Wood Preservation Site Research Articles

Field assessment of organic amendments and spring barley to phytomanage a Cu/PAH-contaminated soil.

The INTENSE project, supported by the EU Era-Net Facce Surplus, aimed at increasing crop production on marginal land, including those with contaminated soils. A field trial was set up at a former wood preservation site to phytomanage a Cu/PAH-contaminated sandy soil. The novelty was to assess the influence of five organic amendments differing in their composition and production process, i.e. solid fractions before and after biodigestion of pig manure, compost and compost pellets (produced from spent mushroom substrate, biogas digestate and straw), and greenwaste compost, on Cu availability, soil properties, nutrient supply, and plant growth. Organic amendments were incorporated into the soil at 2.3% and 5% soil w/w. Total soil Cu varied from 179 to 1520mgkg-1, and 1M NH4NO3-extractable soil Cu ranged from 4.7 to 104mgkg-1 across the 25 plots. Spring barley (Hordeum vulgare cv. Ella) was cultivated in plots. Changes in physico-chemical soil properties, shoot DW yield, shoot ionome, and shoot Cu uptake depending on extractable soil Cu and the soil treatments are reported. Shoot Cu concentration varied from 45 ± 24 to 140 ± 193mgkgDW-1 and generally increased with extractable soil Cu. Shoot DW yield, shoot Cu concentration, and shoot Cu uptake of barley plants did not significantly differ across the soil treatments in year 1. Based on soil and plant parameters, the effects of the compost and pig manure treatments were globally discriminated from those of the untreated, greenwaste compost and digested pig manure treatments. Compost and its pellets at the 5% addition rate promoted soil functions related to primary production, water purification, and soil fertility, and the soil quality index.

Phytomanagement with grassy species, compost and dolomitic limestone rehabilitates a meadow at a wood preservation site

Brownfield surface is expanding in Europe, but as often abandoned or underused, these areas become refuge for microbial, faunal and floral biodiversity. However, brownfield sites are generally contaminated, likely posing severe environmental risks. At a former wood preservation site contaminated with Cu, we evaluated the efficiency of compost and dolomitic limestone incorporation into the soil, followed by revegetation with Cu-tolerant grassy species, as a phytomanagement option to increase vegetation cover and plant diversity while reducing pollutant linkages. 7 years of phytomanagement enhanced natural revegetation through the improvement of soil physicochemical properties, particularly with compost-based amendments. The compost incorporation increased soil Cu solubility; however, no increment in Cu availability and a reduction in Cu-induced phytotoxicity were observed with the compost. The improved soil nutrient availability and the soil phytotoxicity mitigation in compost-amended soils facilitated over the 7 years the growth of beneficial plant colonists, including leguminous species, which can potentially promote essential soil functions. Soil treatments did not affect Cu uptake and translocation by plants and shoot Cu levels indicated no risk for the food chain. Overall, a long-term phytomanagement combining an initial amendment of compost and dolomitic limestone with the cultivation of Cu-tolerant grassy populations can ameliorate such Cu-contaminated soils, by mitigating risks induced by Cu excess, ultimately allowing the development of a meadow that can provide ecological and economic benefits in terms of ecosystem services.

Arsenic removal from natural groundwater using ‘green rust’: Solid phase stability and contaminant fate

Arsenic (As) contamination in groundwater remains a pressing global challenge. In this study, we evaluated the potential of green rust (GR), a redox-active iron phase frequently occurring in anoxic environments, to treat As contamination at a former wood preservation site. We performed long-term batch experiments by exposing synthetic GR sulfate (GRSO4) to As-free and As-spiked (6 mg L−1) natural groundwater at both 25 and 4 °C. At 25 °C, GRSO4 was metastable in As-free groundwater and transformed to GRCO3, and then fully to magnetite within 120 days; however, GRSO4 stability increased 7-fold by lowering the temperature to 4 °C, and 8-fold by adding As to the groundwater at 25 °C. Highest GRSO4 stability was observed when As was added to the groundwater at 4 °C. This stabilizing effect is explained by GR solubility being lowered by adsorbed As and/or lower temperatures, inhibiting partial GR dissolution required for transformation to GRCO3, and ultimately to magnetite. Despite these mineral transformations, all added As was removed from As-spiked samples within 120 days at 25 °C, while uptake was 2 times slower at 4 °C. Overall, we have successfully documented that GR is an important mineral substrate for As immobilization in anoxic subsurface environments.

Field evaluation of one Cu-resistant somaclonal variant and two clones of tobacco for copper phytoextraction at a wood preservation site.

A Cu-resistant somaclonal tobacco variant (NBCu 10-8-F1, C1), its BaG mother clone (C3), and the FoP tobacco clone (C2) were cultivated at a wood preservation site on Cu-contaminated soils (239-1290mg Cu kg-1 soil range) and an uncontaminated control site (CTRL, 21mg Cu kg-1) to assess their shoot DW yields and potential use for bioavailable Cu stripping. The Cu concentration in the soil pore water varied between 0.15 and 0.84mgL-1. Influences of Cu exposure and soil treatments, i.e., untreated soil (Unt), soils amended with compost and either dolomitic limestone (OMDL) or zerovalent iron grit (OMZ), on plant growth and shoot ionome were determined. All transplants survived and grew even at high total soil Cu. Shoots were harvested after 3months (cut 1). Subsequently, bottom suckers developed and were harvested after 2months (cut 2). Total shoot DW yield (cuts 1 + 2) varied between 0.8 and 9.9t DW ha-1year-1 depending on tobacco cultivars, soil treatments, and soil Cu exposure. It peaked for all cultivars in the OMDL plots at moderate Cu exposure (239-518mgkg-1 soil), notably for the C2 plants. Cut 2 contributed for 11-43% to total shoot DW yield. Increase in shoot DW yield diluted shoot Cu concentration. At low Cu exposure, total shoot Cu removal peaked for the variant. At moderate Cu exposure, shoot Cu concentrations were similar in all cultivars, but total shoot Cu removal was highest for the C2 plants. At high Cu exposure (753-1140mgkg-1), shoot Cu concentrations peaked for the C2 plants in the Unt plots, the C1 and C2 plants in the OMZ plot, and the C3 ones in the OMDL plots. Shoot Cu removal (in g Cu ha-1year-1) ranged from 15.4 (C2 on the CTRL soil) to 261.3 (C2 on moderately contaminated OMDL soils). The C2 plants phytoextracted more Cu than the C1 and C3 ones in the Unt plots and in the OMDL plots at moderate Cu exposure. In the OMDL plots with high Cu exposure, shoot Cu removal was highest for the C1 plants. Soil amendments improved shoot Cu removal through increase in either shoot DW yield (OMDL-3-fold) or shoot Cu concentration (OMZ-1.3-fold). Increased shoot Cu concentration induced an ionome imbalance with increased shoot Al, Fe, B, and Mg concentrations and decreased P and K ones. Copper concentrations in plant parts varied in decreasing order: roots > leaves > inflorescence (cymes including seeds) > stem, whereas Cu removal ranked as roots > stem = leaves > inflorescence.

Long-term phytomanagement with compost and a sunflower – Tobacco rotation influences the structural microbial diversity of a Cu-contaminated soil

At a former wood preservation site contaminated with Cu, various phytomanagement options have been assessed in the last decade through physicochemical, ecotoxicological and biological assays. In a field trial at this site, phytomanagement with a crop rotation based on tobacco and sunflower, combined with the incorporation of compost and dolomitic limestone, has proved to be efficient in Cu-associated risk mitigation, ecological soil functions recovery and net gain of economic and social benefits. To demonstrate the long-term effectiveness and sustainability of phytomanagement, we assessed here the influence of this remediation option on the diversity, composition and structure of microbial communities over time, through a metabarcoding approach. After 9 years of phytomanagement, no overall effect was identified on microbial diversity; the soil amendments, notably the repeated compost application, led to shifts in soil microbial populations. This phytomanagement option induced changes in the composition of soil microbial communities, promoting the growth of microbial groups belonging to Alphaproteobacteria, many being involved in N cycling. Populations of Nitrososphaeria, which are crucial in nitrification, as well as taxa from phyla Planctomycetacia, Chloroflexi and Gemmatimonadetes, which are tolerant to metal contamination and adapted to oligotrophic soil conditions, decreased in amended phytomanaged plots. Our study provides an insight into population dynamics within soil microbial communities under long-term phytomanagement, in line with the assessment of soil ecological functions and their recovery.

Phytomanagement and Remediation of Cu-Contaminated Soils by High Yielding Crops at a Former Wood Preservation Site: Sunflower Biomass and Ionome

This long-term field trial aimed at remediating a Cu-contaminated soil to promote crop production and soil functions at a former wood preservation site. Twenty-eight field plots with total topsoil Cu in the 198-1,169 mg kg-1 range were assessed. Twenty-four plots (OMDL) were amended in 2008 with a compost (made of pine bark chips and poultry manure, OM, 5% w/w) and dolomitic limestone (DL, 0.2%), and thereafter annually phytomanaged with a sunflower-tobacco crop rotation. In 2013, one untreated plot (UNT) was amended with a green waste compost (GW, 5%) whereas 12 former OMDL plots received a second compost dressing using this green waste compost (OM2DL, 5%). In 2011, one plot was amended with the Carmeuse basic slag (CAR, 1%) and another plot with a P-spiked Linz-Donawitz basic slag (PLD, 1%). Thus six soil treatments, i.e., UNT, OMDL, OM2DL, GW, CAR, and PLD, were cultivated in 2016 with sunflower (Helianthus annuus L. cv Ethic). Shoots were harvested and their ionome analyzed. At high soil Cu contamination, the 1M NH4NO3-extractable vs. total soil Cu ratio ranked in decreasing order: Unt (2.35) > CAR (1.02), PLD (0.83) > GW (0.58), OMDL (0.44), OM2DL (0.37), indicating a lower Cu extractability in the compost-amended plots. All amendments improved the soil nutrient status and the soil pH, which was slightly acidic in the UNT soil. Total organic C and N and extractable P contents peaked in the OM2DL soils. Both OMDL and OM2DL treatments led to higher shoot DW yields and Cu removals than the GW, CAR, and PLD treatments. Shoot DW yields decreased as total topsoil Cu rose in the OMDL plots, on the contrary to the OM2DL plots, demonstrating the benefits to repeat compost application after 5 years. Shoot Cu concentrations notably of OMDL and OM2DL plants fitted into their common range and can be used by biomass processing technologies and oilseeds as well. In overall, there is a net gain in soil physico-chemical properties and underlying soil functions

Morphological and functional responses of a metal-tolerant sunflower mutant line to a copper-contaminated soil series.

The potential use of a metal-tolerant sunflower mutant line for biomonitoring Cu phytoavailability, Cu-induced soil phytotoxicity, and Cu phytoextraction was assessed on a Cu-contaminated soil series (13-1020mg Cu kg-1) obtained by fading a sandy topsoil from a wood preservation site with a similar uncontaminated soil. Morphological and functional plant responses as well as shoot, leaf, and root ionomes were measured after a 1-month pot experiment. Hypocotyl length, shoot and root dry weight (DW) yields, and leaf area gradually decreased as soil Cu exposure rose. Their dose-response curves (DRC) plotted against indicators of Cu exposure were generally well fitted by sigmoidal curves. The half-maximal effective concentration (EC50) of morphological parameters ranged between 203 and 333mg Cu kg-1 soil, corresponding to 290-430μg Cu L-1 in the soil pore water, and 20 ± 5mg Cu kg-1 DW in the shoots. The EC10 for shoot Cu concentration (13-15mg Cu kg-1 DW) coincided to 166mg Cu kg-1 soil. Total chlorophyll content and total antioxidant capacity (TAC) were early biomarkers (EC10: 23 and 51mg Cu kg-1 soil). Their DRC displayed a biphasic response. Photosynthetic pigment contents, e.g., carotenoids, correlated with TAC. Ionome was changed in Cu-stressed roots, shoots, and leaves. Shoot Cu removal peaked roughly at 280μg Cu L-1 in the soil pore water.

Long-term Cu stabilization and biomass yields of Giant reed and poplar after adding a biochar, alone or with iron grit, into a contaminated soil from a wood preservation site.

A 2-year pot experiment was carried out to examine the aging effect of biochar (B), alone or combined with iron grit (Z), on Cu stabilization and plant growth in a contaminated soil (964mg Cu kg-1) from a wood preservation site. The experiment consisted in 3 soil treatments, either planted with Arundo donax L. (Ad) or Populus nigra L. (Pn): (1) untreated Cu-contaminated soil (Ad, Pn); (2) Unt+1% (w/w) B (AdB, PnB), and (3) Unt+1% B+1% Z (AdBZ, PnBZ). After 22months, the soil pore water (SPW) was sampled and roots and shoots were harvested. The SPW compositions at 3 and 22months were compared, showing that the SPW Cu2+ concentration increased again in the PnB and PnBZ soils. Cultivation of A. donax enhanced the dissolved organic matter concentration in the SPW, which decreased its Cu2+ concentration but promoted its total Cu concentration in the Ad and AdB soils. Adding Z with B reduced both SPW Cu2+ and Cu concentrations in the pots cultivated by A. donax and P. nigra as compared to B alone. The B and BZ treatments did not enhance root and shoot yields of both plant species as compared to the Unt soil but their shoot Cu concentrations were in the range of common values.

Influence of biochars, compost and iron grit, alone and in combination, on copper solubility and phytotoxicity in a Cu-contaminated soil from a wood preservation site

Two biochars, a green waste compost and iron grit were used, alone and in combination, as amendment to improve soil properties and in situ stabilize Cu in a contaminated soil (964mgCukg−1) from a wood preservation site. The pot experiment consisted in 9 soil treatments (% w/w): untreated Cu-contaminated soil (Unt); Unt soil amended respectively with compost (5%, C), iron grit (1%, Z), pine bark-derived biochar (1%, PB), poultry-manure-derived biochar (1%, AB), PB or AB+C (5%, PBC and ABC), and PB or AB+Z (1%, PBZ and ABZ). After a 3-month reaction period, the soil pore water (SPW) was sampled in potted soils and dwarf beans were grown for a 2-week period. In the SPW, all amendments decreased the Cu2+ concentration, but total Cu concentration increased in all AB-amended soils due to high dissolved organic matter (DOM) concentration. No treatment improved root and shoot DW yields, which even decreased in the ABC and ABZ treatments. The PBZ treatment decreased total Cu concentration in the SPW while reducing the gap with common values for root and shoot yields of dwarf bean plants. A field trial is underway before any recommendation for the PB-based treatments.

Aided phytoextraction of Cu, Pb, Zn, and As in copper-contaminated soils with tobacco and sunflower in crop rotation: Mobility and phytoavailability assessment.

Copper-contaminated soils were managed with aided phytoextraction in 31 field plots at a former wood preservation site, using a single incorporation of compost (OM) and dolomitic limestone (DL) followed by a crop rotation with tobacco and sunflower. Six amended plots, with increasing total soil Cu, and one unamended plot were selected together with a control uncontaminated plot. The mobility and phytoavailability of Cu, Zn, Cr and As were investigated after 2 and 3 years in soil samples collected in these eight plots. Total Cu, Zn, Cr and As concentrations were determined in the soil pore water (SPW) and available soil Cu and Zn fractions by DGT. The Cu, Zn, Cr and As phytoavailability was characterized by growing dwarf beans on potted soils and determining the biomass of their plant parts and their foliar ionome. Total Cu concentrations in the SPW increased with total soil Cu. Total Cu, Zn, Cr and As concentrations in the SPW decreased in year 3 as compared to year 2, likely due to annual shoot removals by the plants and the lixiviation. Available soil Cu and Zn fractions also declined in year 3. The Cu, Zn, Cr and As phytoavailability, assessed by their concentration and mineral mass in the primary leaves of beans, was reduced in year 3.

Ammonium citrate as enhancement for electrodialytic soil remediation and investigation of soil solution during the process

Seven electrodialytic experiments were conducted using ammonium citrate as enhancing agent to remediate copper and chromium-contaminated soil from a wood-preservation site. The purpose was to investigate the effect of current density (0.2, 1.0 and 1.5mAcm−2), concentration of enhancing agent (0.25, 0.5 and 1.0M) and remediation times (21, 42 and 117 d) for the removal of Cu and Cr from a calcareous soil. To gain insight on metal behavior, soil solution was periodically collected using suction cups.It was seen that current densities higher than 1.0mAcm−2 did not increase removal and thus using too high current densities can be a waste of energy. Desorption rate is important and both remediation time and ammonium citrate concentration are relevant parameters.It was possible to collect soil solution samples following an adaptation of the experimental set-up to ensure continuous supply of ammonium citrate to the soil in order to keep it saturated during the remediation. Monitoring soil solution gives valuable information on the evolution of remediation and helps deciding when the soil is remediated.Final concentrations in the soil ranged from 220 to 360mg Cukg−1 (removals: 78–86%) and 440–590mgCrkg−1 (removals: 35–51%), being within the 500mgkg−1 limit for a clean soil only for Cu. While further optimization is still required for Cr, the removal percentages are the highest achieved so far, for a real Cu and Cr-contaminated, calcareous soil. The results highlight EDR potential to remediate metal polluted soils at neutral to alkaline pH by choosing a good enhancement solution.

Mobility and phytoavailability of Cu, Cr, Zn, and As in a contaminated soil at a wood preservation site after 4 years of aided phytostabilization.

The remediation of copper-contaminated soils by aided phytostabilisation in 16 field plots at a wood preservation site was investigated. The mobility and bioavailability of four potentially toxic trace elements (PTTE), i.e., Cu, Zn, Cr, and As, were investigated in these soils 4 years after the incorporation of compost (OM, 5 % w/w) and dolomite limestone (DL, 0.2 % w/w), singly and in combination (OMDL), and the transplantation of mycorrhizal poplar and willows. Topsoil samples were collected in all field plots and potted in the laboratory. Total PTTE concentrations were determined in soil pore water (SPW) collected by Rhizon soil moisture samplers. Soil exposure intensity was assessed by Chelex100-DGT (diffusive gradient in thin films) probes. The PTTE phytoavailability was characterized by growing dwarf beans on potted soils and analyzing their foliar PTTE concentrations. OM and DL, singly and in combination (OMDL), were effective to decrease foliar Cu, Cr, Zn, and As concentrations of beans, the lowest values being numerically for the OM plants. The soil treatments did not reduce the Cu and Zn mineral masses of the bean primary leaves, but those of Cr and As decreased for the OM and DL plants. The Cu concentration in SPW was increased in the OM soil and remained unchanged in the DL and OMDL soils. The available Cu measured by DGT used to assess the soil exposure intensity correlated with the foliar Cu concentration. The Zn concentrations in SPW were reduced in the DL soil. All amendments increased As in the SPW. Based on DGT data, Cu availability was reduced in both OM and OMDL soils, while DL was the most effective to decrease soil Zn availability.

Effect of pulse current on acidification and removal of Cu, Cd, and As during suspended electrodialytic soil remediation

The effect of pulse current on the acidification process and the removal of heavy metals during suspended electrodialytic soil remediation were investigated in this work. Eight experiments with constant and pulse current in two polluted soils were conducted using a 3-compartment membrane cell, predominately working under overlimiting current density conditions. Soil 1 was sampled from a pile of excavated soil at a site with mixed industrial pollution (Cu and Cd), and soil 2 was sampled from the top layer of a wood preservation site (Cu and As). Results showed that pulse current improved the acidification by supplying more reactive H+ ions (defined as the H+ ions causing release of heavy metals from soil particles). The molar ratio of reactive H+ ions to total produced H+ ions (RH+/PH+) was higher in every pulse current experiment than in the corresponding constant current experiment. In addition the removal efficiencies of heavy metals were also improved. The carbonate buffering system in a soil is the first mechanism reacting with the produced H+ ions and impeding the heavy metal mobilization. It was found that the effect of improvement on both the acidification process and the removal of heavy metals were more significant in the soil with highest buffering capacity than the soil with low. Energy distribution analysis demonstrated that most energy was consumed by the transport of ionic species through the soil suspension, and then followed by membranes and electrolytes. The pulse current decreased the energy consumption to different extent depending on the pulse frequency. The lowest energy consumption was obtained in the experiment with the highest pulse frequency (96 cycles per day) for both soils.

Seed bank of Cu-contaminated topsoils at a wood preservation site: impacts of copper and compost on seed germination

Is identification of seed bank (SB) species useful for sustainable management of vegetation restoration on Cu-contaminated soils? How does Cu contamination of the soil affect the SB and can incorporating compost into Cu-contaminated soils counter the effects of Cu? The topsoil SB was investigated at seven contaminated sub-sites of a wood preservation site. The germination parameters of the seeds were recorded using three substrates: a washed river sand (Sand), the same sand spiked with CuSO(4) to reach the same Cu concentrations as in the soil pore water (0.3 to 3.2 mg Cu/L) (Cu), and the same Cu-spiked sand amended with compost (CPM). The total number of germinated seeds (NGS) was 1,081. The whole seedling dataset enabled 12 plant species and eight families to be identified in the SB. Species richness and Shannon indexes were low. The addition of Cu in the germination substrate enhanced total NGS at one sub-site and the addition of CPM increased plant diversity at three sub-sites. SB composition varied with the sub-site but did not correlate with total soil Cu or with the Cu concentration in the soil pore water. Three species belonging to the Poaceae family dominated. In terms of total NGS, the dominant species were Portulaca oleracea and Agrostis capillaris. Similarities between SB and established vegetation were low but increased when the soil bulk density was reduced. The Cu-tolerant species P. oleracea and A. capillaris dominated in both the SB and the established vegetation. However, the pattern of SB and established vegetation differed and consequently SB was not a sufficient indicator to predict the future vegetation.

Phytotoxicity testing of lysimeter leachates from aided phytostabilized Cu-contaminated soils using duckweed ( Lemna minor L.)

Aided phytostabilization of a Cu-contaminated soil was conducted at a wood preservation site located in southwest France using outdoor lysimeters to study leaching from the root zone and leachate ecotoxicity. The effects of Cu-tolerant plants ( Agrostis gigantea L. and Populus trichocarpa x deltoides cv. Beaupré) and four amendments were investigated with seven treatments: untreated soil without plants (UNT) and with plants (PHYTO), and planted soils amended with compost (OM, 5% per air-dried soil weight), dolomitic limestone (DL, 0.2%), Linz–Donawitz slag (LDS, 1%), OM with DL (OMDL), and OM with 2% of zerovalent iron grit (OMZ). Total Cu concentrations (mg kg − 1 ) in lysimeter topsoil and subsoil were 1110 and 111–153, respectively. Lysimeter leachates collected in year 3 were characterized for Al, B, Ca, Cu, Fe, Mg, Mn, P, K and Zn concentrations, free Cu ions, and pH. Total Cu concentration in leachates (mg L − 1 ) ranged from 0.15 ± 0.08 (LDS) to 1.95 ± 0.47 (PHYTO). Plants grown without soil amendment did not reduce total Cu and free Cu ions in leachates. Lemna minor L. was used to assess the leachate phytotoxicity, and based on its growth, the DL, LDS, OM and OMDL leachates were less phytotoxic than the OMZ, PHYTO and UNT ones. The LDS leachates had the lowest Cu, Cu 2+, Fe, and Zn concentrations, but L. minor developed less in these leachates than in a mineral water and a river freshwater. Leachate Mg concentrations were in decreasing order OMDL > DL > PHYTO = OM = LDS > UNT = OMZ and influenced the duckweed growth.

Copper distribution and hydrolase activities in a contaminated soil amended with dolomitic limestone and compost

Chemical fractionation of copper in bulk soil and its distribution in the particle-size fractions were analyzed in a Cu-contaminated soil (674±122 μg Cu g −1, up to 1900 μg Cu g −1 in the clay fraction) sampled from a wood preservation site left untreated and subsequently treated with dolomitic limestone (DL, 0.2% w/w) and compost (CM, 5% w/w), singly and in combination (DL+CM). Soil enzymatic activities of leucine aminopeptidase, cellulase, N-acetyl-β-glucosaminidase, arylsulfatase, β-glucosidase, acetate esterase, butyric esterase, and acid phosphatase were determined. Chemical speciation showed that Cu was mostly present in the acid-soluble and reducible fractions in both untreated and treated soils, whereas treatments with DL and CM reduced the soluble and exchangeable Cu fractions, due to Cu precipitation and complexation, and increased Cu bound to soil organic matter. Analysis of the particle-size fractions showed that more than 80% of Cu was in the silt and clay fractions and that treatment with CM increased the concentration of Cu in the sand size fractions. Soil treatment with DL and CM, singly or in combination, increased hydrolase activities, mainly in the clay fraction, with the largest positive effects on N-acetyl-β-glucosaminidase, leucine aminopeptidase, and β-glucosidase activities. Overall, results confirm that (1) Cu in contaminated soils is mainly bound to the silt–clay fraction, (2) CM additions change its allocation in the particle-size fractions, and (3) treatments with DL and CM singly and in combination reduce Cu solubility and its inhibitory effects on soil enzyme activities.

Copper Phytoextraction in Tandem with Oilseed Production Using Commercial Cultivars and Mutant Lines of Sunflower

Use of sunflower (Helianthus annuus L.) for Cu phytoextraction and oilseed production on Cu-contaminated topsoils was investigated in a field trial at a former wood preservation site. Six commercial cultivars and two mutant lines were cultivated in plots with and without the addition of compost (5% w/w) and dolomitic limestone (0.2% w/w). Total soil Cu ranged from 163 to 1170 mg kg−1. In soil solutions, Cu concentration varied between 0.16– 0.93 mg L−1. The amendment increased soil pH, reduced Cu exposure and promoted sunflower growth. Stem length, shoot and capitulum biomasses, seed yield, and shoot and leaf Cu concentrations were measured. At low total soil Cu, shoot Cu mineralomass was higher in commercial cultivars, i.e., Salut, Energic, and Countri, whereas competition and shading affected morphological traits of mutants. Based on shoot yield (7 Mg DW ha−1) and Cu concentration, the highest removal was 59 g Cu ha−1. At high total soil Cu, shoot Cu mineralomass peaked for mutants (e.g., 52 g Cu ha−1 for Mutant 1 line) and cultivars Energic and Countri. Energic seed yield (3.9 Mg air-DW ha−1) would be sufficient to produce oil. Phenotype traits and shoot Cu removal depended on sunflower types and Cu exposure.

Bioremediation of a Soil Industrially Contaminated by Wood Preservatives—Degradation of Polycyclic Aromatic Hydrocarbons and Monitoring of Coupled Arsenic Translocation

Two commercially available aerobic bioremediation methods (Daramend® and BioSan) were utilized to study the aerobic biodegradation of polycyclic aromatic hydrocarbons (PAH) and the effect of the simultaneously present arsenic. The soil was collected at an old wood preservation site, and the initial PAH16-concentration was 46 mg/kg, with mainly high molecular weight congeners. The As concentration was 105 mg/kg with low availability as assessed with sequential extraction. To enhance the availability of PAH, the effect of a nonionic surfactant was evaluated. Degradation of both low and high molecular weight PAH was observed; however, after 30 weeks, the degradation was generally low and no treatment was significantly better than the others. The treatments had, on the other hand, an effect on As remobilization, with increased As concentration in the available fraction after treatment. This may be due to both the microbial activity and the presence of anoxic microsites in the soil. The overall efficiency of the biological treatment was further evaluated using the standardized ecotoxicity test utilizing Vibrio fischeri (Microtox®). The toxicity test demonstrated that the bioremediation led to an increase in toxicity, especially in treatments receiving surfactant. The surfactant implied an increase in contaminant availability but also a decrease in surface tension, which might have contributed to the overall toxicity increase.

Laboratory and pilot scale soil washing of PAH and arsenic from a wood preservation site: Changes in concentration and toxicity

Soil washing of a soil with a mixture of both polycyclic aromatic hydrocarbons (PAH) and As was evaluated in laboratory and pilot scale, utilizing both single and mixtures of different additives. The highest level of decontamination was achieved with a combination of 0.213 M of the chelating agent MGDA and 3.2 × CMC* of a non-ionic, alkyl glucoside surfactant at pH 12 (Ca(OH) 2). This combination managed to reach Swedish threshold values within 10 min of treatment when performed at elevated temperature (50 °C), with initial contaminant concentrations of As = 105 ± 4 mg/kg and US-EPA PAH 16 = 46.0 ± 2.3 mg/kg. The main mechanisms behind the removal were the pH effect for As and a combination of SOM ionization as a result of high pH and micellar solubilization for PAHs. Implementation of the laboratory results utilizing a pilot scale equipment did not improve the performance, which may be due to the shorter contact time between the washing solution and the particles, or changes in physical characteristics of the leaching solution due to the elevated pressure utilized. The ecotoxicological evaluation, Microtox ®, demonstrated that all soil washing treatments increased the toxicity of soil leachates, possibly due to increased availability of contaminants and toxicity of soil washing solutions to the test organism.

Electrodialytic Remediation of Soil Slurry–Removal of Cu, Cr, and As

Severe soil contamination is often found at old wood preservation sites and a common combination of pollutants is Cu, Cr, and As. In the present work it is tested if simultaneous removal of Cu, Cr, and As can be obtained in an electrodialytic cell where the polluted soil is remediated as a stirred suspension (placed as the desalination compartment in accordance to the position of the ion exchange membranes). The soil for the experiments was sampled at an abandoned wood preservation site and contained 2170 mg Cu/kg, 710 mg Cr/kg and 3200 mg As/kg. SEM-EDX analysis showed that Cu, Cr, As and oxygen formed particles that were cementing soil minerals together. The soil was suspended in distilled water, distilled water with I2 crystals to have an oxidizing environment, or in an acidified environment at pH about 1.0. The experiments lasted from 1 to 3 weeks. Good results were obtained in two experiments; an experiment where the soil was suspended in distilled water and the remediation lasted 3 weeks with 2.5 mA and an experiment with acidification of the soil suspension with HNO3 to pH about 1.0 (2 weeks and 5 mA). The best separation of pollutants and soil was obtained in the experiment with suspension in distilled water. Based on soil concentrations, good Cu removal (95%) was obtained in both experiments. Removal of Cr was most efficient from the acidified soil suspension (74%). Both Cu and Cr concentrations were below the limiting values after the remediation. The As concentration, however, was not even although 61% was removed. In the soil remained about 1070 mg As/kg soil and since the limiting value is 40 mg As/kg, the removal was not efficient enough. So simultaneous removal was possible, but the target values were only met in the case of Cu and Cr, and more research is needed to remove As to a sufficiently low concentration, as well.