Ecological restoration of mine degraded soils,with emphasis on metal contaminated soils

This paper reviews the ecological aspects of mined soil restoration, with special emphasis on maintaining a long-term sustainable vegetation on toxic metal mine sites. The metal mined soils are man-made habitats which are very unstable and will become sources of air and water pollution. Establishment of a vegetation cover is essential to stabilize the bare area and to minimize the pollution problem. In addition to remediate the adverse physical and chemical properties of the sites, the choice of appropriate vegetation will be important. Phytostabilization and phytoextraction are two common phytoremediation techniques in treating metal-contaminated soils, for stabilizing toxic mine spoils, and the removal of toxic metals from the spoils respectively. Soil amendments should be added to aid stabilizing mine spoils, and to enhance metal uptake accordingly.     

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.     

Effect of coal mine soil contamination on the elemental uptake and distribution in two edible Amaranthus species, A. dubius and A. hybridus

The impact of coal mine dump contaminated soil on the elemental uptake by two edible plants, namely, Amaranthus dubius (red herbs) and Amaranthus hybridus (green herbs), was studied by investigating their response and ability to tolerate and accumulate varying levels of elements in their roots and shoots. The vegetation was grown on varying amounts of contaminated soil, viz. 0%, 5%, 15%, 25% w/w using coal mine dump soil. The soil was analyzed for soil pH, cation exchange capacity (CEC), soil organic matter (SOM), moisture content, and selected heavy metals. The distribution of six metals, namely, Pb, Cd, Hg, Ni, Mn, and Fe, in roots, stem, and leaves of the plants was determined in two stages of growth after 5 weeks and 10 weeks. All soil and plant samples were microwave digested and subjected to heavy metal analysis using the ICP-OES, GFAAS, and CVAAS. The pH of the coal mine dump contaminated soil decreased with an increase in contamination. Both the SOM and CEC values decreased, which increases the availability of elements, by providing more binding sites in the soil. Relatively, the red herbs had higher elemental concentrations than the green herbs. Both plants recorded high manganese accumulation. No mercury was detected in the soils or plants.     

磁黄铁矿氧化机理及酸性矿山废水防治的研究进展

磁黄铁矿是矿山尾矿堆中最为常见且分布很广的一种硫化铁矿物.由于硫化物矿物氧化后不仅产生酸性废水,还会释放出大量可溶的、生物可利用形态的微量金属,并且酸性环境会进一步增强这些有毒金属的移动性,因此是造成矿山周围水体环境污染的罪魁祸首.为了阻止或降低磁黄铁矿的自然风化反应速度从而达到源头治理酸性矿山废水的目的,首先必须研究它在各种条件下的氧化机理、氧化产物和氧化速度.对近年来国外在磁黄铁矿晶体结构、反应活性以及酸性矿山废水的产生与防治等方面的研究进行了综述.     

Mobility of heavy metals as related to soil chemical and mineralogical characteristics of Brazilian soils

In order to better understand the relationship between soil characteristics and mobility of some heavy metals, correlation studies were conducted in samples of unlimed and limed A, B and C horizons of three Brazilian soils, representative of the majority of the tropical soils. A number of chemical and mineralogical characteristics of one Oxisol and two Ultisols were related to the retardation factors (Rf) for zinc (Zn), cadmium (Cd), copper (Cu) and lead (Pb). The retardation factors, obtained in leaching column experiments, were used as an estimate of solute movement in the profile. Soil types and soil horizons were found to influence metal retardation factors which, in turn, correlated better with the chemical than the mineralogical soil characteristics. For the unlimed soil samples, the soil characteristics that significantly correlated with Zn-Rf and Cd-Rf were the sum of exchangeable bases (SB), and soil exchangeable (Ca-KCl) and non-exchangeable (Ca-HCl) calcium contents. These results showed the strong influence of the cation exchange phenomenon on the retention and mobility of these two metals. For Cu and Pb, not only SB, cation exchange capacity (CEC) and Ca-KCl and Ca-HCl but also the organic matter correlated well with the Rf, showing that complex or chelate formation may play an important role in the movement of these elements. The important soil chemical characteristics related to the retardation factors in the limed soil samples were SB for Cd, and Ca-HCl for Cu and Pb, suggesting that precipitation may also influence the mobility and retention of the latter two heavy metals in these soil samples. Soil pH influenced the heavy metals adsorption and movement as shown by the significant correlation with the retardation factors when the combined data for the unlimed and limed soil samples was considered.     

Heavy metal contamination in water and sediments of an estuary in southeastern Turkey

The geochemical characteristics of some heavy metals (Cr, Cd, Pb, Zn and Ni) in the river and sea sediments, in the soil and in the river and groundwater of an estuary on the southeast coast of Turkey have been studied. In the sea sediments, the wastes from a chromium factory control these metal concentrations. The heavy metal contamination in the river sediments results from an existing chromite mine at the northern part of the area. These heavy metals are concentrated in the soil, but they do not penetrate into the groundwater because of the low permeability of the unsaturated zone in the region.     

城市生活垃圾填埋场渗滤液生化处理过程中重金属离子问题

我国对城市生活填埋场渗滤液处理技术的研究主要集中在COD与NH4 -N的去除上,对渗滤液中重金属离子的专项研究几乎未见报道.本文首先总结了国内外城市生活垃圾渗滤液中重金属的种类及浓度,在渗滤液中的存在状态,渗滤液中重金属与其他成分(有机物、氨氮)的相互作用关系,辨证分析了重金属在渗滤液生化处理过程中的有益作用和毒性,归纳了重金属在渗滤液生化处理过程中的变化规律,同时总结分析了重金属的去除技术.     

Effect of Coal Mine Soil Contamination on the Elemental Uptake and Distribution in Two Edible Amaranthus Species,A. dubius and A. hybridus

The impact of coal mine dump contaminated soil on the elemental uptake by two edible plants, namely, Amaranthus dubius (red herbs) and Amaranthus hybridus (green herbs), was studied by investigating their response and ability to tolerate and accumulate varying levels of elements in their roots and shoots. The vegetation was grown on varying amounts of contaminated soil, viz. 0%, 5%, 15%, 25% w/w using coal mine dump soil. The soil was analyzed for soil pH, cation exchange capacity (CEC), soil organic matter (SOM), moisture content, and selected heavy metals. The distribution of six metals, namely, Pb, Cd, Hg, Ni, Mn, and Fe, in roots, stem, and leaves of the plants was determined in two stages of growth after 5 weeks and 10 weeks. All soil and plant samples were microwave digested and subjected to heavy metal analysis using the ICP-OES, GFAAS, and CVAAS. The pH of the coal mine dump contaminated soil decreased with an increase in contamination. Both the SOM and CEC values decreased, which increases the availability of elements, by providing more binding sites in the soil. Relatively, the red herbs had higher elemental concentrations than the green herbs. Both plants recorded high manganese accumulation. No mercury was detected in the soils or plants.     

氧化亚铁硫杆菌对电子垃圾焚烧迹地重金属形态的影响

采用生物淋滤法处理电子垃圾焚烧迹地重金属严重污染的土壤。所用氧化亚铁硫杆菌是从矿坑废水中通过一系列培养、分离和纯化得到。实验结果表明，生物淋滤法可以有效地去除土壤中重金属Cu、Ph和Zn，去除率的大小顺序为Zn〉Cu〉Pb；采用五步连续提取法分析处理前后土壤中重金属的存在形态，结果表明，通过氧化亚铁硫杆菌处理受重金属污染的土壤，可以促使易移动的重金属结合态的溶解（可交换态、碳酸盐结合态和Fe—Mn氧化物结合态），并使难移动的重金属结合态向易移动的重金属结合态转变。     

氧化亚铁硫杆菌对电子垃圾焚烧迹地重金属形态的影响简

采用生物淋滤法处理电子垃圾焚烧迹地重金属严重污染的土壤。所用氧化亚铁硫杆菌是从矿坑废水中通过一系列培养、分离和纯化得到。实验结果表明，生物淋滤法可以有效地去除土壤中重金属Cu、Pb和Zn，去除率的大小顺序为Zn>Cu>Pb；采用五步连续提取法分析处理前后土壤中重金属的存在形态，结果表明，通过氧化亚铁硫杆菌处理受重金属污染的土壤，可以促使易移动的重金属结合态的溶解（可交换态、碳酸盐结合态和Fe-Mn氧化物结合态），并使难移动的重金属结合态向易移动的重金属结合态转变。     

Heavy metal accumulation, heat shock protein expression and cytogenetic changes in Tetrix tenuicornis (L.) (Tetrigidae, Orthoptera) from polluted areas

The orthopteran insect Tetrix tenuicornis, collected from polluted and unpolluted areas, was used to study heavy metal accumulation and its impact on stress protein levels and on changes in the number and morphology of chromosomes in mitotic and meiotic cells. During two consecutive years, insects were collected from polluted areas of zinc-lead mine spoils near Boles?aw (Poland) and from unpolluted areas near Busko and Staszów (Poland). T. tenuicornis from the polluted area showed 1.5, 4.03, 4.32 and 41.73 times higher concentrations of copper (Cu), zinc (Zn), lead (Pb) and cadmium (Cd), respectively, than insects of the same species collected from unpolluted areas. Insects exposed to heavy metals showed only small changes, and rather a decrease in the concentration of constitutive and inducible heat shock proteins Hsp70, the level of which increases under stress conditions. A cytogenetic study of T. tenuicornis revealed intra-population anomalies in chromosome number and morphology in mitotic and meiotic cells and the presence of an additional B chromosome in germinal cells. In 50% of females collected from polluted areas, mosaic oogonial mitotic chromosome sets and diploid, hypo- or hypertetraploid, tetraploid, and octoploid chromosome numbers were detected. In turn, 14.6% of males showed a heterozygous deficiency of chromatin in L2 and M3 bivalents in addition to the presence of B chromosomes.     

污泥与煤、木屑燃烧过程中重金属排放特性研究

为了考察燃料燃烧过程中重金属的迁移转化规律，对污泥、煤与木屑及其混合物在不同温度下氧气中燃烧灰渣中的重金属元素进行分析。结果表明，燃料中重金属在高温燃烧时表现出不同的挥发特性，大部分元素随着温度的升高挥发率增加，其中Cd、Pb和Zn元素挥发性较强，Cr、Cu和Ni挥发性较弱。污泥与木屑混合燃烧灰渣仍以污泥灰为主，重金属含量与污泥灰相近，污泥中混入煤后使灰中大部分重金属含量有所降低。燃烧过程会改变重金属存在形态，污泥与煤原料中以酸溶态和可还原态存在的重金属含量较高，具有较强的生物有效性和迁移性，而燃烧灰渣中酸溶态和可还原态含量显著下降，混合燃烧灰渣中除As外的其他重金属几乎全部以残渣态存在，其含量达到90％以上，焚烧过程有效降低了燃料灰渣中重金属的生物毒性。     

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.     

Sequential extraction of heavy metals in river sediments of an abandoned pyrite mining area: pollution detection and affinity series

In this paper heavy metal pollution at an abandoned Italian pyrite mine has been investigated by comparing total concentrations and speciation of heavy metals (Fe, Cu, Mn, Zn, Pb and As) in a red mud sample and a river sediment. Acid digestions show that all the investigated heavy metals present larger concentrations in the sediment than in the tailing. A modified Tessier's procedure has been used to discriminate heavy metal bound to organic fraction from those originally present in the mineral sulphide matrix and to detect a possible trend of metal mobilisation from red mud to river sediment. Sequential extractions on bulk and size fractionated samples denote that sediment samples present larger percent concentrations of the investigated heavy metals in the first extractive steps (I-IV) especially in lower dimension size fractionated samples suggesting that heavy metals in the sediment are significantly bound by superficial adsorption mechanisms.     

Assessment of metal availability to vegetation (Betula pendula) in Pb-Zn ore concentrate residues with different features

In this work, characterisation of several ore concentrate remains from an abandoned Pb-Zn mining factory was performed determining chemical and physical properties such as pH, organic carbon content, particle size distribution, total heavy metal content (Pb, Zn, Cu, As and Cd) as well as mineralogical composition which showed, in most cases, the oxidization of the parent ore material (mostly galena: PbS and sphalerite: ZnS) to more mobile fractions as anglesite (PbSO(4)) and goslarite (ZnSO(4)). Moreover, two operational defined extraction procedures commonly used in soil and sediment studies (first and second steps of BCR procedure and DTPA extraction protocol) were applied in the different mining wastes in order to study Pb and Zn mobility and likely bioavailability to Betula pendula growing on the same mining spoils, which presents lead and zinc contents in leaves over ten times background values.     

油页岩循环流化床锅炉底渣和飞灰中重金属元素浸出毒性研究

为了研究我国桦甸油页岩65 t/h循环流化床锅炉的底渣和飞灰中重金属元素Cr、Cu、Pb和Zn的赋存状态及不同酸度条件下的浸出特性,分别进行了逐级提取实验和分批浸出的淋滤实验。逐级提取实验结果表明,这4种元素在底渣和飞灰中具有基本相当的赋存状态。硫化物结合态和稳定的残渣态是各元素的主要赋存状态,元素的潜在浸出能力大小表现为:PbCrCuZn,飞灰中各元素的潜在浸出能力大于底渣中的。浸出实验结果表明,元素的赋存状态决定了其浸提能力,浸提液的pH值对各元素浸出能力的影响不尽相同,各元素的浸出能力随浸提时间的延长都会趋于平衡,Cr和Pb的浸出浓度都高于地表水和饮用水的国家标准。     

Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances

Effective phytoremediation of soils contaminated by heavy metals depends on their availability to plant uptake that, in turn, may be influenced by either the existing soil humus or an exogenous humic matter. We amended an organic and a mineral soil with an exogenous humic acid (HA) in order to enhance the soil organic carbon (SOC) content by 1% and 2%. The treated soils were further enriched with heavy metals (Cu, Pb, Cd, Zn, Ni) to a concentration of 0, 10, 20, and 40 microg/g for each metal and allowed to age at room temperature for 1 and 2 months. After each period, they were extracted for readily soluble and exchangeable (2.5% acetic acid), plant-available (DTPA, Diethylentriaminepentaacetic acid), and occluded (1 N HNO(3)) metal species. Addition of HA generally reduced the extractability of the soluble and exchangeable forms of metals. This effect was directly related to the amount of added HA and increased with ageing time. Conversely, the potentially plant-available metals extracted with DTPA were generally larger with increasing additions of exogenous HA solutions. This was attributed to the formation of metal-humic complexes, which ensured a temporary bioavailability of metals and prevented their rapid transformation into insoluble species. Extractions with 1 N HNO(3) further indicated that the added metals were present in complexes with HA. The observed effects appeared to also depend on the amount of native SOC and its structural changes with ageing. The results suggest that soil amendments with exogenous humic matter may accelerate the phytoremediation of heavy metals from contaminated soil, while concomitantly prevent their environmental mobility.     

Dynamic studies on the mobility of trace elements in soil and sediment samples influenced by dumping of residues of the flood in the Mulde River region in 2002

In the analysis of soil samples, batch sequential extraction procedures are traditionally used for the fractionation of trace elements to access their mobility and potential risk for the contamination of groundwater. In the present work a continuous-flow technique has been used that enables not only the fast and efficient leaching of trace elements but as well as time-resolved studies on the mobilization of arsenic and selected heavy metals in different forms to be made. Rotating coiled columns (RCC) earlier used mainly in countercurrent chromatography have been successfully applied to the dynamic leaching of heavy metals from soils contaminated by flooding sludge's. The sample was retained in a PTFE rotating column as the stationary phase whereas aqueous solutions were continuously pumped through. The contents of elements were determined by on-line coupling of RCC and inductively coupled plasma atomic emission spectrometry (ICP-AES). This enables real-time data on the leaching process to be obtained. Dynamic and traditional batch procedures were compared. It has been shown that the aqueous elution under centrifugal forced conditions is much more effective for the mobilization of heavy metals. Hence, the dynamic leaching is characterized by a substantially more intensive interaction between solid and water and is besides substantially more time-saving than the conventional batch procedure. The RCC procedure was also employed for preliminary leaching studies with a simulated "acid rain". In comparison with the water leaching, the mobilization of heavy metals and arsenic from soil samples with employment of simulated acid rain as eluent was less effective.     

Long-term effects of aided phytostabilisation of trace elements on microbial biomass and activity, enzyme activities, and composition of microbial community in the Jales contaminated mine spoils

We studied the effectiveness of remediation on microbial endpoints, namely microbial biomass and activity, microbial and plant species richness, of an As-contaminated mine spoil, amended with compost (C) alone and in combination with beringite (B) or zerovalent iron grit (Z), to increase organic matter content and reduce trace elements mobility, and to allow Holcus lanatus and Pinus pinaster growth. Untreated spoil showed the lowest microbial biomass and activity and hydrolase activities, and H. lanatus as sole plant species, whereas the presented aided phytostabilisation option, especially CBZ treatment, significantly increased microbial biomass and activity and allowed colonisation by several plant species, comparable to those of an uncontaminated sandy soil. Microbial species richness was only increased in spoils amended with C alone. No clear correlation occurred between trace element mobility and microbial parameters and plant species richness. Our results indicate that the choice of indicators of soil remediation practices is a bottleneck.