The effect of organic materials on the mobility and toxicity of metals in contaminated soils

Organic materials such as compost are often proposed as suitable materials for the remediation of contaminated brownfield sites intended for soft end-use. In addition to vitalising the soil, they are also believed to immobilise metals thereby breaking contaminant-receptor pathways and reducing the ecotoxicity of the contaminants. However, some research has demonstrated contradictory effects between composts on metal immobilisation. In the present study, four different composts and a liming product containing organic matter (LimeX70) were tested to examine both their metal retention and toxicity reduction capabilities on three different metal contaminated soils. Leaching tests, a plant growth test with Greek cress (Lepidium sativum), an earthworm (Eisenia fetida) survival and condition test and a bacterial toxicity test using Vibrio fischeri were carried out. The leaching test results showed that spent mushroom compost caused an increase in metal concentration in the leachates, while LimeX70 caused a decrease. The variation in behaviour between different amendments for each soil was high, so a generic conclusion could not be drawn. Toxicity tests showed significant reduction of metal bioavailability and toxicity for Greek cress, earthworms and bacteria. The results also suggest that more research should be undertaken to understand the mechanisms involved in metal complexation using different types of organic matter, in order to optimise the use of organic materials like compost for soil remediation. Crown Copyright (C) 2007 Published by Elsevier Ltd. All rights reserved.

The effect of organic materials on the mobility and toxicity of metals in contaminated soils

Organic materials such as compost are often proposed as suitable materials for the remediation of contaminated brownfield sites intended for soft end-use. In addition to vitalising the soil, they are also believed to immobilise metals thereby breaking contaminant-receptor pathways and reducing the ecotoxicity of the contaminants. However, some research has demonstrated contradictory effects between composts on metal immobilisation. In the present study, four different composts and a liming product containing organic matter (LimeX70) were tested to examine both their metal retention and toxicity reduction capabilities on three different metal contaminated soils. Leaching tests, a plant growth test with Greek cress (Lepidium sativum), an earthworm (Eisenia fetida) survival and condition test and a bacterial toxicity test using Vibrio fischeri were carried out. The leaching test results showed that spent mushroom compost caused an increase in metal concentration in the leachates, while LimeX70 caused a decrease. The variation in behaviour between different amendments for each soil was high, so a generic conclusion could not be drawn. Toxicity tests showed significant reduction of metal bioavailability and toxicity for Greek cress, earthworms and bacteria. The results also suggest that more research should be undertaken to understand the mechanisms involved in metal complexation using different types of organic matter, in order to optimise the use of organic materials like compost for soil remediation. Crown Copyright (C) 2007 Published by Elsevier Ltd. All rights reserved.

Effects of metals on life cycle parameters of the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils

Two control and eight field-contaminated, metal-polluted soils were inoculated with Eisenia fetida (Savigny, 1826). Three, 7, 14, 21, 28 and 42 days after inoculation, earthworm survival, body weight, cocoon production and hatching rate were measured. Seventeen metals were analysed in E.fetida tissue, bulk soil and soil solution. Soil organic carbon content, texture, pH and cation exchange capacity were also measured. Cocoon production and hatching rate were more sensitive to adverse conditions than survival or weight change. Soil properties other than metal concentration impacted toxicity. The most toxic soils were organic-poor (1-10 g C kg(-1)), sandy soils (c. 74% sand), with intermediate metal concentrations (e.g. 7150-13, 100 mg Ph kg(-1), 2970-53,400 mg Zn kg(-1)). Significant relationships between soil properties and the life cycle parameters were determined. The best coefficients of correlation were generally found for texture, pH, Ag, Cd, Mg, Pb, Tl, and Zn both singularly and in multivariate regressions. Studies that use metal-amended artificial soils are not useful to predict toxicity of field multi-contaminated soils. (c) 2007 Elsevier Ltd. All rights reserved.

A preliminary investigation into the use of ochre as a remedial amendment in arsenic-contaminated soils

Ochre is an unwanted waste product that accumulates in wetlands and streams draining abandoned coal and metal mines. A potential commercial use for ochre is to remediate As contaminated soil. Arsenic contaminated soil (605 mg kg(-1)) was mixed with different ochres (A, B and C) in a mass ratio of 1:1 and shaken in 20 mL of deionised water. After 72 h As concentration in solution was ca. 500 mu g kg(-1) in the control and 1-2.5 mu g kg(-1) in the ochre treated experiments. In a second experiment soil:ochre mixtures of 0.05-1:1 were shaken in 20 mL of deionised water for 24 h. For Ochres A and C, as Solution concentration was reduced to ca. 1 mu gkg(-1) by 0.2-1:1 ochre:soil mixtures. For Ochre B, as concentration only reached ca. 1 mu g kg(-1) in the 1:1 ochre:soil inix. Sorption of As was best modelled by a Freundlich isotherm using As sorption per mass of goethite in the ochre (log K= 1.64, n = 0.79, R-2 = 0.76, p <= 0.001). Efficiency of ochre in removing As from solution increased with increasing total Fe, goethite, citrate dithionite extractable Fe and surface area. (c) 2005 Elsevier Ltd. All rights reserved.

Characterization and identification of mixed-metal phosphates in soils: the application, of Raman spectroscopy

The development of protocols for the identification of metal phosphates in phosphate-treated, metal-contaminated soils is a necessary yet problematical step in the validation of remediation schemes involving immobilization of metals as phosphate phases. The potential for Raman spectroscopy to be applied to the identification of these phosphates in soils has yet to be fully explored. With this in mind, a range of synthetic mixed-metal hydroxylapatites has been characterized and added to soils at known concentrations for analysis using both bulk X-ray powder diffraction (XRD) and Raman spectroscopy. Mixed-metal hydroxylapatites in the binary series Ca-Cd, Ca-Pb, Ca-Sr and Cd-Pb synthesized in the presence of acetate and carbonate ions, were characterized using a range of analytical techniques including XRD, analytical scanning electron microscopy (SEM), infrared spectroscopy (IR), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and Raman spectroscopy. Only the Ca-Cd series displays complete solid solution, although under the synthesis conditions of this study the Cd-5(PO4)(3)OH end member could not be synthesized as a pure phase. Within the Ca-Cd series the cell parameters, IR active modes and Raman active bands vary linearly as a function of Cd content. X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) suggest that the Cd is distributed across both the Ca(1) and Ca(2) sites, even at low Cd concentrations. In order to explore the likely detection limits for mixed-metal phosphates in soils for XRD and Raman spectroscopy, soils doped with mixed-metal hydroxylapatites at concentrations of 5, 1 and 0.5 wt.% were then studied. X-ray diffraction could not confirm unambiguously the presence or identity of mixed-metal phosphates in soils at concentrations below 5 wt.%. Raman spectroscopy proved a far more sensitive method for the identification of mixed-metal hydroxylapatites in soils, which could positively identify the presence of such phases in soils at all the dopant concentrations used in this study. Moreover, Raman spectroscopy could also provide an accurate assessment of the degree of chemical substitution in the hydroxylapatites even when present in soils at concentrations as low as 0.1%.

Uptake kinetics of metals by the earthworm Eisenia fetida exposed to field-contaminated soils

It is well known that earthworms can accumulate metals. However, most accumulation studies focus on Cd-, Cu-, Pb- or Zn-amended soils, additionally few studies consider accumulation kinetics. Here we model the accumulation kinetics of 18 elements by Eisenia fetida, exposed to 8 metal-contaminated and 2 uncontaminated soils. Tissue metal concentration was determined after 3, 7,14, 21, 28 and 42 days. Metal elimination rate was important in determining time to reach steady-state tissue metal concentration. Uptake flux to elimination rate ratios showed less variation and lower values for essential than for non-essential metals. In theory kinetic rate constants are dependent only on species and metal. Therefore it should be possible to predict steady-state tissue metal concentrations on the basis of very few measurements using the rate constants. However, our experiments show that it is difficult to extrapolate the accumulation kinetic constants derived using one soil to another. (C) 2009 Elsevier Ltd. All rights reserved.

Incorporation of lead into calcium carbonate granules secreted by earthworms living in lead contaminated soils

The influence of soil organisms on metal mobility and bioavailability in soils is not currently fully understood. We conducted experiments to determine whether calcium carbonate granules secreted by the earthworm Lumbricus terrestris could incorporate and immobilise lead in lead- and calcium- amended artificial soils. Soil lead concentrations were up to 2000 mg kg-1 and lead:calcium ratios by mass were 0.5-8. Average granule production rates of 0.39 + 0.04 mgcalcite earthworm-1 day-1 did not vary with soil lead concentration. The lead:calcium ratio in granules increased significantly with that of the soil (r2 = 0.81, p = 0.015) with lead concentrations in granules reaching 1577 mg kg-1. X-ray diffraction detected calcite and aragonite in the granules with indications that lead was incorporated into the calcite at the surface of the granules. In addition to the presence of calcite and aragonite X-ray absorption spectroscopy indicated that lead was present in the granules mainly as complexes sorbed to the surface but with traces of lead-bearing calcite and cerussite. The impact that lead-incorporation into earthworm calcite granules has on lead mobility at lead-contaminated sites will depend on the fraction of total soil lead that would be otherwise mobile.

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.

Field trials to assess the uptake of arsenic by vegetables from contaminated soils and soil remediation with iron oxides

The uptake of arsenic (As) by plants from contaminated soils presents a health hazard that may affect the use of agricultural and former industrial land. Methods for limiting the hazard are desirable. A proposed remediation treatment comprises the precipitation of iron (Fe) oxides in the contaminated soil by adding ferrous sulfate and lime. The effects on As bioavailability were assessed using a range of vegetable crops grown in the field. Four UK locations were used, where soil was contaminated by As from different sources. At the most contaminated site, a clay loam containing a mean of 748 mg As kg(-1) soil, beetroot, calabrese, cauliflower, lettuce, potato, radish and spinach were grown. For all crops except spinach, ferrous sulfate treatment caused a significant reduction in the bioavailability of As in some part of the crop. Application of ferrous sulfate in solution, providing 0.2% Fe oxides in the soil (0-10 cm), reduced As uptake by a mean of 22%. Solid ferrous sulfate was applied to give concentrations of 0.5% and 1% Fe oxides: the 0.5% concentration reduced As uptake by a mean of 32% and the 1% concentration gave no significant additional benefit. On a sandy loam containing 65 mg As kg(-1) soil, there was tentative evidence that ferrous sulfate treatment up to 2% Fe oxides caused a significant reduction in lettuce As, but calabrese did not respond. At the other two sites, the effects of ferrous sulfate treatment were not significant, but the uptake of soil As was low in treated and untreated soils. Differences between sites in the bioavailable fraction of soil As may be related to the soil texture or the source of As. The highest bioavailability was found on the soil which had been contaminated by aerial deposition and had a high sand content. (C) 2003 Elsevier Science B.V. All rights reserved.

Field trial using bone meal amendments to remediate mine waste derived soil contaminated with zinc, lead and cadmium

Bone meal amendments are being considered as a remediation method for metal-contaminated wastes. In various forms (biogenic, geogenic or synthetic), apatite, the principal mineral constituent of bone, has shown promise as an amendment to remediate metal-contaminated soils via the formation of insoluble phosphates of Pb and possibly other metals. The efficacy of commercially available bovine bone meal in this role was investigated in a field trial at Nenthead, Cumbria with a mine waste derived soil contaminated with Zn, Pb and Cd. Two 5 m(2) plots were set up: the first as a control and the second, a treatment plot where the soil was thoroughly mixed with bone meal to a depth of 50 cm at a soil to amendment ratio of 25:1 by weight. An array of soil solution samplers (Rhizon SMS (TM)) were installed in both plots and the soil pore water was collected and analysed for Ca, Cd, Zn and Pb regularly over a period of 2 a. Concurrently with the field trial, a laboratory trial with 800 mm high and 100 mm wide leaching Columns Was conducted using identical samplers and with soil from the held site. A substantial release of Zn, Pb, Cd and Ca was observed associated with the bone meal treatment. This release was transient in the case of the leaching columns, and showed seasonal variation in the case of the field trial. It is proposed that this effect resulted from metal complexation with organic acids released during breakdown of the bone meal organic fraction and was facilitated by the relatively high soil pH of 7.6-8.0. Even after this transient release effect had subsided or when incinerated bone meal was substituted in order to eliminate the organic fraction, no detectable decrease in dissolved metals was observed and no P was detected in solution, in contrast with an earlier small column laboratory study. It is concluded that due to the relative insolubility of apatite at above-neutral pH, the rate of supply of phosphate to soil solution was insufficient to result in significant precipitation of metal phosphates and that this may limit the effectiveness of the method to more acidic soils. (c) 2008 Elsevier Ltd. All rights reserved.

Field trials to assess the uptake of arsenic by vegetables from contaminated soils and soil remediation with iron oxides

The uptake of arsenic (As) by plants from contaminated soils presents a health hazard that may affect the use of agricultural and former industrial land. Methods for limiting the hazard are desirable. A proposed remediation treatment comprises the precipitation of iron (Fe) oxides in the contaminated soil by adding ferrous sulfate and lime. The effects on As bioavailability were assessed using a range of vegetable crops grown in the field. Four UK locations were used, where soil was contaminated by As from different sources. At the most contaminated site, a clay loam containing a mean of 748 mg As kg(-1) soil, beetroot, calabrese, cauliflower, lettuce, potato, radish and spinach were grown. For all crops except spinach, ferrous sulfate treatment caused a significant reduction in the bioavailability of As in some part of the crop. Application of ferrous sulfate in solution, providing 0.2% Fe oxides in the soil (0-10 cm), reduced As uptake by a mean of 22%. Solid ferrous sulfate was applied to give concentrations of 0.5% and 1% Fe oxides: the 0.5% concentration reduced As uptake by a mean of 32% and the 1% concentration gave no significant additional benefit. On a sandy loam containing 65 mg As kg(-1) soil, there was tentative evidence that ferrous sulfate treatment up to 2% Fe oxides caused a significant reduction in lettuce As, but calabrese did not respond. At the other two sites, the effects of ferrous sulfate treatment were not significant, but the uptake of soil As was low in treated and untreated soils. Differences between sites in the bioavailable fraction of soil As may be related to the soil texture or the source of As. The highest bioavailability was found on the soil which had been contaminated by aerial deposition and had a high sand content. (C) 2003 Elsevier Science B.V. All rights reserved.

Does ochre have the potential to be a remedial treatment for As-contaminated soils?

Ochre is an iron oxyhydroxide-rich waste that accumulates in water bodies associated with disused mines. Laboratory experiments were conducted to examine the potential of four different ochres to be used as remedial agents for As contaminated soils. The ochres removed As from solution (200 and 500 mg L−1) in adsorption experiments at pH 3 and 8 and, when added to As contaminated soil (5% w/w) significantly reduced As release to solution. In both these experiments the highest surface area ochres performed best. The impact of ochre amendments on uptake of As from soil by plants and humans and release of As to ground water was assessed in a year-long incubation study. Ochres increased soil pH and reduced CaCl2 extractable As but had no consistent effect on plant growth, plant As uptake or As extraction in physiologically-based extraction tests. Ochre may be better used for water treatment than soil remediation.

A review of biochars’ potential role in the remediation, revegetation and restoration of contaminated soils

Biochars are biological residues combusted under low oxygen conditions, resulting in a porous, low density carbon rich material. Their large surface areas and cation exchange capacities, determined to a large extent by source materials and pyrolysis temperatures, enables enhanced sorption of both organic and inorganic contaminants to their surfaces, reducing pollutant mobility when amending contaminated soils. Liming effects or release of carbon into soil solution may increase arsenic mobility, whilst low capital but enhanced retention of plant nutrients can restrict revegetation on degraded soils amended only with biochars; the combination of composts, manures and other amendments with biochars could be their most effective deployment to soils requiring stabilisation by revegetation. Specific mechanisms of contaminant-biochar retention and release over time and the environmental impact of biochar amendments on soil organisms remain somewhat unclear but must be investigated to ensure that the management of environmental pollution coincides with ecological sustainability.

The impact of Eisenia veneta on As, Cu, Pb and Zn uptake by ryegrass (Lolium perenne L)

Earthworms are an essential part of the soil fauna in many global soils, represent a significant proportion of the soil biomass and are regarded as a useful indicator of soil health and quality (Edwards, 2004). They are also often the subject of inoculation programmes during the restoration of degraded lands (Butt, 1999) and the inoculation of earthworms to metal-contaminated soils has been suggested (Dickinson, 2000) largely due to the role earthworms are known to play in soil formation at such sites (Frouz et al., 2007).