Trace element mobility in a contaminated soil two years after field-amendment with a greenwaste compost mulch

Application of greenwaste compost to brownfield land is increasingly common in soil and landscape restoration. Previous studies have demonstrated both beneficial and detrimental effects of this material on trace element mobility. A pot experiment with homogenised soil/compost investigated distribution and mobility of trace elements, two years after application of greenwaste compost mulch to shallow soils overlying a former alkali-works contaminated with Pb, Cu and As (∼900, 200 and 500 mg kg⁻¹, respectively). Compost mulch increased organic carbon and Fe in soil pore water, which in turn increased As and Sb mobilization; this enhanced uptake by lettuce and sunflower. A very small proportion of the total soil trace element pool was in readily-exchangeable form (<0.01% As, <0.001% other trace elements), but the effect of compost on behaviour of metals was variable and ambiguous. It is concluded that greenwaste compost should be applied with caution to multi-element contaminated soils.     

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.     

Mercury in United Kingdom topsoils; concentrations, pools, and Critical Limit exceedances

The median total mercury concentration in 898 UK rural topsoils, sampled between 1998 and 2008, was 0.095 μg g⁻¹. Approximate adjustment for unreactive metal produced an estimate of 0.052 μg g⁻¹ for reactive Hg. The highest concentrations were in the north and west, where organic-rich soils with low bulk densities dominate, but the spatial pattern was quite different if soil Hg pools (mg m⁻²) were considered, the highest values being near to the industrial north of England and London. Possible toxic effects of Hg were best evaluated by comparison with soil Critical Limits expressed as ratios of Hg to soil organic matter, or soil solution Hg²⁺ concentrations, estimated by chemical speciation modelling. Only a few percent of the rural UK soils showed exceedance, and this also applied to rural soils from the whole of Europe. UK urban and industrial soils had higher Hg concentrations and more cases of exceedance.     

Distribution, speciation and availability of antimony (Sb) in soils and terrestrial plants from an active Sb mining area

Here, we present one of the first studies investigating the mobility, solubility and the speciation-dependent in-situ bioaccumulation of antimony (Sb) in an active Sb mining area (Xikuangshan, China). Total Sb concentrations in soils are high (527-11,798 mg kg⁻¹), and all soils, including those taken from a paddy field and a vegetable garden, show a high bioavailable Sb fraction (6.3-748 mg kg⁻¹), dominated by Sb(V). Elevated concentrations in native plant species (109-4029 mg kg⁻¹) underpin this. Both chemical equilibrium studies and XANES data suggest the presence of Ca[Sb(OH)₆]₂, controlling Sb solubility. A very close relationship was found between the citric acid extractable Sb in plants and water or sulfate extractable Sb in soil, indicating that citric acid extractable Sb content in plants may be a better predictor for bioavailable Sb in soil than total acid digestible Sb plant content.     

Influence of tidal regime on the distribution of trace metals in a contaminated tidal freshwater marsh soil colonized with common reed (Phragmites australis)

A historical input of trace metals into tidal marshes fringing the river Scheldt may be a cause for concern. Nevertheless, the specific physicochemical form, rather than the total concentration, determines the ecotoxicological risk of metals in the soil. In this study the effect of tidal regime on the distribution of trace metals in different compartments of the soil was investigated. As, Cd, Cu and Zn concentrations in sediment, pore water and in roots were determined along a depth profile. Total sediment metal concentrations were similar at different sites, reflecting pollution history. Pore water metal concentrations were generally higher under less flooded conditions (mean is (2.32 ± 0.08) × 10⁻³ mg Cd L⁻¹ and (1.53 ± 0.03) × 10⁻³ mg Cd L⁻¹). Metal concentrations associated with roots (mean is 202.47 ± 2.83 mg Cd kg⁻¹ and 69.39 ± 0.99 mg Cd kg⁻¹) were up to 10 times higher than sediment (mean is 20.48 ± 0.19 mg Cd kg⁻¹ and 20.42 ± 0.21 mg Cd kg⁻¹) metal concentrations and higher under dryer conditions. Despite high metal concentrations associated with roots, the major part of the metals in the marsh soil is still associated with the sediment as the overall biomass of roots is small compared to the sediment.     

Avoidance tests with Folsomia candida for the assessment of copper contamination in agricultural soils

The feasibility of assessing copper accumulation in agricultural soils using avoidance tests with a Canadian strain of Folsomia candida was investigated under laboratory conditions. The avoidance response to nominal copper sulfate concentrations of 0, 200, 800, 1600 and 3200 mg kg⁻¹ in OECD soil was inconsistent between trials with the standard plastic cup or a modified Petri dish method requiring less soil. However, combined results from three Petri dish trials decreased variability and provided a 75% avoidance level, close to the 80% criterion proposed for avoidance tests. A Copper avoidance EC_50s of 18 mg kg⁻¹was obtained using the Petri dish method whether tests were conducted with or without light. While Petri dish tests have potential as a cheap tool to distinguish metal contaminated soils from uncontaminated soils they would be unsuitable for tracking or quantifying changes in metal concentrations. throughout remediation. Advantages and limitations of the method have been presented.     

Enhancing p-cresol extraction from soil

Soil washing is a potential technology for rapid removal of organic hydrocarbons sorbed to soils. In this work, p-cresol desorption with different non-ionic surfactants (Tween 80, Brij 30 and Triton X-100) was compared to cyclodextrine and citrate as solubilizer. A series of batch extraction experiments were conducted at 20 °C using the field soil with different extracting solutions at various concentrations to investigate the removal efficiency and to optimize the concentration of the extractant. The use of the different extracting agents was very selective to p-cresol extraction, minimizing soil organic matter releasing and maintaining the natural pH of the soil. The highest asymptotic values of desorption percentages were obtained for Tween 80 and Brij 30 at 48 h. However, Brij 30 ecotoxicity (EC₅₀ = 0.5 mg L⁻¹) is in the same order of that obtained for p-cresol, being this surfactant clearly ruled out. Liquid to solid ratio of 2.5 mL g⁻¹ presented the best extraction results, while concentrations higher than 1 g L⁻¹ for Tween 80 and Citrate did not produce any significant effect on the desorption efficiency. p-Cresol extraction efficiencies higher than 70% and 60% for Tween 80 and Citrate, respectively.     

Correlation of foliar MT2b expression with Cd and Zn concentrations in hybrid aspen (Populus tremula × tremuloides) grown in contaminated soil

Metal uptake and its effect on foliar metallothionein 2b (MT2b) mRNA levels were studied in hybrid aspen (Populus tremula × tremuloides) in field conditions. The trees were planted on a site contaminated with several metals, including cadmium (mean 5.1 mg kg⁻¹), chromium (80 mg kg⁻¹), copper (180 mg kg⁻¹), nickel (81 mg kg⁻¹), vanadium (240 mg kg⁻¹) and zinc (520 mg kg⁻¹). Of the ten trace elements analyzed, only Cd and Zn accumulated in the leaves with maximal foliar concentrations of 35 and 2400 mg kg⁻¹ (dry weight), respectively. There was a strong correlation between Cd and Zn concentrations and bioaccumulation factors (concentration in plant/soil) in the leaves, branches and roots, suggesting similar transport mechanisms for these two metals. The levels of MT2b correlated with Cd and Zn concentrations in the leaves, demonstrating that increased MT2b expression is one of the responses of hybrid aspen to chronic metal exposure.     

Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40 g kg⁻¹) and steel slag (3 and 6 g kg⁻¹) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

A root exudates based approach to assess the long-term phytoavailability of metals in biosolids-amended soils

Organic acids present in the rhizosphere of growing plants are widely recognized to be responsible for dissolving the solid phase metals in the soil and making them available for plant absorption. We proposed a root exudates-based model to assess the long-term phytoavailability of metals in biosolids-amended soils. The phytoavailability of biosolids-borne metals was defined in terms of a capacity factor and an intensity factor. The plant available metal pool, C₀ (capacity factor, mg kg⁻¹), can be estimated by fitting the successive organic acids extraction data to an exponential decay kinetic equation. The field metal removal rate, k (intensity factor, yr⁻¹), can be estimated from the successive extraction-based metal release rate through an effective annual organic acid production in the rhizosphere which was found to be characteristic of plant species. The protocol was successfully used to assess the long-term phytoavailability of metals in biosolids-amended soil from two biosolids land application sites.     

Chelant-aided enhancement of lead mobilization in residential soils

Chelation of metals is an important factor in enhancing solubility and hence, availability to plants to promote phytoremediation. We compared the effects of two chelants, namely, ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS) in enhancing mobilized lead (Pb) in Pb-based paint contaminated residential soils collected from San Antonio, Texas and Baltimore, Maryland. Batch incubation studies were performed to investigate the effectiveness of the two chelants in enhancing mobilized Pb, at various concentrations and treatment durations. Over a period of 1 month, the mobilized Pb pool in the San Antonio study soils increased from 52 mg kg⁻¹ to 287 and 114 mg kg⁻¹ in the presence of 15 mM kg⁻¹ EDTA and EDDS, respectively. Stepwise linear regression analysis demonstrated that pH and organic matter content significantly affected the mobilized Pb fraction. The regression models explained a large percentage, from 83 to 99%, of the total variation in mobilized Pb concentrations.     

Accumulation of mercury and methylmercury by mushrooms and earthworms from forest soils

Accumulation of total and methyl-Hg by mushrooms and earthworms was studied in thirty-four natural forest soils strongly varying in soil physico-chemical characteristics. Tissue Hg concentrations of both receptors did hardly correlate with Hg concentrations in soil. Both total and methyl-Hg concentrations in tissues were species-specific and dependent on the ecological groups of receptor. Methyl-Hg was low accounting for less than 5 and 8% of total Hg in tissues of mushrooms and earthworms, respectively, but with four times higher concentrations in earthworms than mushrooms. Total Hg concentrations in mushrooms averaged 0.96 mg Hg kg⁻¹ dw whereas litter decomposing mushrooms showed highest total Hg and methyl-Hg concentrations. Earthworms contained similar Hg concentrations (1.04 mg Hg kg⁻¹ dw) whereas endogeic earthworms accumulated highest amounts of Hg and methyl-Hg.     

Feasibility of phytoextraction to remediate cadmium and zinc contaminated soils

A Cd and Zn contaminated soil was mixed and equilibrated with an uncontaminated, but otherwise similar soil to establish a gradient in soil contamination levels. Growth of Thlaspi caerulescens (Ganges ecotype) significantly decreased the metal concentrations in soil solution. Plant uptake of Cd and Zn exceeded the decrease of the soluble metal concentrations by several orders of magnitude. Hence, desorption of metals must have occurred to maintain the soil solution concentrations. A coupled regression model was developed to describe the transfer of metals from soil to solution and plant shoots. This model was applied to estimate the phytoextraction duration required to decrease the soil Cd concentration from 10 to 0.5 mg kg⁻¹. A biomass production of 1 and 5 t dm ha⁻¹ yr⁻¹ yields a duration of 42 and 11 yr, respectively. Successful phytoextraction operations based on T. caerulescens require an increased biomass production.     

Triclosan affects the microbial community in simulated sewage-drain-field soil and slows down xenobiotic degradation

Effects of the common antibacterial agent triclosan on microbial communities and degradation of domestic xenobiotics were studied in simulated sewage-drain-field soil. Cultivable microbial populations decreased 22-fold in the presence of 4 mg kg⁻¹ of triclosan, and triclosan-resistant Pseudomonas strains were strongly enriched. Exposure to triclosan also changed the general metabolic profile (Ecoplate substrate profiling) and the general profile (T-RFLP) of the microbial community. Triclosan degradation was slow at all concentrations tested (0.33-81 mg kg⁻¹) during 50-days of incubation. Mineralization experiments (¹⁴C-tracers) and chemical analyses (LC-MS/MS) showed that the persistence of a linear alkylbenzene sulfonate (LAS) and a common analgesic (ibuprofen) increased with increasing triclosan concentrations (0.16-100 mg kg⁻¹). The largest effect was seen for LAS mineralization which was severely reduced by 0.16 mg kg⁻¹ of triclosan. Our findings indicate that environmentally realistic concentrations of triclosan may affect the efficiency of biodegradation in percolation systems.     

Effect of natural organic matter and green microalga on carboxyl-polyethylene glycol coated CdSe/ZnS quantum dots stability and transformations under freshwater conditions

The influence of pH, ionic strength, presence of humic or alginic acids, extracellular polymeric substances (EPS), or freshwater microalga Chlorella kesslerii on the stability and transformation of carboxyl-PEG-CdSe/ZnS core/shell quantum dots (QDs) in terms of number, hydrodynamic size and fluorescence of individual particles, was studied by fluorescence correlation spectroscopy. Obtained results demonstrated that QDs form stable dispersions at nanomolar concentrations under conditions typical for freshwaters. The presence of 5 or 15 mg C L⁻¹ of humic acid or 50 mg C L⁻¹ EPS did not significantly affect these parameters. In contrast, 5 or 50 mg C L⁻¹ alginate at ionic strength of 10 mM shifted the hydrodynamic radius toward larger values, suggesting a possible capture of QDs by the linear alginate chains. The addition of microalga to the QD dispersions resulted in a slight reduction of the number of QDs and a significant decline in the fluorescence of individual QDs.     

Planting woody crops on dredged contaminated sediment provides both positive and negative effects in terms of remediation

There is currently a requirement for studies focusing on the long-term sustainability of phytoremediation technologies. Trace element uptake by Salix, Populus and Alnus species planted in dredged contaminated canal sediment and concentrations in sediment and pore waters were investigated, eight years after a phytoremediation trial was initiated in NW England. Soil biological activity was also measured using invertebrate and microbial assays to determine soil quality improvements. Zinc was the dominant trace metal in foliage and woody stems, and the most mobile trace element in sediment pore water (∼14 mg l⁻¹). Biological activity had improved; earthworm numbers had increased from 5 to 24, and the QBS index (an index of microarthropod groups in soil) had increased from 70 to 88. It is concluded that biological conditions had improved and natural processes appear to be enhancing soil quality, but there remains a potential risk of trace element transfer to the wider environment.     

Leaching of copper and zinc from spent antifouling paint particles

Leaching of Cu and Zn from a composite of spent antifouling paint particles, containing about 300 mg g⁻¹ and 110 mg g⁻¹ of the respective metals, was studied in batch experiments. For a given set of simulated environmental conditions, release of Cu was independent of paint particle concentration due to attainment of pseudo-saturation, but Zn was less constrained by solubility effects and release increased with increasing particle concentration. Leaching of Cu increased but Zn decreased with increasing salinity, consistent with mechanisms governing the dissolution of Cu₂O in the presence of chloride and Zn acrylates in the presence of seawater cations. Because of complex reaction kinetics and the presence of calcium carbonate in the paint matrix, metal leaching appeared to be greater at 4 °C than 19 °C under many conditions. These findings have important environmental and biological implications regarding the deliberate or inadvertent disposal of antifouling paint residues.     

Effectiveness of urea in enhancing the extractability of 2,4,6-trinitrotoluene from chemically variant soils

One of the major challenges in developing an effective phytoremediation technology for 2,4,6-trinitrotoluene (TNT) contaminated soils is limited plant uptake resulting from low solubility of TNT. The effectiveness of urea as a solubilizing agent in increasing plant uptake of TNT in hydroponic systems has been documented. Our preliminary greenhouse experiments using urea were also very promising, but further characterization of the performance of urea in highly-complex soil-solution was necessary. The present study investigated the natural retention capacity of four chemically variant soils and optimized the factors influencing the effectiveness of urea in enhancing TNT solubility in the soil solutions. Results show that the extent of TNT sorption and desorption varies with the soil properties, and is mainly dependent on soil organic matter (SOM) content. Hysteretic desorption of TNT in all tested soils suggests irreversible sorption of TNT and indicates the need of using an extractant to increase the release of TNT in soil solutions. Urea significantly (p < 0.0001) enhanced TNT extraction from all soils, by increasing its solubility at the solid/liquid interface. Soil organic matter content and urea application rates showed significant effects, whereas pH did not exert any significant effect on urea catalysis of TNT extraction from soil. The optimum urea application rates (125 or 350 mg kg⁻¹) for maximizing TNT extraction were within the limits set by the agronomic fertilizer-N rates used for major agricultural crops. The data obtained from this batch study will facilitate the optimization of a chemically-catalyzed phytoremediation model for cleaning up TNT-contaminated soils.     

Influence of humified organic matter on copper behavior in acid polluted soils

The main purpose of this work was to identify the role of soil humic acids (HAs) in controlling the behavior of Cu(II) in vineyard soils by exploring the relationship between the chemical and binding properties of HA fractions and those of soil as a whole. The study was conducted on soils with a sandy loam texture, pH 4.3-5.0, a carbon content of 12.4-41.0 g kg⁻¹ and Cu concentrations from 11 to 666 mg kg⁻¹. The metal complexing capacity of HA extracts obtained from the soils ranged from 0.69 to 1.02 mol kg⁻¹, and the stability constants for the metal ion-HA complexes formed, log K, from 5.07 to 5.36. Organic matter-quality related characteristics had little influence on Cu adsorption in acid soils, especially if compared with pH, the degree of Cu saturation and the amount of soil organic matter.