Release of trace metals, sulfate and complexed cyanide from soils contaminated with gas-purifier wastes: a microcosm study

Deposited gas-purifier wastes are commonly contaminated with trace metals, sulfate and cyanide (CN) compounds. We investigated their release from three soils contaminated with gas-purifier wastes into solution in microcosm experiments under varying redox conditions (E(H) 170-620 mV). The soils differed in pH (2.2; 4.9; 7.4) and featured low amounts of trace metals, but large amounts of total S and total CN. The pH governed trace metal release in the case of the acidic soil and CN release in the case of the slightly alkaline soil. The redox potential controlled trace metal and CN release in the case of the moderately acidic soil. Sources of dissolved SO(4)(2-) were dissolution of gypsum, desorption from Fe oxides and probably oxidation of elemental S. The geochemical behaviors of trace metals (soluble under acidic and reducing conditions) and CN (soluble under alkaline and oxidizing conditions) were diametrically opposed.     

Factors affecting accumulation of thallium and other trace elements in two wild Brassicaceae spontaneously growing on soils contaminated by tailings dam waste

Thallium is a scarce, highly toxic element. There are several investigations that report Tl accumulation in plants of the family Brassicaceae. These plants could pose a risk in areas where Tl is present at higher concentrations than normal soils. The present study reports analyses of two wild Brassicaceae, Hirschfeldia incana and Diplotaxis catholica, growing spontaneously at five sampling sites moderately polluted with Tl and other trace elements in the Green Corridor of the Guadiamar river, Seville, S. Spain. In general, trace element content was unremarkable in all part plants, despite the concentrations present in soil. Thallium was the only element whose concentration in both plant species was above normal for plants (maximum values of 5.00 mgkg(-1) in H. incana flowers). There were significant positive correlations between total Tl in soil and Tl in both plant species. Transfer Coefficients (TC) for all elements were, in general, <1 for both species, except for Tl in flowers and fruits at some sites. The highest Enrichment Factor (EF) was found for Tl in H. incana fruits (EF = 607) and D. catholica flowers (EF = 321). H. incana was studied in a previous growing season (2004) in the same area, although the rainfall was 3 times more than in the year of the present study (2005), giving a maximum Tl content of 46.5 mgkg(-1) in H. incana flowers. The data presented here show that Tl content of plants growing in semi-arid conditions can be significantly influenced by precipitation. In dry years, plant Tl accumulation may be significantly reduced.     

Remediation of PCB contaminated soils using iron nano-particles

In this study, iron nano-particles were used to remediate PCB contaminated soil and an attempt was made to maximize PCB destruction in each treatment step. The results show that nano-particles do aid in the dechlorination process and high PCB destruction efficiencies can be achieved. The destruction efficiency during the preliminary treatment (mixing of soil and iron nano-particles in water) can be increased by increasing the water temperature. The maximum thermal destruction (pyrolysis/combustion of soil after preliminary treatment) of soil-bound PCBs occurs at 300 degrees C in air. A minimum total PCB destruction efficiency of 95% can be achieved by this process. The effect of changing treatment parameters such as type of mixing, time of mixing and mixing conditions and application of other catalysts like iron oxide and V(2)O(5)/TiO(2) was also investigated. It was found that at 300 degrees C in air, iron oxide and V(2)O(5)/TiO(2) are also good catalysts for remediating PCB contaminated soils.     

Effects of incubation on solubility and mobility of trace metals in two contaminated soils

Much research has focused on changes in solubility and mobility of trace metals in soils under incubation. In this experiment, changes in solubility and mobility of trace metals (Pb, Cu and As) and Fe in two contaminated soils from Tampa, Florida and Montreal, Canada were examined. Soils of 30 g were packed in columns and were incubated for 3-80 days under water-flooding incubation. Following incubation, metal concentrations in pore water (water soluble) and in 0.01 M CaCl2 leachates (exchangeable+water soluble) were determined. While both soils were contaminated with Pb (1600-2500 mg kg(-1)), Tampa soil was also contaminated with As (230 mg kg(-1)). Contrast to the low pH (3.8) of Tampa soil, Montreal soil had an alkaline pH of 7.7 and high Ca of 1.6%. Concentrations of Fe(II) increased with incubation time in the Tampa soil mainly due to reductive Fe dissolution, but decreased in the Montreal soil possibly due to formation of FeCO3. The inverse relationship between concentrations of Pb and Fe(II) in pore water coupled with the fact that Fe(II) concentrations were much greater than those of Pb in pore water may suggest the importance of Fe(II) in controlling Pb solubility in soils. However, changes in concentrations of Fe(II), Pb, Cu and As in pore water with incubation time were similar to those in leachate, i.e. water soluble metals were positively related to exchangeable metals in the two contaminated soils. This research suggests the importance of Fe in controlling metal solubility and mobility in soils under water-flooded incubation.     

Impact of earthworms on trace element solubility in contaminated mine soils amended with green waste compost

The common practice of remediating metal contaminated mine soils with compost can reduce metal mobility and promote revegetation, but the effect of introduced or colonising earthworms on metal solubility is largely unknown. We amended soils from an As/Cu (1150 mgAs kg⁻¹ and 362 mgCu kg⁻¹) and Pb/Zn mine (4550 mgPb kg⁻¹ and 908 mgZn kg⁻¹) with 0, 5, 10, 15 and 20% compost and then introduced Lumbricus terrestris. Porewater was sampled and soil extracted with water to determine trace element solubility, pH and soluble organic carbon. Compost reduced Cu, Pb and Zn, but increased As solubility. Earthworms decreased water soluble Cu and As but increased Pb and Zn in porewater. The effect of the earthworms decreased with increasing compost amendment. The impact of the compost and the earthworms on metal solubility is explained by their effect on pH and soluble organic carbon and the environmental chemistry of each element.     

Health risks of heavy metals in contaminated soils and food crops irrigated with wastewater in Beijing, China

Consumption of food crops contaminated with heavy metals is a major food chain route for human exposure. We studied the health risks of heavy metals in contaminated food crops irrigated with wastewater. Results indicate that there is a substantial buildup of heavy metals in wastewater-irrigated soils, collected from Beijing, China. Heavy metal concentrations in plants grown in wastewater-irrigated soils were significantly higher (P相似文献   

Comparison between fractionation and bioavailability of trace elements in rhizosphere and bulk soils

Rhizosphere is a microbiosphere and has quite different chemical, physical and biological properties from bulk soils. A greenhouse experiment was performed to compare the difference of fractionation and bioavailability of trace elements Cr, Ni, Zn, Cu, Pb and Cd between rhizosphere soil and bulk soil. In the meantime, the influence of air-drying on the fractionation and bioavailability was also investigated by using wet soil sample as a control. Soils in a homemade rhizobox were divided into four zones: rhizosphere, near rhizosphere, near bulk soil and bulk soil zones, which was designated as S1, S2, S3 and S4. Elemental speciations were fractionated to water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), and organic and sulfide bound (B3) by a sequential extraction procedure. Speciation differences were observed for elements Cr, Ni, Zn, Cu, Pb and Cd between the rhizosphere and bulk soils, and between the air-dried and wet soils as well. The concentrations of all six heavy metals in fraction B1 followed the order of S2 > S3 > S1 > S4 and for B2, the order was S2 > S3 S4 > S1. For B3, the order was S1 > S3 S4 > S2, while for Cd the order was S2 > S3 approximately/= S4 > S1. The air-drying increased elemental concentration in fractions B1 and B2 by 20-50% and decreased in fraction B3 by about 20-100%. Correlation analysis also indicated that the bioavailability correlation coefficient of fraction B1 in rhizosphere wet soil to plants was better than that between either air-dried or nonrhizosphere soils. Therefore, application of rhizosphere wet soils should be recommended in the future study on the speciation analysis of trace elements in soils and bioavailability.     

Inactivation of cadmium in contaminated soils using synthetic zeolites

The addition of synthetic zeolite pellets to soils contaminated with cadmium significantly reduced the concentrations of cadmium in the roots and shoots of a range of crop plants. Use of synthetic foyazite group zeolites types 4A and 13X, at application rates of 1% by soil weight, caused reductions in cadmium concentrations of up to 86% in leaves of lettuce grown in pots, compared to controls with no added zeolites. The potential of these substances to reduce cadmium entry into the food chain, and as a clean up method, is noted.     

Solid speciation and mobility of potentially toxic elements from natural and contaminated soils: a combined approach

The study area (Szklary Massif, SW Poland) comprises three sites of different soil provenance: (1) natural serpentine Cambisol, (2) anthroposol situated on waste dump and (3) cultivated Inceptisol developed on glacial tills next to the dump. Potentially toxic elements (PTE) have either lithogenic or anthropogenic origins in these sites. The chemical partitioning of Co, Cr, Cu, Ni, Pb and Zn among solid forms was determined by sequential extractions coupled with direct mineral identifications (SEM, electron microprobe analysis - EMPA, and XRD). Examination of solid residues after several extraction steps was conducted in order to discuss the indirect speciation obtained by the extraction method. Total concentrations of PTE having anthropogenic origin greatly exceed those of lithogenic origin. Mobility of studied PTE is variable in the different environments except for Cr which is always mostly found in residual fractions of extractions. Cu and Pb are more mobile than Cr and Co in all soils. Zn is more stable (Cu>Pb>Ni>Co>Zn>Cr) in the serpentine soil and cultivated epipedon (Pb>Cu>Zn>Ni>Co>Cr) than in the anthroposol (Zn>CuPb>Ni>Co>Cr). PTE of lithogenic origin are generally less mobile than those from anthropogenic origin except Ni which is more mobile in the serpentine soil. Nonetheless, mineral forms of metals better determine their mobility than metal origin. Identification by direct methods of the PTE mineral form was not possible for metals present at low concentrations (Cu, Pb). However, direct mineralogical examinations of the solid residues of several extractions steps improved the assessment of the PTE solid speciation and mobility, particularly for Cr, Ni and Zn.     

Leaching of heavy metals from contaminated soils using EDTA

Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.     

粘土矿物修复重金属污染土壤

简要介绍了我国土壤重金属污染的现状与危害.通过粘土矿物在重金属污染土壤中净化功能的阐述,提出利用粘土矿物修复土壤重金属污染的观点.继而从天然和改性粘土矿物特性,叙述了粘土矿物修复土壤重金属污染的机制与应用进展及其影响因素.最后讨论了粘土矿物在修复土壤重金属污染过程中值得注意的几个问题,并展望了粘土矿物在该领域应用中的发展方向.     

Enrichment of trace elements in the clay size fraction of mining soils

Reactive waste dumps with sulfide minerals promote acid mine drainage (AMD), which results in water and soil contamination by metals and metalloids. In these systems, contamination is regulated by many factors, such as mineralogical composition of soil and the presence of sorption sites on specific mineral phases. So, the present study dedicates itself to understanding the distribution of trace elements in different size fractions (<2-mm and <2-μm fractions) of mining soils and to evaluate the relationship between chemical and mineralogical composition. Cerdeirinha and Penedono, located in Portugal, were the waste dumps under study. The results revealed that the two waste dumps have high degree of contamination by metals and arsenic and that these elements are concentrated in the clay size fraction. Hence, the higher degree of contamination by toxic elements, especially arsenic in Penedono as well as the role of clay minerals, jarosite, and goethite in retaining trace elements has management implications. Such information must be carefully thought in the rehabilitation projects to be planned for both waste dumps.     

海泡石及其复配材料钝化修复镉污染土壤

选取湖北大冶Cd污染土壤,采用室外盆栽实验,研究了海泡石、酸改性海泡石以及二者与石灰、磷酸盐配合使用对油菜生物量、体内Cd含量以及土壤pH和有效态Cd含量的影响。结果表明,不同钝化剂处理均能有效提高油菜地上部和根部生物量,最大分别提高1.03和1.43倍,复合处理以及改性海泡石单一处理的增产效果优于海泡石单一处理。不同钝化剂处理均能显著降低油菜地上部和根部Cd含量,最大分别降低66.40%和22.68%。钝化剂复合处理比单一处理对降低油菜Cd吸收的效果显著,6%的钝化剂添加量较为合适。钝化剂复合处理以及海泡石单一处理均能显著提高土壤pH。不同钝化剂处理均能显著降低土壤有效态Cd含量,钝化剂复合处理对土壤Cd有效性的影响要比单一处理显著。综合实验结果,海泡石与磷酸盐复合处理对土壤Cd污染的钝化修复效果最佳。     

In situ remediation of soils contaminated with toxic metal ions using microwave energy

Following onto our work on the in situ remediation of soils contaminated with PAH's, PCB's and other polychlorinated organic compounds using microwave energy, we now report a preliminary investigation on the in situ remediation of soils contaminated with toxic metal ions: Cd(II), Mn(II), Th(IV), Cr(III) and mainly Cr(VI). The soil is partially vitrified in the process, and extraction with hot (70 degrees C) 35% nitric acid for 4.5 h leads to the recovery of very small amounts of the metals which had been spiked into the clean soil: Cd, Mn, and Cr(III) are completely immobilized (unextractable), Th is mostly unextractable, and Cr(VI) partially extractable at very high levels of spiking, but almost completely unextractable using the US EPA Toxicity Characteristic Leaching Procedure. This suggests that contaminated soils which are not going to be used for agricultural purposes can be remediated safely to preset depths without fear of the toxic metal ions leaching out for a long time.     

Combined treatment of PAHs contaminated soils using the sequence extraction with surfactant-electrochemical degradation

Polycyclic aromatic hydrocarbons (PAHs) cause a high environmental impact when released into the environment. The objective of this study was to evaluate the capacity of decontamination of polluted soils with PAHs using the sequence extraction-electrochemical treatment: extraction of PAHs from the soil with surfactant followed by electrochemical degradation of the liquid collected. Several PAHs (anthracene, benzo[a]pyrene, and phenanthrene) have been used as model compounds since such PAHs are found in high concentrations in contaminated environmental samples. Due to their hydrophobic nature, soil extraction has been limited. In this work, the use of six surfactants, Brij 35, Merpol, Tergitol, Tween 20, Tween 80 and Tyloxapol, has been evaluated on the PAH extraction from a model soil such as kaolin. Furthermore, the electrochemical degradation of PAHs with the surfactant that gave the best result was investigated working with neat solutions. The electrochemical treatment of these solutions was carried out in two electrochemical cells with different working volumes, 0.4 and 1.5l, and electrode material (graphite or titanium). Near complete degradation was reached for all the experiments in both cells.     

砷污染土壤柠檬酸萃取修复技术研究

伴随着砷工业的发展,含砷化学品引发的重大环境污染事故时有发生。一般砷污染事件发生后,土壤是其最直接的受害者,有必要寻找一种快速且行之有效的方法对砷污染土壤进行控制修复。针对此问题,通过实验探讨了柠檬酸萃取修复砷污染土壤的效果,研究了柠檬酸浓度、液土比、萃取时间及土壤共存离子对柠檬酸萃取砷的效果的影响,为砷污染土壤的治理提供依据。结果表明,柠檬酸是一种高效的砷萃取剂;随着柠檬酸浓度、液土比、萃取时间的增加,砷的萃取率均有所升高;当柠檬酸摩尔浓度为0.25 mol/L、液土比为20 mL/g、萃取时间为21 h时,柠檬酸对砷的萃取率达到最高值(70.58%);土壤中共存的PO43-、Zn2+、Fe2+,由于其竞争作用,能使柠檬酸对砷的萃取率降低。     

Plant responses to a phytomanaged urban technosol contaminated by trace elements and polycyclic aromatic hydrocarbons

Medicago sativa was cultivated at a former harbor facility near Bordeaux (France) to phytomanage a soil contaminated by trace elements (TE) and polycyclic aromatic hydrocarbons (PAH). In parallel, a biotest with Phaseolus vulgaris was carried out on potted soils from 18 sub-sites to assess their phytotoxicity. Total soil TE and PAH concentrations, TE concentrations in the soil pore water, the foliar ionome of M. sativa (at the end of the first growth season) and of Populus nigra growing in situ, the root and shoot biomass and the foliar ionome of P. vulgaris were determined. Despite high total soil TE, soluble TE concentrations were generally low, mainly due to alkaline soil pH (7.8–8.6). Shoot dry weight (DW) yield and foliar ionome of P. vulgaris did not reflect the soil contamination, but its root DW yield decreased at highest soil TE and/or PAH concentrations. Foliar ionomes of M. sativa and P. nigra growing in situ were generally similar to the ones at uncontaminated sites. M. sativa contributed to bioavailable TE stripping by shoot removal (in g ha^?1 harvest^?1): As 0.9, Cd 0.3, Cr 0.4, Cu 16.1, Ni 2.6, Pb 4, and Zn 134. After 1 year, 72 plant species were identified in the plant community across three subsets: (I) plant community developed on bare soil sowed with M. sativa; (II) plant community developed in unharvested plots dominated by grasses; and (III) plant community developed on unsowed bare soil. The shoot DW yield (in mg ha^?1 harvest^?1) varied from 1.1 (subset I) to 6.9 (subset II). For subset III, the specific richness was the lowest in plots with the highest phytotoxicity for P. vulgaris.     

有机改性蒙脱石负载巯基修复汞污染土壤

以蒙脱石作为原始材料,对其进行有机改性,将巯基基团负载在有机改性的蒙脱石上制备出重金属汞的稳定剂以稳定化修复汞污染土壤。考察稳定化时间、稳定剂添加量、浸出液pH及有机质含量对稳定化效果的影响,探究稳定化前后土壤汞形态变化。通过XRD、FTIR和SEM分析了蒙脱石、有机改性蒙脱石（Mont-OR）和负载巯基有机改性蒙脱石（Mont-OR-SH）的物理化学特征,通过原子吸收法测定汞浓度。稳定化修复结果表明,稳定化时间为30 d,稳定剂添加量为9%时,汞浸出浓度为0.066 mg·L-1,稳定率为98.3%,达到GB 5085.3-2007规定的汞限值0.10 mg·L-1。添加不同质量的小麦秸秆作为有机质的来源,均对整个稳定化有促进作用,其中添加量为6%时,促进作用最明显,改变浸出液pH,在强酸性和强碱性条件下,利用此稳定剂对汞的稳定作用降低。TESSIER五步提取法结果表明,负载巯基的有机改性蒙脱石的添加导致可交换态汞、碳酸盐结合态汞、铁锰氧化物结合态汞含量下降,而有机结合态汞、残渣态汞含量增加。实验结果证明有机改性蒙脱石负载巯基能够有效地应用于汞污染土壤修复。     

Comparison of solid and liquid-phase bioassays using ecoscores to assess contaminated soils

Bioassays on aqueous and solid phases of contaminated soils were compared, belonging to a wide array of trophic and response levels and using ecoscores for evaluating ecotoxicological and genotoxicological endpoints. The method was applied to four coke factory soils contaminated mainly with PAHs, but also to a lesser extent by heavy metals and cyanides. Aquatic bioassays do not differ from terrestrial bioassays when scaling soils according to toxicity but they are complementary from the viewpoint of ecological relevance. Both aquatic and terrestrial endpoints are strongly correlated with concentrations of 3-ring PAHs. This evaluation procedure allows us to propose a cost-effective battery which embraces a wide array of test organisms and response levels: it includes two rapid bioassays (Microtox(?) and springtail avoidance), a micronucleus test and three bioassays of a longer duration (algal growth, lettuce germination and springtail reproduction). This battery can be recommended for a cost-effective assessment of polluted/remediated soils.     

The water-soluble fraction of potentially toxic elements in contaminated soils: relationships between ecotoxicity, solubility and geochemical reactivity

To better understand the impacts posed by soil contamination to aquatic ecosystems it is crucial to characterise the links between ecotoxicity, chemical availability and geochemical reactivity of potentially toxic elements (PTE’s) in soils. We evaluated the adverse effects of water extracts obtained from soils contaminated by chemical industry and mining, using a test battery including organisms from different trophic levels (bacteria, algae and daphnids). These tests provided a quick assessment of the ecotoxicity of soils with respect to possible adverse effects on aquatic organisms although the ecotoxicological responses could be related to the solubility of PTE’s only to a limited extent.The analysis of results of bioassays together with the chemical characterisation of water extracts provided additional relevant insight into the role of conductivity, pH, Al, Fe, and Mn of soil extracts on toxicity to organisms. Furthermore, an important conclusion of this study was that the toxicity of extracts to the aquatic organisms could also be related to the soil properties (pH, Org C and Fe_ox) and to the reactivity of PTE’s in soils which in fact control the soluble fraction of the contaminants.The combined assessment of ecotoxicity in water fractions, solubility and geochemical reactivity of PTE’s in soils provided a more comprehensive understanding of the bioavailability of inorganic contaminants than ecotoxicological or chemical studies alone and can therefore be most useful for environmental risks assessment of contaminated soils.