Biochar- and phosphate-induced immobilization of heavy metals in contaminated soil and water: implication on simultaneous remediation of contaminated soil and groundwater

Long-term wastewater irrigation or solid waste disposal has resulted in the heavy metal contamination in both soil and groundwater. It is often separately implemented for remediation of contaminated soil or groundwater at a specific site. The main objective of this study was to demonstrate the hypothesis of simultaneous remediation of both heavy metal contaminated soil and groundwater by integrating the chemical immobilization and pump-and-treat methods. To accomplish the objective, three experiments were conducted, i.e., an incubation experiment was first conducted to determine how dairy-manure-derived biochar and phosphate rock tailing induced immobilization of Cd in the Cd-contaminated soils; second, a batch sorption experiment was carried out to determine whether the pre-amended contaminated soil still had the ability to retain Pb, Zn and Cd from aqueous solution. BCR sequential extraction as well as XRD and SEM analysis were conducted to explore the possible retention mechanism; and last, a laboratory-scale model test was undertaken by leaching the Pb, Zn, and Cd contaminated groundwater through the pre-amended contaminated soils to demonstrate how the heavy metals in both contaminated soil and groundwater were simultaneously retained and immobilized. The incubation experiment showed that the phosphate biochar were effective in immobilizing soil Cd with Cd concentration in TCLP (toxicity characteristics leaching procedure) extract reduced by 19.6 % and 13.7 %, respectively. The batch sorption experiment revealed that the pre-amended soil still had ability to retain Pb, Zn, and Cd from aqueous solution. The phosphate-induced metal retention was mainly due to the metal–phosphate precipitation, while both sorption and precipitation were responsible for the metal stabilization in the biochar amendment. The laboratory-scale test demonstrated that the soil amended with phosphate removed groundwater Pb, Zn, and Cd by 96.4 %, 44.6 %, and 49.2 %, respectively, and the soil amended with biochar removed groundwater Pb, Zn, and Cd by 97.4 %, 53.4 %, and 54.5 %, respectively. Meanwhile, the metals from both groundwater and soil itself were immobilized with the amendments, with the leachability of the three metals in the CaCl₂ and TCLP extracts being reduced by up to 98.1 % and 62.7 %, respectively. Our results indicate that the integrated chemical immobilization and pump-and-treat method developed in this study provides a novel way for simultaneous remediation of both metal-contaminated soil and groundwater.     

Phytostabilization of a metal contaminated sandy soil. II: Influence of compost and/or inorganic metal immobilizing soil amendments on metal leaching

A lysimeter approach (under natural climatologic conditions) was used to evaluate the effect of four metal immobilizing soil treatments [compost (C), compost+cyclonic ashes (C+CA), compost+cyclonic ashes+steel shots (C+CA+SS)) and cyclonic ashes+steel shots (CA+SS)] on metal leaching through an industrially contaminated soil. All treatments decreased Zn and Cd leaching. Strongest reductions occurred after CA+SS and C+CA+SS treatments (Zn: -99.0% and -99.2% respectively; Cd: -97.2% and -98.3% respectively). Copper and Pb leaching increased after C (17 and >30 times for Cu and Pb respectively) and C+CA treatment (4.4 and >3.7 times for Cu and Pb respectively). C+CA+SS or CA+SS addition did not increase Cu leaching; the effect on Pb leaching was not completely clear. Our results demonstrate that attention should be paid to Cu and Pb leaching when organic matter additions are considered for phytostabilization of metal contaminated soils.     

Mobility of Pb, Cu, and Zn in the phosphorus-amended contaminated soils under simulated landfill and rainfall conditions

Phosphorus-bearing materials have been widely applied in immobilization of heavy metals in contaminated soils. However, the study on the stability of the initially P-induced immobilized metals in the contaminated soils is far limited. This work was conducted to evaluate the mobility of Pb, Cu, and Zn in two contrasting contaminated soils amended with phosphate rock tailing (PR) and triple superphosphate fertilizer (TSP), and their combination (P?+?T) under simulated landfill and rainfall conditions. The main objective was to determine the stability of heavy metals in the P-treated contaminated soils in response to the changing environment conditions. The soils were amended with the P-bearing materials at a 2:1 molar ratio of P to metals. After equilibrated for 2 weeks, the soils were evaluated with the leaching procedures. The batch-based toxicity characteristic leaching procedure (TCLP) was conducted to determine the leachability of heavy metals from both untreated and P-treated soils under simulated landfill condition. The column-based synthetic precipitation leaching procedure (SPLP) were undertaken to measure the downward migration of metals from untreated and P-treated soils under simulated rainfall condition. Leachability of Pb, Cu, and Zn in the TCLP extract followed the order of Zn?>?Cu?>?Pb in both soils, with the organic-C- and clay-poor soil showing higher metal leachability than the organic-C- and clay-rich soil. All three P treatments reduced leachability of Pb, Cu, and Zn by up to 89.2, 24.4, and 34.3 %, respectively, compared to the untreated soil, and TSP revealed more effectiveness followed by P?+?T and then PR. The column experiments showed that Zn had the highest downward migration upon 10 pore volumes of SPLP leaching, followed by Pb and then Cu in both soils. However, migration of Pb and Zn to subsoil and leachate were inhibited in the P-treated soil, while Cu in the leachate was enhanced by P treatment in the organic-C-rich soil. More than 73 % P in the amendments remained in the upper 0–10 cm soil layers. However, leaching of P from soluble TSP was significant with 24.3 % of P migrated in the leachate in the organic-C-poor soil. The mobility of heavy metals in the P-treated soil varies with nature of P sources, heavy metals, and soils. Caution should be taken on the multi-metal stabilization since the P amendment may immobilize some metals while promoting others’ mobility. Also, attention should be paid to the high leaching of P from soluble P amendments since it may pose the risk of excessive P-induced eutrophication.     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验，测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣，并为矿区重金属污染土壤的修复提供技术支持，采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理；通过浸出毒性实验对固化/稳定化处理效果进行综合分析，试图寻求一种最佳的稳定剂。结果表明，无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加，样品浸出液的pH都有升高，As、Cd的浸出浓度都有明显下降，而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中，粉煤灰混合堆肥化污泥的处理效果最好，浸出液的pH值达到7.82，As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳，同时具有以废治污的资源化生态效能。     

Immobilization of potentially toxic metals using different soil amendments

The in situ stabilization of potentially toxic metals (PTMs), using various easily available amendments, is a cost-effective remediation method for contaminated soils. In the present study, we investigated the effectiveness of apatite and a commercial mixture of dolomite, diatomite, smectite basaltic tuff, bentonite, alginite and zeolite (Slovakite) on Pb, Zn, Cu and Cd stabilization by means of decreasing their bioavailability in contaminated soil from an old lead and zinc smelter site in Arnoldstein, Austria. We also investigated the impact of 5% (w/w) apatite and Slovakite applications on soil functionality and quality, as assessed by glucose-induced soil respiration, dehydrogenase, acid and alkaline phosphatase and β-glucosidase activity. Both amendments resulted in increased soil pH and decreased PTM potential bioavailability assessed by diethylenetriamine pentaacetic acid extraction and by sequential extractions in the water-soluble and exchangeable fractions. The efficiency of stabilization was reflected in the soil respiration rate and in enzymatic activity. The β-glucosidase activity assay was the most responsive of them.     

石灰干化污泥对土壤重金属稳定化处理的效果

以采自湖南省嘉禾县重金属复合污染土壤为研究对象,采用城市污水处理石灰干化污泥作为稳定剂,对污染土壤进行稳定化处理,并采用TCLP和BCR连续提取法对稳定化效果进行分析和评价。研究结果表明,单独使用石灰干化污泥,TCLP浸出浓度随着干化污泥质量分数的增加而显著减少,干化污泥的质量分数为40%时,稳定化率最大为Zn-98.92%、Cd-99.06%、Pb-96.84%;但是干化污泥的高pH值导致稳定后土壤中As的浸出增加。为了恢复植物生长功能,经过亚铁盐和磷酸调节pH后,石灰干化污泥稳定过的土壤pH有效降低,同时亚铁盐和磷酸有利于促进Pb和Zn的稳定效果;但是对Cd的稳定有负面影响;另外,亚铁盐的加入同时可以减少As的浸出浓度。经处理后土壤中重金属形态由不稳定态转为稳定态,使重金属的浸出浓度明显降低,减少了土壤重金属的浸出毒性。该研究结果表明,石灰干化污泥可以作为资源回收利用,应用于重金属污染土壤的修复中,并能改善稳定后土壤适宜植物生长的理化性质。     

Multi-step leaching of Pb and Zn contaminated soils with EDTA

The efficiency of multi-step leaching of heavy metal contaminated soils was evaluated in a laboratory scale study. Four different soils contaminated with Pb (1136+/-16-4424+/-313mgkg(-1)) and Zn (288+/-5-5489+/-471mgkg(-1)) were obtained from industrial sites in the Mezica Valley, Slovenia and Príbram district, Czech Republic. Different dosages (2.5-40mmolkg(-1)) of ethylenediamine tetraacetate (EDTA) were used to treat soils in 1-10 leaching steps. Higher EDTA dosages did not result in a proportional gain in Pb and Zn removal. EDTA extracted Pb more efficiently than Zn from three of four tested soils. The percentage of removed Zn did not exceed 75% regardless of the soil, EDTA dosage and leaching steps. Significantly more Pb (in three of four soils) and Zn were removed from soils when the same amount of EDTA was applied in several leaching steps. The interference of major soil cations Fe and Ca with EDTA complexation as a possible factor affecting Pb and Zn removal efficiency with multi-step heap leaching was examined and is discussed. The results of our study indicate that, for some soils, using multi-step leaching instead of the more traditionally used single dose EDTA treatment could improve heavy metal removal efficiency and thus the economics of soil remediation.     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Remediation of metal contaminated soil with mineral-amended composts

This study examined the use of two composts derived from green waste and sewage sludge, amended with minerals (clinoptilolite or bentonite), for the remediation of metal-contaminated brownfield sites to transform them into greenspace. Soils contaminated with high or low levels of metals were mixed with the mineral-enhanced composts at different ratios and assessed by leaching tests, biomass production and metal accumulation of ryegrass (Lolium perenne L.). The results showed that the green waste compost reduced the leaching of Cd and Zn up to 48% whereas the composted sewage sludge doubled the leachate concentration of Zn. However, the same soil amended with composted sewage sludge showed an efficient reduction in plant concentrations of Cd, Cu, Pb or Zn by up to 80%. The results suggest that metal immobilisation and bioavailability are governed by the formation of complexes between the metals and organic matter. The amendment with minerals had only limited effects.     

可渗透反应复合电极法对土壤重金属的电动去除

将零价铁(Fe0)、沸石等活性材料附着在电极上形成可渗透反应层并构成可渗透反应复合电极,采用不同的复合电极对Cd2+、Ni 2+、Pb2+和Cu2+等4种阳离子型重金属污染土壤进行了电动力学修复。研究了不同可渗透反应复合电极对土壤pH的控制效果以及对重金属的去除作用,分析了迁移到复合电极中的重金属形态变化。结果表明,复合电极中添加酸、碱性沸石并适时更换,可有效中和、截留阴阳极电解产生的OH-和H+,避免或减缓土壤酸碱迁移带的形成,防止重金属离子的过早沉淀及土壤过度酸化,极大提高了重金属的去除率。复合电极中Fe0可将迁移进来的重金属离子进行还原稳定,实现重金属污染物的捕获与固定,与迁移到沸石复合电极中的4种重金属不稳定态相比,"Fe0+沸石"复合电极中重金属不稳定态分别下降了61.4、60.5、61.4、57.1百分点。结果还显示,阴极采用"Fe0+沸石"复合电极并适时进行更换,施加1.5V/cm的直流电压修复10d后,土壤中Cd、Ni、Pb、Cu的总去除率分别为44.5%、41.5%、33.5%和36.7%,且进一步延长修复时间和持续更换电极可获得更为理想的修复效果。     

Techniques for the stabilization and assessment of treated copper-, chromium-, and arsenic-contaminated soil

Remediation mainly based on excavation and burial of the contaminated soil is impractical with regard to the large numbers of sites identified as being in need of remediation. Therefore, alternative methods are needed for brownfield remediation. This study was conducted to assess a chemical stabilization procedure of CCA-contaminated soil using iron (Fe)-containing blaster sand (BS) or oxygen-scarfing granulate (OSG). The stabilization technique was assessed with regard to the feasibility of mixing ameliorants at an industrial scale and the efficiency of the stabilization under different redox conditions. The stability was investigated under natural conditions in 1-m3 lysimeters in a field experiment, and the effect of redox conditions was assessed in a laboratory experiment (10 L). The treatments with high additions of ameliorant (8% and 17%) were more successful in both the laboratory and field experiments, even though there was enough Fe on a stochiometric basis even at the lowest addition rates (0.1% and 1%). The particle size of the Fe and the mixing influenced the stabilization efficiency. The development of anaerobic conditions, simulated by water saturation, increases the fraction of arsenic (AsIII) and, consequently, As mobility. The use of high concentrations of OSG under aerobic conditions increased the concentrations of nickel (Ni) and copper (Cu) in the pore water. However, under anaerobic conditions, it decreased the As leaching compared with the untreated soil, and Ni and Cu leaching was not critical. The final destination of the treated soil should govern the amendment choice, that is, an OSG concentration of approximately 10% may be suitable if the soil is to be landfilled under anaerobic conditions. Alternatively, the soil mixed with 1% BS could be kept under aerobic conditions in a landfill cover or in situ at a brownfield site. In addition, the treatment with BS appeared to produce better effects in the long term than treatment with OSG.     

Recycling EDTA solutions used to remediate metal-polluted soils

The objective of this research was to investigate the recycling of ethylenediamine-tetraacetic acid (EDTA) used for the removal of trace metals from contaminated soils. We successfully used Na2S combined with Ca(OH)2 to precipitate the trace metals allowing us to recycle the EDTA. The results of batch and column leaching experiments show that both Ca-EDTA and Na-EDTA are powerful chelating agents with a similar soil remediation potential. The major advantage of Ca-EDTA is the preservation of soil organic matter. We found that Na2S was capable of separating the metals Cd, Cu and Pb from EDTA; however, the precipitation of Zn required the addition of Ca(OH)2. After reusing the reclaimed EDTA seven times, over a 14-day period, EDTA reagent losses ranged from 19.5% to 23.5%. Successive washing cycles enhanced the removal of trace metals from contaminated soils. The metal sulfide precipitates contain high concentrations of metals and could potentially be recycled.     

Leaching variations of heavy metals in chelator-assisted phytoextraction by Zea mays L. exposed to acid rainfall

Chelant-enhanced phytoextraction method has been put forward as an effective soil remediation method, whereas the heavy metal leaching could not be ignored. In this study, a cropping-leaching experiment, using soil columns, was applied to study the metal leaching variations during assisted phytoextraction of Cd- and Pb-polluted soils, using seedlings of Zea mays, applying three different chelators (EDTA, EDDS, and rhamnolipid), and artificial rainfall (acid rainfall or normal rainfall). It showed that artificial rainfall, especially artificial acid rain, after chelator application led to the increase of heavy metals in the leaching solution. EDTA increased both Cd and Pb concentrations in the leaching solution, obviously, whereas EDDS and rhamnolipid increased Cd concentration but not Pb. The amount of Cd and Pb decreased as the leaching solution increased, the patterns as well matched LRMs (linear regression models), with R-square (R ²) higher than 90 and 82% for Cd and Pb, respectively. The maximum cumulative Cd and Pb in the leaching solutions were 18.44 and 16.68%, respectively, which was amended by EDTA and acid rainwater (pH 4.5), and followed by EDDS (pH 4.5), EDDS (pH 6.5), rhamnolipid (0.5 g kg⁻¹ soil, pH 4.5), and rhamnolipid (pH 6.5).

     

Migration of heavy metals in soil as influenced by compost amendments

Soils contaminated with heavy metals can pose a major risk to freshwaters and food chains. In this study, the success of organic and inorganic intervention strategies to alleviate toxicity in a highly acidic soil heavily contaminated with As, Cu, Pb, and Zn was evaluated over 112 d in a mesocosm trial. Amelioration of metal toxicity was assessed by measuring changes in soil solution chemistry, metal leaching, plant growth, and foliar metal accumulation. Either green waste- or MSW-derived composts increased plant yield and rooting depth, reduced plant metal uptake, and raised the pH and nutrient status of the soil. We conclude that composts are well suited for promoting the re-vegetation of contaminated sites; however, care must be taken to ensure that very short-term leaching pulses of heavy metals induced by compost amendment are not of sufficient magnitude to cause contamination of the wider environment.     

Assessment of zerovalent iron for stabilization of chromium, copper, and arsenic in soil

Stabilization of soil contaminated with trace elements is a remediation practice that does not reduce the total content of contaminants, but lowers the amounts of mobile and bioavailable fractions. This study evaluated the efficiency of Fe(0) to reduce the mobility and bioavailability of Cr, Cu, As and Zn in a chromated copper arsenate (CCA)-contaminated soil using chemical, biochemical and biotoxicity tests. Contaminated soil was stabilized with 1% iron grit. This treatment decreased As and Cr concentrations in leachates (by 98% and 45%, respectively), in soil pore water (by 99% and 94%, respectively) and in plant shoots (by 84% and 95%, respectively). The stabilization technique also restored most of analyzed soil enzyme activities and reduced microbial toxicity, as evaluated by the BioTox test. After stabilization, exchangeable and bioaccessible fractions of Cu remained high, causing some residual toxicity in the treated soil.     

Heavy metal availability,bioaccessibility, and leachability in contaminated soil: effects of pig manure and earthworms

A pot experiment and a leaching experiment were conducted to investigate the effects of earthworms and pig manure on heavy metals (Cd, Pb, and Zn) immobility, in vitro bioaccessibility and leachability under simulated acid rain (SAR). Results showed manure significantly increased soil organic carbon (SOC), dissolved organic carbon (DOC), available phosphorus (AP), total N, total P and pH, and decreased CaCl₂-extractable metals and total heavy metals in water and SAR leachate. The addition of earthworms significantly increased AP (from 0.38 to 1.7 mg kg^?1), and a downward trend in CaCl₂-extractable and total leaching loss of heavy metals were observed. The combined earthworm and manure treatment decreased CaCl₂-extractable Zn, Cd, and Pb. For Na₄P₂O₇-extractable metals, Cd and Pb were decreased with increasing manure application rate. Application of earthworm alone did not contribute to the remediation of heavy metal polluted soils. Considering the effects on heavy metal immobilization and cost, the application of 6% manure was an alternative approach for treating contaminated soils. These findings provide valuable information for risk management during immobilization of heavy metals in contaminated soils.

     

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.     

Arsenic and copper stabilisation in a contaminated soil by coal fly ash and green waste compost

In situ metal stabilisation by amendments has been demonstrated as an appealing low-cost remediation strategy for contaminated soil. This study investigated the short-term leaching behaviour and long-term stability of As and Cu in soil amended with coal fly ash and/or green waste compost. Locally abundant inorganic (limestone and bentonite) and carbonaceous (lignite) resources were also studied for comparison. Column leaching experiments revealed that coal fly ash outperformed limestone and bentonite amendments for As stabilisation. It also maintained the As stability under continuous leaching of acidic solution, which was potentially attributed to high-affinity adsorption, co-precipitation, and pozzolanic reaction of coal fly ash. However, Cu leaching in the column experiments could not be mitigated by any of these inorganic amendments, suggesting the need for co-addition of carbonaceous materials that provides strong chelation with oxygen-containing functional groups for Cu stabilisation. Green waste compost suppressed the Cu leaching more effectively than lignite due to the difference in chemical composition and dissolved organic matter. After 9-month soil incubation, coal fly ash was able to minimise the concentrations of As and Cu in the soil solution without the addition of carbonaceous materials. Nevertheless, leachability tests suggested that the provision of green waste compost and lignite augmented the simultaneous reduction of As and Cu leachability in a fairly aggressive leaching environment. These results highlight the importance of assessing stability and remobilisation of sequestered metals under varying environmental conditions for ensuring a plausible and enduring soil stabilisation.     

Impact of the earthworm Lumbricus terrestris (L.) on As, Cu, Pb and Zn mobility and speciation in contaminated soils

To assess the risks that contaminated soils pose to the environment properly a greater understanding of how soil biota influence the mobility of metal(loid)s in soils is required. Lumbricus terrestris L. were incubated in three soils contaminated with As, Cu, Pb and Zn. The concentration and speciation of metal(loid)s in pore waters and the mobility and partitioning in casts were compared with earthworm-free soil. Generally the concentrations of water extractable metal(loid)s in earthworm casts were greater than in earthworm-free soil. The impact of the earthworms on concentration and speciation in pore waters was soil and metal specific and could be explained either by earthworm induced changes in soil pH or soluble organic carbon. The mobilisation of metal(loid)s in the environment by earthworm activity may allow for leaching or uptake into biota.