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Two soils contaminated with potentially toxic metals (PTMs) contrasting in pH and mineralogy were remediated with CaEDTA, and changes in soil organic matter (SOM) composition were investigated. Previous studies showed no significant loss of SOM from CaEDTA-treated soils, but the results of our study reflected significant decreases (from 46 to 49%) in the free fraction of humic acids (HAs). Remediation affected the composition of the free HA fraction via disturbance of intermolecular bonds — an increase in phenolic and aromatic groups with a simultaneous decrease in carbohydrates — which was confirmed by FTIR spectroscopy in both soils. Because non-radical molecules such as carbohydrates were selectively removed, the concentration of free radicals in the free HA fraction increased in acidic soil. The bound fraction of HAs and fulvic acids (FAs) in SOM, which are important due to their stability and the permanent effects they have on the soil’s physical properties, remained unchanged in both remediated soils. The effect of soil recultivation was observed only in the excitation emission matrix (EEM) fluorescence spectra of HAs. In terms of SOM, CaEDTA soil washing can be considered moderately conservative; however, the restoration of free humic fractions is likely to be a long-term process. Supplementary Information The online version contains supplementary material available at 10.1007/s11356-021-15406-z.

Sewage sludge (SS) is a potential resource for P and other nutrients, but often contaminated with metals. SS containing Pb-102, Zn-968, Cu-267, Cr-101, Mn-222, and Fe-8374 mg kg$^{-1}$ was washed in a batch process for 1 h with a recycled washing solution containing 50 mmol L$^{-1}$ of recycled EDTA and 50 mmol L$^{-1}$ H$_2$SO$_4$, solid/liquid ratio 1/7 (w/V). After solid/liquid separation, the washed SS was further rinsed 3-times with cleansed recycled solutions. EDTA and process solutions were recycled/cleansed in a pH gradient of 12.5–2.0 imposed by addition of CaO and H$_2$SO$_4$ (the ReSoil® method). EDTA, recycled as ineffective Ca-EDTA, was activated by capturing Ca with H$_2$SO$_4$. The process was closed-looped, no wastewater was generated, solid waste was centrifuged away. 10 consecutive SS washing batches preserved the quality of the process solutions. Metals were mainly removed from the SS organic fraction, the average removal was Pb-35, Zn-59, Cu-60, Cr-19, Mn-25, and Fe-1%. Washing reduced the leachability of Cu and Cr from SS by 13.4 and 3.5 times, but increased the leachability of Pb, Zn, Mn, and Fe by 2.5, 3.8, 1.9, and 1.6 times, respectively. Metal concentrations in the leachates were below the limits stipulated as hazardous. The content of accessible P and K in washed SS decreased by 24 and 45%, and the total N decreased by 10%. Overall, the results prove the feasibility of the novel SS washing process.

In this study, we evaluated the impact of washing of Pb, Zn and Cd contaminated soil using EDTA-based technology (ReSoil®) on soil biological properties by measuring some of the most commonly used/sensitive biological indicators of soil perturbation. We estimated the temporal dynamics of the soil respiration, the activities of soil enzymes (dehydrogenase, β-glucosidase, urease, acid and alkaline phosphatase), and the effect of the remediation process on arbuscular mycorrhizal (AM) fungi in original (Orig), remediated (Rem) and remediated vitalized (Rem+V) soils during a more than one-year garden experiment. ReSoil® technology initially affected the activity level of soil microbial respiration and all enzyme activities except urease and reduced AM fungal potential in the soil. However, after one year of vegetable cultivation and standard gardening practices, soil microbial respiration, acid and alkaline phosphatase in the Rem and Rem+V reached similar activities as in the Orig. Only the activities of dehydrogenase and β-glucosidase remained lower in the remediated soil compared to the Orig. The frequency of arbuscular mycorrhiza in the root system, arbuscular density in the colonized root fragment, and the intensity of mycorrhizal colonization in the colonized root fragments in the remediated treatments increased with time; at the end of the experiment, no consistent differences in these parameters of mycorrhizal colonization were found among the treatments. Our results suggest a restored biological functioning of the remediated soil after one year of vegetable cultivation. In general, no differences were found between the Rem and Rem+V treatments, indicating that simple common garden practices are sufficient to restore soil functioning after remediation.

The viable chelator-based soil washing has yet to be demonstrated on a larger scale. Soil containing 1850, 3830 and 21 mg kg$^{−1}$ Pb, Zn and Cd, respectively, was washed with 100 mmol EDTA kg$^{−1}$ in a series of 16 batches (1 ton soil/batch) using the new ReSoil® technology. The ReSoil® recycled the process water and 85% of the EDTA, producing no wastewater and 14.4 kg ton$^{−1}$ of waste. The soil washing removed 71, 28 and 53% of Pb, Zn and Cd, respectively, mainly from the carbonate fraction, saturated the soil with basic cations and increased the soil pH by up to 0.5 units. Raised beds (4 × 1 × 0.5 m) with original (contaminated) and remediated soil were constructed as lysmeters, and local produce was grown from July 2018 to November 2019. Throughout the gardening period, the concentration of Pb and Cd in the leachates from the remediated soil was lower and that of Zn was higher than in the original soil. Remediation decreased the concentration of plant-available and mobile toxic metals, as determined by CaCl$_2$ and NH$_4$NO$_3$ extractions, and reduced the bioavailability of Pb, Zn, and Cd in the simulated human gastrointestinal phase by an average of 4.3, 1.7 and 2.7-fold, respectively. Revitalization with vermicompost, earthworms and rhizosphere soil, and spring fertilisation with compost and manure, had no significant effect on the mobility and accessibility of the toxic metals. The ReSoil® is a cost-effective technology (material cost = 18.27 € ton$^{−1}$ soil) and showed the prospect of sustainable reuse of remediated soil.

Efficiency and the preservation of soil functions are key requirements for sustainable remediation of contaminated soil. Microbial decomposition and conversion of substrates is a fundamental soil function. Pilot-scale EDTA-based soil washing recycled chelant generated no wastewater and removed 78% of Pb from acidic farmland soil with 860 mg kg−1 Pb and 60% of Pb from calcareous garden soil with 1030 mg kg−1 Pb. Remediation had an insignificant effect on microbial respiration in acidic soil induced by sequential additions of glucose, micro-cellulose, starch and alfa-alfa sprout powder (mimicking litter components, C-cycle). In contrast, remediation of calcareous soil reduced cumulative CO2 production after glucose (simple) and alfalfa (complex substrate) addition, by up to 40%. Remediation reduced the nitrification rate (denoting the N-cycle) in acidic soil by 30% and halved nitrification in calcareous soil. Remediation in both soils slightly or positively affected dehydrogenase and β-glucosidase activity (associated with C-cycle), and decreased urease activity (N-cycle). Generally, EDTA remediation modestly interfered with substrate utilisation in acidic soil. A more prominent effect of remediation on the functioning of calcareous soil could largely be attributed to the use of a higher EDTA dose (30 vs. 100 mmol kg−1, respectively).

The increasing occurrence of cyanobacterial blooms in water bodies is a serious threat to the environment. Efficient in-lake treatment methods for the control of cyanobacteria proliferation are needed, their in-vivo detection to obtain a real-time response to their presence, as well as the information about their physiological state after the applied treatment. In-vivo fluorescence measurements of photosynthetic pigments have proved to be effective for quantitative and qualitative detection of phytoplankton in a water environment. In the experiment, chlorophyll and phycocyanin fluorescence sensors were used concurrently to detect stress caused by electrochemical oxidation applying an electrolytic cell equipped with borondoped diamond electrodes on a laboratory culture of cyanobacteria Microcystis aeruginosa PCC 7806. The inflicted injuries were reflected in a clear transient increase in the phycocyanin fluorescence signal (for 104 %± 43%) 24 h after the treatment, which was not the case for the chlorophyll fluorescence signal. In the next 72 h of observation, the fluorescence signals decreased (on 40% of the starting signal) indicating a reduction of cell number, which was confirmed by cell count (24% reduction of the starting concentration) and analysis of extracted chlorophyll and phycocyanin pigment. These results demonstrate the viability of the combined application of two sensors as a useful tool for in-vivo detection of induced stress, providing real-time information needed for the evaluation of the efficiency of the in-lake treatment and decision upon the necessity of its repetition. The electrochemical treatment also resulted in a lower free microcystins concentration compared to control.

Soil chemistry of toxic metalloids and metals differs, making their simultaneous removal difficult. Soil contaminated with As, Pb, Zn and Cd was washed with oxalic acid, Na-dithionite and EDTA solution. Toxic elements were removed from the washing solution by alkalinisation with CaO to a pH 12.5: As was co-precipitated with Fe from Fe-EDTA chelate formed after the soil washing. The toxic metals precipitated after substitution of their EDTA chelates with Ca. The novel method was scaled up on the ReSoil® platform. On average, 60, 76, 29, and 53% of As, Pb, Zn, and Cd were removed, no wastewater was generated and EDTA was recycled. Addition of zero-valent iron reduced the toxic elements' leachability. Remediation was most effective for As: phytoaccessibility (CaCl

Soil remediation mitigates hazards from contaminants but could deprive soils of initial biota and enzymes. Historically contaminated acidic soil from Arnoldstein (Austria) and calcareous soil from Meza (Slovenia) were washed with 30 and 100 mmol kg−1 ethylenediaminetetraacetate (EDTA) to remove 78 and 60% of Pb as a main pollutant. Remediation of the Arnoldstein soil decreased urease activity and increased β-glucosidase activity, measured in a 15-week experiment. The dehydrogenase activity and microbial gene abundances were not significantly impeded compared to the original soil. Conversely, the use of a high dose of EDTA in the Meza soil, necessary for effective remediation of calcareous soils, resulted in pronouncedly decreased enzyme activities (3.2 times on average) and repressed fungal ITS and increased bacterial 16S rRNA gene abundance. Remediation shifted the microbial community composition in both soils. For revitalisation, the remediated soils were amended with compost, inocula of un-contaminated soil and (Arnoldstein soil) biochar enriched with soil extract. Amendments inconsistently affected the Arnoldstein soil: compost increased the dehydrogenase activity and altered the microbial community composition, biochar enhanced the β-glucosidase activity, and all amendments decreased the microbial abundance (1.6 times on average). In contrast, amendments efficiently revitalised the remediated Meza soil; compost and soil inoculum returned the enzyme activities back to the baseline in the original soil, increased the fungal abundance above that in the original soil and restored the microbial community composition.

Remediation with chelants can restore metal-contaminated soils for use as a natural resource. Calcareous soil from Meza Valley, Slovenia, and acidic soils from Arnoldstein, Austria, and Pribram, Czech Republic (with 1,028, 862, and 926 mg ∙Pb∙kg−1, respectively), were washed with 60–100 mmol EDTA per kilogram of air-dried soil in series of 30 batches (50 kg soil batch−1). The approach involves a novel reaction that incorporates alkaline substitution, precipitation and adsorption of toxic metals on polysaccharides, and chelant acidic precipitation via 83% EDTA (on average) and complete process water recycling (no wastewater was generated). The pH gradient was imposed by Ca(OH)2 and H2SO4, and excess reagent was removed with the remediated soil as CaSO4, thereby preventing the salification of the recycled waters. Remediation removed 60%, 78%, and 71% of the Pb from the Meza, Arnoldstein, and Pribram soils, respectively, and reduced the Pb bioaccessibility levels in the simulated human gastrointestinal phase by 5.0, 7.7, and 8.1 times. Residual emissions (EDTA, toxic metals) were reduced with soil aging and remediated soil deposition on a reactive permeable barrier. The solid waste generated from the process totaled 10.8 kg tons−1 of the air-dried soil, and the material/energy costs of remediation reached 20.6 € tons−1. These results demonstrate the robustness, efficiency, and safety of this novel approach.

In washing soils contaminated with toxic metals, the replacement of recalcitrant EDTA with biodegradable chelators has gained high expectations. Herein we investigated the feasibility of using EDTA and biodegradable GLDA, EDDS and IDS under conditions pertinent to operational remediation technology, in a pilot-scale experiment. GLDA and IDS did not precipitate from process solutions, which lessened their recyclability. In other process parameters, chelator supplement, Na-saturation of process solutions and processing time, EDTA outperformed biodegradable chelators. Treatment with EDTA was also the most effective in total Pb and Zn removal and least impacted soil properties. GLDA was slightly better in Cd removal. EDDS and IDS were inefficient. All chelators effectively removed easily-available Pb, Zn and Cd from the exchangeable soil fraction. EDTA was the most efficient chelator in reducing the bioaccessibility of Pb and GLDA in reducing the bioaccessibility of Cd from simulated human gastrointestinal tract. Treatment with GLDA had an edge in reducing plant bioaccessibility of toxic metals, but induced worrying leachability of Pb. This was 8.3-times higher than with the process with EDTA and 3.4-times higher than in original soil. In general, our results demonstrate the advantage of EDTA over tested biodegradable chelators in process and remediation efficiency and environmental safety.

The ability of contaminated farmland soils reclaimed by remediation to dissipate pesticides and thus to mitigate their unwanted environmental effects, i.e., leaching and run-off, was studied. Novel EDTA-based soil washing technology (EDTA and process waters recycling; no toxic emissions) removed 79 and 73% of Pb from acidic and calcareous soil with 740 and 2179 mg kg−1 Pb, respectively. The dissipation kinetics of four herbicides: mecoprop-P, isoproturon, bentazon and S-metolachlor was investigated under field conditions in beds with maize (Zea mays) and barley (Hordeum vulgare). The biphasic First-Order Multi-Compartment (FOMC) model was used to fit experimental data and calculate the herbicides’ half-life (DT50) in soil. Remediation significantly (up to 64%) decreased dehydrogenase activity assessed as a marker of soil microbial activity and prolonged the DT50 of herbicides in acidic soils from 16% (isoproturon) to 111% (S-metachlor). Remediation had a less significant effect on herbicide dissipation in calcareous soils; i.e., mecoprop-P DT50 increased by 3%, while isoproturon and S-metachlor DT50 decreased by 29%. Overall, the dissipation from remediated soils was faster than the average DT50 of tested herbicides published in the Pesticides Properties DataBase. Results demonstrate that EDTA-based remediation of the studied soils does not pose any threat of extended herbicide persistence.

Soil is a limited resource often contaminated with heavy metals. Recently, several soil remediation processes have been developed, including an EDTA (ethylenediaminetetraacetic acid) chelating agent extraction that results in high removal efficiency of the contaminants. There is a limited knowledge on how this procedure affects soil microorganisms, including plant root endosymbiotic arbuscular mycorrhizal fungi. In this paper we present data on the mycorrhizal potential of soil after the remediation procedure, as well with the molecular characterization of arbuscular mycorrhizal fungal diversity before and after soil remediation, and before and after soil inoculation with commercial and indigenous (local) fungal inocula using an examination of 18S rRNA clone libraries. After the remediation treatment soils had very low mycorrhizal potential. Functional mycorrhizal symbiosis with plants was established either by commercial or local (grassland roots and rhizosphere soil) inoculum addition to the soil and remediated soil was successfully revitalized after the treatment. The use of the local inoculum resulted in a higher arbuscular mycorrhizal fungal diversity in the roots of plants growing in the remediated soil compared to the ones revitalized with the commercial inoculum.

EDTA-based remediation is reaching maturity but little information is available on the state of chelant in remediated soil. EDTA soil retention was examined after extracting 20 soil samples from Pb contaminated areas in Slovenia, Austria, Czech Republic and USA with 120 mM kg(-1) Na2H2EDTA, CaNa2EDTA and H4EDTA for 2 and 24 h. On average, 73% of Pb was removed from acidic and 71% from calcareous soils (24 h extractions). On average, 15% and up to 64% of applied EDTA was after remediation retained in acidic soils. Much less; in average 1% and up to the 22% of EDTA was retained in calcareous soils. The secondary emissions of EDTA retained in selected remediated soil increased with the acidity of the media: the TCLP (Toxicity Characteristic Leaching Procedure) solution (average pH end point 3.6) released up to 36% of EDTA applied in the soil (28.1 mmol kg(-1)). Extraction with deionised water (pH > 6.0) did not produce measurable EDTA emissions. Exposing soil to model abiotic (thawing/freezing cycles) and biotic (ingestion by earthworms Lumbricus rubellus) ageing factors did not induce additional secondary emissions of EDTA retained in remediated soil.

Soils contaminated with Pb, Zn and Cd are hazardous. Persistent EDTA and biodegradable GLDA, EDDS and IDS have been used as chelators in the ReSoil soil washing technology, which recycles chelator and curbs toxic emissions. The washed soils supported similar growth of buckwheat (F. esculentum) and better growth of Chinese cabbage (B. rapa) compared with the original (not-remediated) soil. The growth of buckwheat on EDDS-washed soil was an exception and was 67% suppressed. The activities of enzymes of the plant antioxidant preventive system were assessed in roots and leaves of Chinese cabbage on all soils. Similar activities were measured, confirming that washed soils are not harmful to the plants. Plant uptake of potentially toxic elements was reduced from all washed soils, i.e. buckwheat grown on GLDA-washed soils accumulated up to 27 and 83 times less Pb and Cd than in the original soil. The initial Pb emissions in leachate from GLDA and IDS washed soils were up to 89 and 92% higher than those of the original soil, respectively. The latter emissions ceased to the levels measured in original, EDTA and EDDS washed soils. Soil physical properties (water holding capacity, aggregate stability) and soil functionality, assessed as soil respiration and activity of enzymes indicative for soil C, N and P cycle, were similar in all soils after 10 weeks of plant growth experiment. The overall results indicate a low impact of the remediation on soil quality. Soils washed with EDTA performed slightly better compared to GLDA-, EDDS- and IDS-washed soils.

The use of EDTA-based soil washing is prevented by chelant environmental persistence and the hazard of toxic post-remedial emissions. Calcareous and acidic soils with 828 and 673 mg Pb kg−1, respectively, and co-contaminated with Zn and Cd, were washed with 90 and 60 mM EDTA, respectively, to remove 67 and 80% of Pb. Washed soils were rinsed until 6.5 and 5.1 mM EDTA, respectively, was measured in the final rinsing solutions. Emissions of residual EDTA and chelated metals from remediated soils were mitigated by adsorption on zero-valent Fe (ZVI), which was added (0.5–1.5%, w/w) to the slurry of washed soil immediately before rinsing. ZVI addition prevented the initial post-remedial surge of toxic metals leachability and minimised toxic emissions from calcareous and acidic soil as soon as 6 and 7 days after remediation, respectively. The extractability/leachability of EDTA and toxic metals from remediated and ZVI amended soils diminished to close to emissions from the original soils, frequently below the limit of quantification by flame-AAS, and was not affected by the pH of the leaching solutions. Efficient curbing of toxic post-remediation emissions as demonstrated herein is of paramount importance for recognition of EDTA-based remediation as environmentally safe.

Soil remediation using stringent chemical extractions deteriorates soil’s properties and functions, and creates the need for efficient soil revitalization measures. Garden soil contaminated with 4037, 2527, and 26 mg kg −1 of Pb, Zn, and Cd, respectively, was washed with a high EDTA dose (120 mmol kg −1 of soil) to final values of 1246, 2138, and 11 mg kg −1 of Pb, Zn, and Cd, respectively. After remediation, the concentration of Mn decreased by 53%, and concentrations of other essential metals: Cu, Fe, Mg, and Ca remained unchanged after remediation. The effect of remediation on the fractionation of soil metals was assessed using modified Tessier sequential extraction procedure. The soil was further amended with fertilizer (N, K, Mn and Mg), manure, hydrogel, vermiculite, apatite, and commercial absorbent (Slovakite) and subjected to spinach ( Spinacia oleracea L.) cultivation in a column experiment. Remediation reduced plant growth, photosynthesis and plant uptake of Pb, Zn, and Cd 2.4, 1.8, and 6.4 times, respectively. Fertilization partly restored net photosynthesis, stomatal conductance, transpiration, and yield of the tested plants. Growth depression was found to be mitigated further by hydrogel (up to 53%). The other tested amendments did not significantly affect the water potential of remediated soil, the leaching and plant uptake of toxic and essential metals, or the growth and photosynthetic functions of the test plant.

article i nfo Geostatistical technique was used to predicted spatial reduction of metal contamination after applying EDTA- based soil remediation. Soil samples from 268 locations in the Meza Valley, Slovenia with Pb and Zn concentra- tions up to 8955 and 15518 mg kg �1 were extracted with the chelating agent ethylenediamine tetraacetate (EDTA). On average, 63 and 22% of Pb and Zn, respectively, were removed with washing solution containing 60 mmol EDTA per kg of soil and 75 and 34% of Pb and Zn with 120 mmol EDTA kg �1 soil. Spatial structure anal- ysis revealed a good spatial structure and little spatial variation of data, which were further interpolated using Empirical Bayesian kriging to produce a continuous surface of Pb and Zn concentrations before and after remedi- ation. Geostatistical simulations showed that the contaminated area covers 19.4 km 2 and that soil remediation (60 mmolEDTAkg �1 )has thepotentialtoreduce theareawith Pb and Zn abovethe criticalregulatorythreshold limit by 91 and 42%, respectively. Validated by pilot-scale remediation trials, soil extractions exhibit little scale- dependency of extraction efficiency. EDTA extraction also significantly reduced the bio-accessibility of toxic metals that remained in the soil after remediation using the unified bio-accessibility method. Pb and Zn concen- trations accessible from the simulated intestinal phase were reduced by up to 99 and 96%, respectively.

In a field experiment on metal contaminated and EDTA-remediated soil we studied plant performance, mycorrhizal associations and prospects of potential re-use of remediated soil as a garden substrate. Two experimental plots of 4 × 1 × 0.3 m were filled, one with remediated and the other with original contaminated soil. Selected cultivars were rotated over the course of 16months. Pb, Zn, Cd and micronutrient plant uptake was measured and their phytoaccessibility was analyzed by the DTPA method. Plant fitness was assessed by chlorophyll fluorescence and gas exchange measurements and evaluation of root colonization were analyzed with mycorrhizal fungi. Remediation reduced Pb and Cd concentrations in roots, green parts and fruits in most of the plants. Phytoaccumulation of Zn was reduced in one half of the cultivars. Some plants suffered from Mn deficiency as total soil Mn was reduced 4-fold and phytoaccessibility of micronutrients Cu, Fe and Mn for 54, 26 and 79%, respectively. Plant biomass was reduced. Photosynthetic parameters of plants grown in original and remediated soil were similar, except for the reduction in Spinacia oleracea. The frequency of mycorrhizal colonization in the roots of Pisum sativum was reduced five-fold and no significant changes were found in Allium cepa roots. Remediation reduced plant uptake of Pb below the concentration stipulated by legislation. Measures to reduce plant accumulation of other toxic metals and to revitalize remediated soil are needed.

We applied a multi-level approach assessing the quality, toxicity and functioning of Pb, Zn and Cd contaminated/remediated soil from a vegetable garden in Meza Valley, Slovenia. Contaminated soil was extracted with EDTA and placed into field experimental plots equipped with lysimeters. Soil properties were assessed by standard pedological analysis. Fractionation and leachability of toxic metals were analyzed by sequential extraction and TCLP and metal bioaccessibility by UBM tests. Soil respiration and enzyme activities were measured as indicators of soil functioning. Remediation reduced the metal burden by 80, 28 and 72% for Pb, Zn and Cd respectively, with a limited impact on soil pedology. Toxic metals associated with labile soil fractions were largely removed. No shifts between labile and residual fractions were observed during the seven months of the experiment. Initial metal leaching measured through lysimeters eventually ceased. However, remediation significantly diminished potential soil enzyme activity and no trends were observed of the remediated soil recovering its biological properties. Soil washing successfully removed available forms of Pb, Zn and Cd and thus lowered the human and environmental hazards of the remediated soil; however, remediation also extracted the trace elements essential for soil biota. In addition to reduced water holding capacity, soil health was not completely restored.

The terrestrial isopod ( Porcellio scaber ) was used to assess the remediation efficiency of limestone and a mixture of gravel sludge and red mud as stabilizing agents of Pb, Zn and Cd in industrially polluted soil, which contains 800, 540 and 7 mg kg −1 of Pb, Zn and Cd, respectively. The aim of our study was to compare and evaluate the results of the biological and non-biological assessment of metal bioavailability after soil remediation. Results of a 14 d bioaccumulation test with P. scaber showed that that Pb and Zn stabilization were more successful with gravel sludge and red mud, while Cd was better stabilized and thus less bioavailable following limestone treatment. In vivo bioaccumulation tests confirmed the results of chemical bioaccessibility, however it was more sensitive. Biotesting with isopods is a relevant approach for fast screening of bioavailability of metals in soils which includes temporal and spatial components. Capsule Bioavailability assessed by P . scaber is a more relevant and sensitive measure of metal bioavailability than chemical bioaccessibility testing in remediated industrially polluted soil.

The effect of remediation using three EDTA doses (10, 30, 60 mmol kg−1) on soil functioning was assessed using column experiment and Brassica rapa. Soil washing removed up to 77, 29 and 72% of metals from soil contaminated with 1378, 578 and 8.5 mg kg−1 of Pb, Zn and Cd, respectively. Sequential extraction indicated removal from the carbonate soil fraction. Metal oral-accessibility from the stomach phase was reduced by up to 75 and from the small intestine by up to 79% (Pb). Part of metals (up to 0.8% Cd) was lost due to leaching from columns. Remediation reduced toxic metal soil-root transfer by up to 61% but did not prevent metal accumulation in leaves. The fitness of plants grown on EDTA washed soils (gas exchange, fluorescence) was not compromised. Remediation initially reduced the soil DNA content (up to 29%, 30 mmol kg−1 EDTA) and changed the structure of microbial population.

Pb, Zn and Cd contaminated garden soil (5249, 3348 and 20.6 mg kg(-1), respectively) rich with fines and organic matter was washed with a solution of 120 mmol EDTA kg(-1) of soil in a pilot-scale remediation plant operating in a batch (60 kg of soil) mode. After soil washing, the solid phase and used washing solution were separated in a chamber filter press. A base/acid pair Ca(OH)(2)/H(2)SO(4) was used to impose a pH gradient for EDTA recycling from used washing solution and, coupled with an electrochemical advanced oxidation process using a graphite anode, for cleansing and recycling the process water, which was used for rinsing the soil solid phase in the press. On average (5 batches), 75%, 26% and 66% of Pb, Zn and Cd, respectively, was removed from the soil, 71% of EDTA was recycled and no waste water was generated. The variable costs of the novel remediation process (materials, energy but not labour) amounted to 66 € t(-1) of remediated soil. The results of the pilot-scale testing indicate that scaling-up the process to a commercial level is technically and economically feasible.

Remediation soil is exposed to various environmental factors over time that can affect the final success of the operation. In the present study, we assessed Pb bioaccessibility and microbial activity in industrially polluted soil (Arnoldstein, Austria) stabilized with 5% (w/w) of Slovakite and 5% (w/w) of apatite soil after exposure to two earthworm species, Lumbricus terrestris and Dendrobaena veneta, used as model environmental biotic soil factors. Stabilization resulted in reduced Pb bioaccessibility, as assessed with one-step extraction tests and six-step sequential extraction, and improved soil functioning, mirrored in reduced β-glucosidase activity in soil. Both earthworm species increased Pb bioaccessibility, thus decreasing the initial stabilization efficacy and indicating the importance of considering the long-term fate of remediated soil. The earthworm species had different effects on soil enzyme activity, which can be attributed to species-specific microbial populations in earthworm gut acting on the ingested soil.

We demonstrate here, in a laboratory scale experiment, the feasibility of using the base/acid pair Ca(OH)(2)/H(2)SO(4) to impose a pH gradient for EDTA recycling and, coupled with an electrochemical advanced oxidation process using a graphite anode, of recycling process water as part of a novel remediation technology for multi-metal contaminated soils. In the first batch, 60 mmol EDTA kg(-1) of soil removed 72, 27, and 71% of Pb, Zn, and Cd, respectively, from soil contaminated with 5329±685, 3401±193, and 35±6 mg kg(-1) of Pb, Zn, and Cd, respectively. In the subsequent four batches, we demonstrated that up to 88% of EDTA was recycled from each batch, with the potential to extract up to 98, 94, and 109% of Pb, Zn, and Cd, respectively, that the fresh EDTA extracted. Accumulation of salts in the process water through multiple remediation batches/recycles was prevented by CaSO(4) precipitation. Recycled process water toxicity testing indicated no significant effect on plant seed germination but some inhibition of root elongation.

Ten batches (75 kg each) of garden soil with >50% of silt and clay and average 1935 mg kg −1 Pb, 800 mg kg −1 Zn, 10 mg kg −1 Cd and 120 mg kg −1 As were remediated in a pilot-scale chemical extraction plant. Washing with 60 mmol ethylenediaminetetraacetic acid (EDTA) per kg of soil on average removed 79, 38, 70, and 80% of Pb, Zn, Cd and As, respectively, and significantly reduced the leachability, phyto-accessibility and oral-availability of residual toxic metals, as assessed using deionised water, toxicity characteristic leaching procedure (TCLP), diethylenetriamine pentaacetic acid extraction (DTPA) and physiologically based extraction test (PBET) tests. The used soil washing solution was treated before discharge using an electrochemical advanced oxidation process with graphite anode: EDTA was removed by degradation and toxic metals were electro-precipitated onto a stainless steel cathode. The novelty of the remediation technique is separation of the soil from the washing solution and soil rinsing (removal of mobilized contaminants) carried out in the same process step. Another novelty is the reuse of the soil rinsing solution from the previous batch for cleansing the soil sand, soil rinsing and for preparation of the washing solution in subsequent batches. The cost of energy and material expenses and disposal of waste products amounted to approximately 75€ ton −1 of soil.

The use of EDTA in soil washing technologies to remediate soils contaminated with toxic metals is prohibitive because of the large volumes of waste washing solution generated, which must be treated before disposal. Degradation of EDTA in the waste solution and the removal of Pb, Zn and Cd were investigated using electrochemical advanced oxidation processes (EAOP) with a boron-doped diamond anode (BDDA), graphite and iron anodes and a stainless-steel cathode. In addition to EAOP, the efficiency of electro-Fenton reactions, induced by the addition of H2O2 and the regulation of electrochemical systems to pH 3, was also investigated. Soil extraction with 15 mmol kg−1 of soil EDTA yielded waste washing solution with 566 ± 1, 152 ± 1 and 5.5 ± 0.1 mg L−1 of Pb, Zn and Cd, respectively. Treatments of the waste solution in pH unregulated electrochemical systems with a BDDA and graphite anode (current density 67 mA cm−2) were the most efficient and removed up to 98 ± 1, 96 ± 1, 99 ± 1% of Pb, Zn and Cd, respectively, by electrodeposition on the cathode and oxidatively degraded up to 99 ± 1% of chelant. In the electrochemical system with an Fe anode operated at pH 3, the chelant remained preserved in the treated solution, while metals were removed by electrodeposition. This separation opens up the possibility of a new EDTA recycling method from waste soil washing solution.

The development of EDTA-based soil washing technologies is hampered by the lack of treatment methods of the spent solution, particularly when multi-metal contaminated soils have to be remediated. Extraction of Pb (5329 mg kg −1 ), Zn (3401 mg kg −1 ), Cd (35 mg kg −1 ) and As (279 mg kg −1 ) contaminated soil with 60 mmol EDTA kg −1 of soil removed 72%, 27%, 71%, and 80% of contaminants, respectively. We demonstrate here, on a laboratory scale experiment, the feasibility of using acid precipitation with HCl and H 2 SO 4 , coupled to initial alkaline Fe removal, to recover up to 88% of EDTA from a spent soil washing solution containing 11,578 mg L −1 of EDTA and 1109, 267, 7.1 and 64 mg L −1 of Pb, Zn, Cd and As, respectively. An electrochemical advanced oxidation process with a graphite anode was subsequently used to degrade 99.9% of the remaining EDTA in the spent washing solution and remove 99.7% Pb, 100% Zn, 96.6% Cd and 100% of As as (electro)precipitate. The cleansed process water obtained after electrochemical treatment was then used to prepare recycled washing solution by re-dissolving the recovered/recycled part of the EDTA. Washing solutions prepared from recycled EDTA had the same potential to extract Pb, Zn, Cd and As from soil as washing solution prepared from fresh EDTA of the same molarity. The novel recycling method is simple and robust and enables reuse of both EDTA and process water in a closed process loop.

Various artificial soil mixtures were prepared by mixing two different toxic metals containing sewage sludge from Ljubljana and Maribor wastewater treatment plants with natural mineral soil. The plots with mixtures were exposed to field environmental conditions for a period of 1 year, after which we assessed soil toxicity (germination test with Lactuca sativa ), potential metal phyto-accessibility (diethylenetriamine pentaacetic acid – DTPA extraction test), soil functioning (by soil enzymes activity) and conducted a field growth test with Lollium perenne L. as a metal bio-indicator plant. The metal phyto-accessibility extraction test (DTPA) showed lower values than the metal accumulation test with L. perenne L., which also showed higher metal concentrations in roots compared to leaves. With the exception of the mixture containing 30% (w/w) of sludge from the Ljubljana wastewater treatment plant, all mixtures containing more than 20% of sludge negatively affected root elongation of L . sativa seeds, indicating an increase in artificial soils toxicity. Increasing the ratio of sludge from the Ljubljana plant increased dehydrogenase and decreased phosphomonoesterase, while the addition of sludge from the Maribor plant increased phosphomonoesterase activity. Overall, the effect of sludge addition on artificial soil properties, toxicity and functioning not only depended on dosage but was also sensitive to the source and pre-treatment of the sewage sludge.

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.

Recycling of chelant decreases the cost of EDTA-based soil washing. Current methods, however, are not effective when the spent soil washing solution contains more than one contaminating metal. In this study, we applied electrochemical treatment of the washing solution obtained after EDTA extraction of Pb, Zn and Cd contaminated soil. A sacrificial Al anode and stainless steel cathode in a conventional electrolytic cell at pH 10 efficiently removed Pb from the solution. The method efficiency, specific electricity and Al consumption were significantly higher for solutions with a higher initial metal concentration. Partial replacement of NaCl with KNO3 as an electrolyte (aggressive Cl− are required to prevent passivisation of the Al anode) prevented EDTA degradation during the electrolysis. The addition of FeCl3 to the acidified washing solution prior to electrolysis improved Zn removal. Using the novel method 98, 73 and 66% of Pb, Zn and Cd, respectively, were removed, while 88% of EDTA was preserved in the treated washing solution. The recycled EDTA retained 86, 84 and 85% of Pb, Zn and Cd extraction potential from contaminated soil, respectively.

Changes in the behavior of earthworms (for example avoidance of a particular substrate) can influence the soil ecosystem. Our aim was to determine whether the earthworms Eisenia fetida and Lumbricus terrestris are able to avoid ivermectin (a veterinary endectocide belonging to the avermectins). A standard avoidance test with earthworms was conducted using standardized Lufa 2.3 soil (Speyer, Germany) and sandy soil provided by Cinkarna Celje (Slovenia). A two-chamber system of avoidance test as described in ISO guideline 17512-1 (ISO 2008) was applied. We investigated the substrate preference of E. fetida and L. terrestris after 48 h at ivermectin concentrations of 8, 32, 64, and 256 mg kg−1 dry soil. No deterrent effects were observed for either species and either soil types. E. fetida in Lufa 2.3 soil was clearly attracted to ivermectin. More than 70% of the earthworms preferred soil with ivermectin concentrations of 8, 64, and 256 mg kg−1. No observed effect concentration and lowest observed effect concentration, 2-day exposure, for effects on the avoidance of both species are >256 mg kg−1 dry soil in two different soils. High percentage of earthworms in the test soil was observed in the experiment with E. fetida in Lufa 2.3 soil treated with 8, 64, and 256 mg ivermectin kg−1. We can conclude that earthworms, as it was observed in E. fetida in Lufa 2.3 soil treated with ivermectin, may be attracted by some chemicals. The percentage of L. terrestris in soil from Cinkarna Celje treated with ivermectin ranged from 39% to 52% and of E. fetida from 33% to 55%.

Remediation by means of soil leaching with ethylenediaminetetraacetic acid (EDTA) is capable of extracting the most labile soil fractions, leaving the residual metals in biologically non-available forms. We evaluated the feasibility of the standardized earthworm (Eisenia fetida) avoidance test for assessing the efficiency of soil remediation of Pb, Zn and Cd polluted soil. Chemical extraction tests (six-step sequential extraction, toxicity characteristic leaching procedure, physiologically based extraction test, diethylenediaminepentaacetic acid extraction) indicated that the mobility, oral bioaccessibility and phytoavailability of Pb, Zn and Cd were consistently reduced. However, the avoidance test showed no significant avoidance of polluted soil in favor of that which had been remediated. Pb, Zn and Cd accumulation in E. fetida mirrored the decreasing pattern of metal potential bioavailability gained by leaching the soil with increasing EDTA concentrations. The calculated bioaccumulation factors indicated the possibility of underestimating the metal bioavailability in soil using chemical extraction tests.

In a laboratory study, Portland cement (15%, w/w) was used for solidification/stabilisation (S/S) of Cd, Pb, Zn, Cu, Ni and As contaminated soils from the former industrial site. Soils formed solid monoliths with cement. S/S effectiveness was assessed by measuring the mechanical strength of the monoliths, concentrations of metals in deionised water and TCLP (toxicity characteristic leaching procedure) soil extracts, and mass transfer of metals. Concentrations of Cd, Pb, Zn and Ni in water extracts from S/S soils generally decreased, concentrations of As remained unchanged, while concentrations of Cu increased. Concentrations of Cd, Pb, Zn and Ni in the TCLP extracts from S/S soils were lower than from original soils. Cu extractability was lower in most soil samples, while the extractability of As from S/S soils increased. Overall, the concentration of metals in deionised water and TCLP solution, obtained after extraction of the S/S soils, was below the regulatory limits. S/S greatly reduced the mass transfer of Cd (up to 83-times), Pb (up to 13.7-times) and Zn (up to 294-times). Mass transfer of Ni and As was generally also reduced, while that of Cu increased in some S/S soils. Based on the findings of mass-transfer mechanism analysis the predominant mechanism of release was surface wash-off of metals otherwise physically encapsulated within the cementous soil matrix.

After soil remediation with ethylenediamine tetraacetate (EDTA) leaching/washing, the residual Pb, Zn, and Cd species are left in the soil in non-labile forms. The effect of earthworms as main soil biotic factors on the residual Pb, Zn, and Cd fraction lability (mobility, bioavailability to plants, and oral-availability) was investigated. Contaminated soil from a smelter site was treated with increasing EDTA concentrations (2.5 to 4-times 40 mmol kg(-1) to gradually reduce the heavy metal content and lability. Leached soils were processed by Eiseniafetida and heavy metal lability and fractionation determined in casts and earthworm-processed soils. In general E. fetida increased heavy metal accessibility/mobility, but the induced changes diminished with the intensity of soil EDTA treatment. Fractionation results indicate the possibility of a time-dependent complexation of heavy metals to carbonates favoured by earthworms' gut processes. The transition of residual heavy metals in time (ageing) should be considered.

Electrocoagulation with an Al sacrificial anode was tested for the separation of chelant and heavy metals from a washing solution obtained after leaching Pb (3200 mg kg(-1)), Zn (1100 mg kg(-1)), and Cd (21 mg kg(-1)) contaminated soil with EDTA. In the electrochemical process, the sacrificial anode corroded to release Al(3+) which served as coagulant for precipitation of chelant and metals. A constant current density of 16-128 mAc m(-2) applied between the Al anode and the stainless-steel cathode removed up to 95% Pb, 68% Zn and 66% Cd from the soil washing solution. Approximately half of the initial EDTA remained in the washing solution after treatment, up to 16.3% of the EDTA was adsorbed on Al coagulant and precipitated, the rest of the EDTA was degraded by anodic oxidation. In a separate laboratory-scale remediation experiment, we leached a soil with 40 mmol EDTA per kg of soil and reused the washing solution (after electrocoagulation) in a closed loop. It removed 53% of Pb, 26% of Zn and 52% of Cd from the soil. The discharge solution was clear and colourless, with pH 7.52 and 170 mg L(-1) Pb, 50 mg L(-1) Zn, 1.5 mg L(-1) Cd and 11 mM EDTA.

Soil remediation with ethylenediamine tetraacetic acid (EDTA) leaching is capable of removing only part of the total metal concentration in the soil, mostly the labile, bioavailable metal species (metal bioavailability stripping). However, reintroduction of remediated soil in the environment exposes the soil to various environmental factors, which could potentially shift nonlabile residual metals back to labile bioavailable forms. We studied the effect of autochthonous earthworm species as model biotic environmental factor on the fractionation and bioavailability of Cu residual in soil after remediation.We used soil from a 50-year-old vineyard regularly managed and treated with CuSO(4)*5H(2)O (Bordeaux mixture) as fungicide. Soil containing 400 mg kg(-1) of Cu was leached with total 15 mmol kg(-1) EDTA. Remediated and nonremediated soil was processed by fully clitellated adult specimens of Lumbricus terrestris L., a prevailing autochthonous soil earthworm species. Cu fractionation, phytoavailability, and oral-bioavailability in processed and nonprocessed soil were determined using six-step sequential extraction, extraction with diethylenediamine pentaacetic acid, and in vitro physiologically based extraction test, respectively.EDTA leaching removed 41% of the pseudototal Cu, mostly from the soil Fe- and Mn-oxides, carbonates, and organic matter. A 2.7-fold decrease in Cu phytoavailability and a 4.4- and 2.8-fold decrease in Cu oral-bioavailability in the stomach and small intestine fractions, respectively, were achieved after remediation. In nonremediated soil, earthworms increased the share of nonlabile Cu in residual soil fraction, while in remediated soil they increased the share of Cu bound to carbonates. A statistically significant 1.1- and 1.7-fold increase in Cu phytoavailability and intestinal oral-bioavailability, respectively, was observed in earthworm processed remediated soil.Cu occurs in various soil "pools" of different solubilities with different chemical characteristics and consequently different functions. By removing the labile part of the metals from the soil during remediation, we disrupt the chemical equilibrium; the nonlabile residual metals left in soil after remediation might become more labile in time in tendency to re-establish that equilibrium. Earthworms alter the physical and chemical properties of soil affecting consequently the fractionation of metals. The increase in earthworm's gut pH due to the excretion of ammonia and/or calcium carbonate into the intestine could lead to the transbounding of metals into the carbonate fraction. However, their activity in remediated soil increased Cu phytoavailability and intestinal oral-bioavailability, and it would, therefore, be improper to generalize the influence of earthworms on metal availability in soil.The results presented here show that residual Cu in remediated soil is affected by environmental factors such as earthworms, which should be considered in evaluating the effect of Cu polluted soil remediation.Information on the behavior of residual metals in soil after its remediation is surprisingly scarce. The development of new effective remediation techniques should imply also the evaluation of postremediation effects on remediated soil. The results presented in this work indicate a possible tool for assessing the effect of biotic environmental factors on residual metals left in soil after its remediation.

Mixtures of artificial soil (10, 30 and 50% w/w) were prepared by adding sewage sludge (contaminated with 200 ± 13 mg kg − 1 Cu, 867 ± 18 mg kg − 1 Zn, 7 ± 0 mg kg − 1 Cd, 122 ± 6 mg kg − 1 Pb, 74 ± 2 mg kg − 1 Ni) to the fraction of infertile mineral soil. The effect of accelerated ageing of artificial soils on metal fractionation (assessed by sequential extractions), mobility (assessed by extraction with deionised water and using the Toxicity Leaching Procedure, TCLP), phyto-accessibility (diethylenetriamine pentaacetic acid, DTPA, extraction) and oral-accessibility ( in vitro Physiologically Based Extraction Test, PBET) was simulated by exposing soils to alternate high (105 °C) and low (− 25 °C) temperatures. Accelerated ageing affected the fractionation of contaminants metal-specifically and increased heavy metal mobility when assessed with the deionised water extraction test. On the other hand, accelerated ageing significantly decreased heavy metal mobility assessed with TCLP, phyto-accessibility (DTPA) and oral bio-accessibility in a simulated human gastrointestinal tract (PBET) and thus decreased the potential toxicity of metals in artificial soil mixtures. We propose accelerated ageing model as a simple tool to assess the long-term effect of environmental conditions on the metal availability status in artificial soils.

An electrochemical advanced oxidation process (EAOP) was used for treatment of the washing solution obtained during leaching of Cu (364 +/- 2 mg kg(-1)) contaminated soil, with chelant S,S isomer of ethylenediamine disuccinate ([S,S]-EDDS). In the EAOP (constant current density 40 mA cm(-2)), a boron-doped diamond anode was used for the generation of hydroxyl radicals and oxidative decomposition of [S,S]-EDDS-metal complexes in the washing solution. The released Cu was mostly electro-deposited on the stainless-steel cathode. Three consecutive additions of 5 mmol kg(-1) [S,S]-EDDS removed 46% of the Cu from the soil, mostly from carbonate and oxide soil fractions (87 and 99% Cu reduction). The soil Cu oral availability in the simulated stomach and intestinal phases (in vitro physiologically based extraction test) was reduced by 5.5 and 4.6-times. Cu plant availability (in vitro diethylenetriamine pentaacetate test) was reduced by 3.6-times. The discharge solution was clear, almost colorless, with pH 8.4, 0.45 mg L(-1) Cu and 0.01 mM EDDS.

The objectives of this study were to investigate the effectiveness of ozone treatment on degradation of polychlorinated biphenyl (PCB) contaminated soils and to observe the subsequent changes in soil physico-chemical properties. Furthermore, the ability of plants to grow on the ozone-treated soils was evaluated. Soils with different physico-chemical characteristics spiked with seven PCB congeners in two different time periods were chosen. Ozonation was more efficient for PCB degradation in freshly spiked soils and the removal efficiency increased with increasing ozonation time. The highest decrease was found in the soil with a lower soil organic matter (SOM) content and a coarser soil structure indicating the substantial effect of soil characteristics on the efficiency of ozonation. The composition of individual PCB congeners changed in all treatments in terms of higher accumulation rate of highly chlorinated biphenyls with a higher ozonation time. Increased mobility of several elements, changes in SOM content and in soil pH were detected after ozonation. Vulnerability of plants to these modifications was documented on rape seedlings. No inhibition in growth during any treatment and predominantly higher concentration of PCB in non-ozonated treatments were observed. Results suggest that this method can present a promising environmental friendly remediation technology for PCB contaminated soils.

The feasibility of a novel two-phase method for remediation of Pb (1374 mg kg −1 ), Zn (1007 mg kg −1 ), and Cd (9.1 mg kg −1 ) contaminated soil was evaluated. In the first phase we used EDTA for leaching heavy metals from the soil. In the second phase we used an electrochemical advanced oxidation process (EAOP) for the treatment and reuse of washing solution for soil rinsing (removal of the soil-retained, chelant-mobilized metallic species). In EAOP, a boron-doped diamond anode was used for the generation of hydroxyl radicals and oxidative decomposition of EDTA–metal complexes at a constant current density (15 mA cm −2 ). The released metals were removed from the solution by filtration as insoluble participate and by electro-deposition on the cathode. Four consecutive additions of 5.0 mmol kg −1 EDTA (total 20 mmol kg −1 ) removed 44% Pb, 14% Zn and 35% Cd from the soil. The mobility of the Pb, Zn and Cd (Toxicity Characteristic Leaching Procedure) left in the soil after remediation was reduced by 1.6, 3.4 and 1.5 times, respectively. The Pb oral availability (Physiologically Based Extraction Test) in the simulated stomach phase was reduced by 2.4 and in the intestinal phase by 1.7 times. The discharge solution was clear, almost colorless, with pH 7.73 and 0.47 mg L −1 Pb, 1.03 mg L −1 Zn, bellow the limits of quantification of Cd and 0.023 mM EDTA. The novel method enables soil leaching with small water requirements and no wastewater generation or other emissions into the environment.

The effect of two ecologically contrasting earthworm species Eisenia fetida (epigeic) and Octolasion tyrtaeum (endogeic) on the fractionation (accessed using sequential extractions), mobility (toxicity characteristic leaching procedure, TCLP) and oral bioavailability (Ruby's physiologically based extraction test, PBET) of Pb, Zn and Cd was studied before and after soil remediation with soil leaching. Twenty-step leaching, with 2.5 mmol kg(-1) EDTA used in each step, removed 58.4%, 25.0% and 68.0% of initial soil Pb, Zn and Cd, respectively, shifted the fractionation of residual heavy metals toward less labile forms, and decreased their mobility by 83.7%, 80.3%, and 90.9%. Pb oral bioavailability was reduced by 3.1-times (in each stomach and intestinal phase). After soil leaching, both earthworm species enriched the carbonate soil fraction in their casts with residual Pb, and increased the Pb bioavailability in the simulated intestinal phase by a factor of 2.4 (E. fetida) and 2.8 (O. tyrtaeum). The concentration of Pb in TCLP leachate from E. fetida casts was 6.2-times higher than in the bulk of the remediated soil. These results indicate that the effect of biotic factors on the availability of heavy metals residual in soil after soil leaching requires consideration.

The effect of two earthworm species, Lumbricus rubellus and Eisenia fetida, on the fractionation/bioavailability of Pb and Zn before and after soil leaching with EDTA was studied. Four leaching steps with total 12.5 mmol kg −1 EDTA removed 39.8% and 6.1% of Pb and Zn, respectively. EDTA removed Pb from all soil fractions fairly uniformly (assessed using sequential extractions). Zn was mostly present in the chemically inert residual soil fraction, which explains its poor removal. Analysis of earthworm casts and the remainder of the soil indicated that L. rubellus and E. fetida actively regulated soil pH, but did not significantly change Pb and Zn fractionation in non-remediated and remediated soil. However, the bioavailability of Pb (assessed using Ruby's physiologically based extraction test) in E. fetida casts was significantly higher than in the bulk of the soil. In remediated soil the Pb bioavailability in the simulated stomach phase increased by 5.1 times.

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 ± 313 mg kg−1) and Zn (288 ± 5–5489 ± 471 mg kg−1) were obtained from industrial sites in the Mežica Valley, Slovenia and Pribram district, Czech Republic. Different dosages (2.5–40 mmol kg−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.

Cyanobacterial blooms are global phenomena that can occur in calm and nutrient-rich (eutrophic) fresh and marine waters. Human exposure to cyanobacteria and their biologically active products is possible during water sports and various water activities, or by ingestion of contaminated water. Although the vast majority of harmful cyanobacterial products are confined to the interior of the cells, these are eventually released into the surrounding water following natural or artificially induced cell death. Electrochemical oxidation has been used here to damage cyanobacteria to halt their proliferation, and for microcystin degradation under in-vitro conditions. Partially spent Jaworski growth medium with no addition of supporting electrolytes was used. Electrochemical treatment resulted in the cyanobacterial loss of cell-buoyancy regulation, cell proliferation arrest, and eventual cell death. Microcystin degradation was studied separately in two basic modes of treatment: batch-wise flow, and constant flow, for electrolytic-cell exposure. Batch-wise exposure simulates treatment under environmental conditions, while constant flow is more appropriate for the study of boron-doped diamond electrode efficacy under laboratory conditions. The effectiveness of microcystin degradation was established using high-performance liquid chromatography-photodiode array detector analysis, while the biological activities of the products were estimated using a colorimetric protein phosphatase-1 inhibition assay. The results indicate potential for the application of electro-oxidation methods for the control of bloom events by taking advantage of specific intrinsic ecological characteristics of bloom-forming cyanobacteria. The applicability of the use of boron-doped diamond electrodes in remediation of water exposed to cyanobacteria bloom events is discussed.

Ozone and UV irradiation were used for oxidative decomposition of EDTA-Cu complexes in washing solution obtained during multi-step leaching of Cu (344,1 ± 36.5 mg kg−1) contaminated vineyard soil with EDTA as a chelant. The released Cu was absorbed from the washing solution on a commercial mixture of metal absorbing minerals, and the treated washing solution then reused for removal of soil residual Cu-EDTA complexes in a closed-loop process. Six consecutive leaching steps (6 × 2.5 mmol kg−1 of EDTA) removed 38.8 % of Cu from soils, and reduced Cu soil mobility, determined using the toxicity characteristic leaching test (TCLP), by 28.5%. The final washing solution obtained after soil remediation was colourless, with a pH close to neutral (7.5 ± 0.2) and with low concentrations of Cu and EDTA (0.51 ± 0.22 mg L−1 and 0.083 mM, respectively). The proposed remediation method has therefore potential not just to recycle and save process water, but also not to produce toxic wastewaters. Soil treatment did not substantially alter the soil properties determined by pedological analysis, and had relatively little impact on soil hydraulic conductivity and soil water sorption capacity.