and particle size on removal efficiency. Pb and Cu removal improved when increasing current density, while Zn and Cd removal did not. In contrast Zn and Cd removal improved by grinding the tailings, while Pb and Cu removal did not. At the highest current density (1.2?mA/cm²), 94%, 75%, 71% and 67% removal of Pb, Zn, Cu and Cd could be achieved, respectively, on grinded tailings in 28 days. Sequential chemical extraction made before and after EDR revealed larger oxidisable fractions of Zn, Cu and Cd, representing large fractions of sulphides, which was likely to be the main barrier to be removed as efficiently as Pb. This was in accordance with acid/base extraction tests in which Pb showed high solubility at both high and low pH (up to 65% and 86% of extraction, respectively), while considerable extraction of Zn (55%) happened only at low pH; and very limited extraction (<20%) of Cu and Cd occurred at any pH.     

Human bioaccessibility of Cr, Cu, Ni, Pb and Zn in urban soils from the city of Torino, Italy

Several physiologically based extraction procedures have been proposed to estimate the fraction of the potentially toxic element content that would be bioaccessible in the human gastro-intestinal tract following accidental ingestion of soil. Many of these procedures are complex, they have been applied to a very limited range of soils, and most work has focussed on arsenic and lead. In the present study, a simplified, two-stage extraction, simulating the human stomach and intestine, was developed and applied to urban soil samples from ten public-access areas in the City of Torino, Italy. The human oral bioaccessibility of chromium, copper, nickel, lead and zinc was estimated. Lead and zinc bioaccessibilities were found to be higher in the stomach, but chromium was more bioaccessible in the intestine. Analyte concentrations were higher in roadside soils than in soils from parks. A higher proportion of the soil metal content was found in bioaccessible forms at roadsides than in parks. Comparison of the current findings with results of earlier work involving sequential extraction of the same soils indicated that the sequential procedure gave a relative, but not an absolute, indication of bioaccessibility. Calculations based on the bioaccessible analyte concentrations suggest that ingestion of only 2–3 g of some of the roadside soil samples from Torino could deliver the tolerable daily oral intake of chromium, nickel and lead to a 20-kg child. The developed procedure is useful for preliminary screening of soils and prediction of whether their bioaccessible metal contents are likely to pose a risk to human health.     

电镀废水中铜锌铬镍对农业环境的影响

电镀废水排入河涌会污染农业环境。以广东省南 海市平洲地区为例,农田灌溉水中Ｃｕ、Ｚｎ、Ｎｉ的含量超过允许限值１ ～１４ 倍,河涌底泥Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ超标１２ ～３７倍,土壤超标０．５ ～２．９倍,作物超标０．３ ～８ 倍。进入河涌的Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ能较快沉积于底泥中。进入土壤的Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ主要累积在耕作层中。作物对Ｃｕ、Ｚｎ 的吸收能力远远高于对Ｃｒ、Ｎｉ的吸收能力,作物吸收系数是Ｚｎ ＞ Ｃｕ ＞ Ｎｉ＞ Ｃｒ     

矿区污染土壤Pb、Cd、Cu和Zn的形态分布及其生物活性的研究

调查湘南某铅锌矿区周围的菜园土和水稻土Pb、Cd、Cu和Zn的形态分布及其生物活性和迁移性。结果表明:两种土壤中Pb、Cd、Cu和Zn的总量分别超过国家土壤环境质量相应的标准。运用Tessier连续提取法研究发现,土壤中Pb、Cd、Cu和Zn的各形态含量之和与其总量非常的接近,其中菜园土Pb的提取率为96.3%,Cd的为94.1%,Cu的为93.4%和Zn的为91.7%;水稻土Pb的为97.6%,Cd的为92.0%,Cu的为92.1%和Zn的为91.7%,表明该形态分析方法的结果是合理的。土壤中Pb、Cd、Cu和Zn各形态的分布存在很大的差别,残渣态是主要形态,其中Pb的含量占60.7%~58.2%,Cd的是50.4%~59.2%,Cu的是37.3%~53.4%,Zn的是54.9%~46.9%,而交换态所占的比例最小。菜园土重金属的生物活性系数的大小是:Cd>Cu>Pb>Zn,迁移能力的顺序是Cd>Cu>Zn>Pb;水稻土重金属的活性大小和迁移能力的顺序都是:Cd>Pb>Zn>Cu。菜园土重金属的生物活性和迁移性较水稻土的大,其中Cd的生物活性和迁移性的最大。研究结果将为评估矿区污染土壤中重金属的危害提供科学依据。     

Modelling the potential mobility of Cd,Cu, Ni,Pb and Zn in Mollic Fluvisols

European floodplain soils are frequently contaminated with potentially toxic inorganic substances. We used a multi-surface model to estimate the aqueous concentrations of Cd, Cu, Ni, Pb and Zn in three Mollic Fluvisols from the Central Elbe River (Germany). The model considered complexation in solution and interactions with soil organic matter (SOM), a clay mineral and hydrous Al, Fe and Mn oxides. The amounts of reactive metals were derived from extraction with 0.43 M HNO₃. Modelling was carried out as a function of pH (soil pH ± 1.4) because it varies in floodplain soils owing to redox processes that consume or release protons. The fraction of reactive metals, which were dissolved according to the modelling, was predominantly <1%. Depending on soil properties, especially pH and contents of SOM and minerals of the clay fraction, the modelled concentrations partially exceeded the trigger values for the soil–groundwater pathway of the German soil legislation. This differentiation by soil properties was given for Ni, Pb and Zn. On the other hand, Cd was more mobile, i.e., the trigger values were mostly exceeded. Copper represented the opposite, as the modelling did not predict exceeding the trigger values in any horizon. Except for Pb and partially Zn (where oxides were more important), SOM was the most important adsorbent for metals. However, given the special composition and dynamics of SOM in mollic horizons, we suggest further quantitative and qualitative investigations on SOM and on its interaction with metals to improve the prediction of contaminant dynamics.     

Zn,Cu和Ni污染土壤中重金属的化学固定

利用化学固定剂处理被污泥中Zn,Cu和Ni污染的土壤,研究不同化学药剂对重金属离子的固定技术.结果表明,石灰、硫化物和硅酸盐对Zn都有较好的稳定效果,硫化物对Cu的稳定效果较好,硅酸盐和石灰对Ni的稳定效果较好;对于被Zn,Cu和Ni污染的土壤,混合药剂对重金属污染物的固定效果最佳.研究表明通过调解系统的pH和生成稳定化合物形态使土壤中Zn,Cu和Ni得以固定.通过硫化物 石灰化学固定处理,固定前后Zn,Cu和Ni的不稳定形态含量分别减少了69%,56%和59%.     

Human risk assessment of As,Cd, Cu and Zn in the abandoned metal mine site

The cancer risk and the non-cancer hazard index for inhabitants exposed to As, Cd, Cu and Zn in the soils and stream waters of the abandoned Songcheon Au–Ag mine area were evaluated. Mean concentrations of As, Cd, Cu, Pb and Zn in agricultural soils were 230, 2.5, 120, 160, and 164 mg kg⁻¹, respectively. Mean concentrations of As, Cd and Zn of the water in the stream where drinking water was drawn was 246 μg L⁻¹, 161 μg L⁻¹ and 3899 μg L⁻¹, respectively. These levels are significantly higher than the permissible levels for drinking water quality recommended by Korea and WHO. The resulting human health risks to farmers who inhabited the surrounding areas due to drinking water were summarized as follows: (1) the non-cancer health hazard indices showed that the toxic risk due to As and Cd in drinking water were 10 and 4 times, respectively, greater than those induced by the safe average daily dosages of the respective chemicals. (2) the cancer risk of As for exposed individuals through the drinking water pathway was 5 in 1000, exceeded the acceptable risk of 1 in 10,000 set for regulatory purposes.     

Contamination by Cd, Cu, Pb, and Zn in mine wastes from abandoned metal mines classified as mineralization types in Korea

The objective of this study was to investigate heavy metal contamination and geochemical characteristics of mine wastes, including tailings, from 38 abandoned mines classified as five mineralization types. Mine waste materials including tailings and soils were sampled from the mines and the physical and chemical characteristics of the samples were analyzed. The particle size of tailings was in the range of 10–100 μm. The pH of the waste covered a wide range, from 1.73 to 8.11, and was influenced by associated minerals and elevated levels of Cd, Cu, Pb, and Zn, extracted by a Korean Standard Method (digestion with 0.1 mol L⁻¹ HCl), which were found in the wastes. Half of the samples contained heavy metals at levels above those stipulated by the Soil Environmental Conservation Act (SECA) in Korea. In addition, extremely high concentrations of the metals were also found in mine wastes extracted by aqua regia, especially those from mines associated with sulfide minerals. Thus, it can be expected that trace elements in mine wastes may be dispersed both downstream and downslope through water and wind. Eventually they may pose a potential health risk to residents in the vicinity of the mine. It is necessary to control mine wastes by using a proper method for their reclamation, such as neutralization of the mine wastes using a fine-grained limestone.     

Adsorptive removal of mercury from acid mine drainage: a comparison of silica and maghemite nanoparticles

Mercury adsorption by silica and maghemite nanoparticles (NPs) was studied with the aim of comparing their performance in the remediation of acid mine drainage (AMD) contaminated water. Calculated distribution coefficients (K_d) showed that both NPs are exceptional adsorbents. However, adsorbate coverage per unit area was 30 times higher for maghemite than for silica NPs, despite the latter having a surface area ～15 times greater. Maghemite adsorbed 75% of available Hg compared to 56% by silica, making it a more efficient sorbent than silica under AMD conditions. Kinetics and isotherm data for both adsorbents were fitted by the pseudo-second-order (R² = 1) and the Freundlich (R² ≥ 0.98) models, implying that adsorption to both NP types was by chemisorption. Adsorption increased with NP concentrations and pH and was enhanced in the presence of manganese and sulfate ions although adsorption to silica was inhibited in 1:2 Hg-to-Mn systems. Importantly, trends in simulated wastewater were replicated in actual AMD-contaminated water samples. This study highlights the fact that properties besides surface area and charge of adsorbents determine adsorbent performance, and superior attributes may not always lead to higher adsorption efficiencies.     

The non-participation of organic sulphur in acid mine drainage generation

Acid mine drainage is commonly associated with land disturbances that encounter and expose iron sulphides to oxidising atmospheric conditions. The attendant acidic conditions solubilise a host of trace metals. Within this flow regime the potential exists to contaminate surface drinking water supplies with a variety of trace materials. Accordingly, in evaluating the applications for mines located in the headwaters of water sheds, the pre-mining prediction of the occurrence of acid mine drainage is of paramount importance.There is general agreement among investigators that coal organic sulphur is a nonparticipant in acid mine drainage generation; however, there is no scientific documentation to support this concensus. Using simulated weathering, kinetic, mass balance, petrographic analysis and a peroxide oxidation procedure, coal organic sulphur is shown to be a nonparticipant in acid mine drainage generation. Calculations for assessing the acid-generating potential of a sedimentary rock should not include organic sulphur content.     

大宝山矿水外排的环境影响:Ⅱ.农业生态系统

大宝山外排酸性矿水对周边农村地区农业生态系统具严重的负面影响，表现在：农田所用的灌溉水酸度很强，灌溉水中多种重金属含量高于国家农田灌溉水质标准，其中Cd超标约16倍；土壤严重酸化，pH值可低至3．9，总实际酸度平均达47mmol／kg，比水溶性酸度高147倍，表明由矿水带进土壤的无机酸通过土壤的缓冲作用暂时转化为非水溶态并在土壤中累积；土壤重金属含量超标，以Zn、Cu和Cd为甚；粮食和果蔬等作物重金属污染严重，其中尤以Cd最为突出，最高可超标近150倍。     

Modelling the concentrations of dissolved contaminants (Cd,Cu, Ni,Pb, Zn) in floodplain soils

Central European floodplain soils are often contaminated with potentially toxic metals. The prediction of their aqueous concentrations is a prerequisite for an assessment of environmental concerns. We tested the aqueous concentrations of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) derived from multi-surface adsorption modelling (on hydrous iron, aluminum and manganese oxides, clay and soil organic matter) against those analyzed in situ in the soil solution of four horizons of floodplain soils at the Elbe River, Germany. The input data for the reactive metals were derived from a seven-step sequential extraction scheme or from extraction with 0.43 M nitric acid (HNO₃) and evaluated in four modelling scenarios. In all scenarios, measured and modelled concentrations were positively related, except partially for Pb. Close reproduction of the measured data was obtained using measured data of accompanying cations and anions together with amounts of reactive metals from both the sequential extraction or from 0.43 M HNO₃ extraction, except for Cu, which was often strongly overestimated, and partially Cd. We recommend extraction with 0.43 M HNO₃ to quantify reactive metals in soil because the modelling results were metal-specific with better or equal results using the single extractant, the application of which is also less laborious. Approximations of ion concentrations and water contents yielded similar results. Modelled solid-phase speciation of metals varied with pH and differed from that from sequential extraction. Multi-surface modelling may be an effective tool to predict both aqueous concentrations and solid-phase speciation of metals in soil.     

Acid mine drainage from inactive eastern coal operations

The most widely used technique for abatement of acid drainage from inactive surface mines and refuse disposal areas is revegetation of a soil cover applied to the waste material. Nonetheless, acid production often persists and in some cases, limits establishment of vegetation. This paper reports on several field studies intended to determine the location of pyrite oxidation zones and migration pathways of oxidation products at inactive spoil and refuse sites.Oxygen required for pyrite oxidation is believed to he provided in the gaseous state from the atmosphere. Therefore, the oxygen concentration in unsaturated mine waste should provide an estimate of the weathering tendency in the local environment. We are currently monitoring gas composition in refuse and spoil at six sites. Barren refuse appeared to be oxygenated (>2% 0₂) in a shallow zone extending less than 1 metre below the surface during most of the year. Preliminary data from coal spoil showed that oxygen can be available throughout the unsaturated thickness, even at a revegetated site. Gas composition varied vertically and laterally at a single site and also appeared to show seasonal dependence.Hydrologic factors are also important in acid production and transport. Discharge monitoring alone does not adequately describe the mass transport of acid products through the spoil. For example, at one reclaimed mine the mean sulfate content in six monitoring wells ranged from 24% to 240% of the mean concentration at the discharge point. Sources of recharge and relative flow rates determine the contribution of a particular zone to overall discharge quality.These basic studies of acid production and transport indicate some shortcomings of standard reclamation practices at certain sites. This information will he used to develop alternative abatement technology designed to mitigate acid production at the source.     

Acid mine drainage from inactive eastern coal operations

The most widely used technique for abatement of acid drainage from inactive surface mines and refuse disposal areas is revegetation of a soil cover applied to the waste material. Nonetheless, acid production often persists and in some cases, limits establishment of vegetation. This paper reports on several field studies intended to determine the location of pyrite oxidation zones and migration pathways of oxidation products at inactive spoil and refuse sites. Oxygen required for pyrite oxidation is believed to he provided in the gaseous state from the atmosphere. Therefore, the oxygen concentration in unsaturated mine waste should provide an estimate of the weathering tendency in the local environment. We are currently monitoring gas composition in refuse and spoil at six sites. Barren refuse appeared to be oxygenated (>2% 0₂) in a shallow zone extending less than 1 metre below the surface during most of the year. Preliminary data from coal spoil showed that oxygen can be available throughout the unsaturated thickness, even at a revegetated site. Gas composition varied vertically and laterally at a single site and also appeared to show seasonal dependence. Hydrologic factors are also important in acid production and transport. Discharge monitoring alone does not adequately describe the mass transport of acid products through the spoil. For example, at one reclaimed mine the mean sulfate content in six monitoring wells ranged from 24% to 240% of the mean concentration at the discharge point. Sources of recharge and relative flow rates determine the contribution of a particular zone to overall discharge quality. These basic studies of acid production and transport indicate some shortcomings of standard reclamation practices at certain sites. This information will he used to develop alternative abatement technology designed to mitigate acid production at the source.     

金昌市郊农田土壤Cu,Zn,Ni形态分布特征与生物有效性评价

通过野外调查和室内测试分析,研究了金昌市郊农田土壤重金属Cu,Zn和Ni的形态特征,并以麦粒中重金属含量为重点进行了Cu,Zn和Ni的生物有效性评价.结果表明,研究区域土壤重金属Cu和Ni污染严重;Cu的主要存在形态为有机结合态,Zn的主要存在形态为残渣态,而Ni的主要存在形态为潜在可利用态;三种元素的生物有效性大小顺序为NiZnCu.对麦粒中重金属健康风险进行评价反映出麦粒中Ni含量对人体健康风险较大,而Cu和Zn对人体健康风险较小.逐步回归分析结果表明,农田土壤中Cu可交换态和碳酸盐结合态对麦粒中Cu含量贡献最大,而对麦粒吸收Zn和Ni贡献最大的形态分别为Zn的碳酸盐结合态和Ni的可交换态、碳酸盐结合态、铁锰氧化态和有机结合态.土壤重金属Cu,Zn和Ni各形态分配系数较总量和各形态含量更适合表征本研究区域土壤重金属的生物有效性.     

大宝山矿水外排的环境影响:Ⅲ.综合治理对策

大宝山外排酸性矿水对下游水生生态系统及周边农村地区农业生态系统带来严重影响，并可能已危及当地人民的健康。文章根据大宝山矿所在地区的实际情况，对大宝山矿区及周围地区生态退化和环境污染的综合治理途径进行探讨，提出：(1)必须走系统整治的路径才能做到既治标又治本；(2)治理污染源是整个治理方案的关键环节；(3)为了使深受污染之害的矿区周边人民尽快脱离危险，近期最迫切的治理地段是受矿水严重污染的农田，尤其是重污染区一上坝村；(4)在治理方法上，必须将化学治理、生物治理与工程治理相结合；(5)为了更好地实施各项治理工程，可考虑运用经济杠杆，以便有效地筹集足够的矿山治理资金；(6)着眼于未来更严格的环境质量标准，建立水质的生物预警系统；(7)目前制约大宝山矿地区生态环境治理的主要瓶颈之一是缺乏适合中国国情的高效低投入治理技术，政府应考虑提供研究经费支持相关的应用基础研究和技术开发，以便能加快治理的步伐。     

大宝山矿水外排的环境影响:Ⅰ.下游水生生态系统

通过水质生物检测、理化分析及野外水生大型无脊椎动物多样性实地调查等综合方法，就广东大宝山矿区南侧拦泥库溢出的酸性矿水对下游横石水河生态系统的影响进行了系统研究。结果表明，大宝山矿区拦泥库溢出的酸性矿水对隆线溞具有较强的急性生物毒性，酸性矿水24h，48h及96h对水溞的半致死体积分数LC50分别为13．55%、10．30％、6．20％；安全体积分数为0．06％。通过在暴雨期间对拦泥库上游洪水的各项指标的分析结果表明，拦泥库溢出的酸性矿水pH值可低至2．15，其中铁及重金属的质量浓度分别为：铁216．79mg/L、锌73．23mg/L、铜32．63mg/L、铅1．82mg/L、镉0．87mg/L。在尾矿坝下游3．5km处，重金属质量浓度分别为：铁51．63mg／L、锌2．83mg/L；铜1．64mg／L、铅2．67mg／L、镉0．1mg／L，和锰20．50mg／L。从矿水排放口到受矿水影响的下游50km范围内，河水pH的变化幅度为3．36-7．42。大型无脊椎动物多样性的调查显示，从尾矿坝到受矿水影响的下游25km范围内，未发现任何底栖动物，而在横石水河上游未受矿水影响的对照点中至少有36利底栖动物存在。可见由大宝山矿区排出的酸性矿水对下游溪流的水生生物多样性和河流生态系统造成了严重的破坏。     

Potential application of sludge produced from coal mine drainage treatment for removing Zn(II) in an aqueous phase

Various analyses of physico-chemical characteristics and batch tests were conducted with the sludge obtained from a full-scale electrolysis facility for treating coal mine drainage in order to find the applicability of sludge as a material for removing Zn(II) in an aqueous phase. The physico-chemical analysis results indicated that coal mine drainage sludge (CMDS) had a high specific surface area and also satisfied the standard of toxicity characteristic leaching procedure (TCLP) because the extracted concentrations of certain toxic elements such as Pb, Cu, As, Hg, Zn, and Ni were much less than their regulatory limits. The results of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that the CMDS mainly consists of goethite (70%) and calcite (30%) as a weight basis. However, the zeta potential analysis represented that the CMDS had a lower isoelectric point of pH (pH(IEP)) than that of goethite or calcite. This might have been caused by the complexation of negatively charged anions, especially sulfate, which usually exists with a high concentration in coal mine drainage. The results of Fourier transform infrared (FT-IR) spectrometry analysis revealed that Zn(II) was dominantly removed as a form of precipitation by calcite, such as smithsonite [ZnCO?] or hydrozincite [Zn?(CO?)?(OH)?]. Recycling sludge, originally a waste material, for the removal process of Zn(II), as well as other heavy metals, could be beneficial due to its high and speedy removal capability and low economic costs.