The Phytomanagement of PFAS-Contaminated Land.

Globally, several hundred thousand hectares of both agricultural and urban land have become contaminated with per- and polyfluoroalkyl substances (PFAS). PFAS compounds are resistant to degradation and are mobile in soil compared to other common contaminants. Many compounds have KD values (matrix/solution concentration quotients) of <10. PFAS compounds endanger the health of humans and ecosystems by leaching into groundwater, exposure via dust, and, to a lesser extent, through plant uptake. This review aims to determine the feasibility of phytomanagement, the use of plants, and the use of soil conditioners to minimize environmental risk whilst also providing an economic return in the management of PFAS-contaminated land. For most sites, PFAS combinations render phytoextraction, the use of plants to remove PFAS from soil, inviable. In contrast, low Bioaccumulation Coefficients (BAC; plant and soil concentration quotients) timber species or native vegetation may be usefully employed for phytomanagement to limit human/food chain exposure to PFAS. Even with a low BAC, PFAS uptake by crop plants may still exceed food safety standards, and therefore, edible crop plants should be avoided. Despite this limitation, phytomanagement may be the only economically viable option to manage most of this land. Plant species and soil amendments should be chosen with the goal of reducing water flux through the soil, as well as increasing the hydrophobic components in soil that may bind the C-F-dominated tails of PFAS compounds. Soil conditioners such as biochar, with significant hydrophobic components, may mitigate the leaching of PFAS into receiving waters. Future work should focus on the interactions of PFAS with soil microbiota; secondary metabolites such as glomalin may immobilize PFAS in soil.

Plant uptake and availability of antimony, lead, copper and zinc in oxic and reduced shooting range soil.

Shooting ranges polluted by antimony (Sb), lead (Pb), copper (Cu) and zinc (Zn) are used for animal grazing, thus pose a risk of contaminants entering the food chain. Many of these sites are subject to waterlogging of poorly drained soils. Using field lysimeter experiments, we compared Sb, Pb, Cu and Zn uptake by four common pasture plant species (Lolium perenne, Trifolium repens, Plantago lanceolata and Rumex obtusifolius) growing on a calcareous shooting range soil under waterlogged and drained conditions. To monitor seasonal trends, the same plants were collected at three times over the growing season. Additionally, variations in soil solution concentrations were monitored at three depths over the experiment. Under reducing conditions, soluble Sb concentrations dropped from ∼50 µg L-1 to ∼10 µg L-1, which was attributed to the reduction of Sb(V) to Sb(III) and the higher retention of the trivalent species by the soil matrix. Shoot Sb concentrations differed by a factor of 60 between plant species, but remained at levels <0.3 µg g-1. Despite the difference in soil solution concentrations between treatments, total Sb accumulation in shoots for plants collected on the waterlogged soil did not change, suggesting that Sb(III) was much more available for plant uptake than Sb(V), as only 10% of the total Sb was present as Sb(III). In contrast to Sb, Pb, Cu and Zn soil solution concentrations remained unaffected by waterlogging, and shoot concentrations were significantly higher in the drained treatment for many plant species. Although showing an increasing trend over the season, shoot metal concentrations generally remained below regulatory values for fodder plants (40 µg g-1 Pb, 150 µg g-1 Zn, 15-35 µg g-1 Cu), indicating a low risk of contaminant transfer into the food chain under both oxic and anoxic conditions for the type of shooting range soil investigated in this study.

Biochar as possible long-term soil amendment for phytostabilisation of TE-contaminated soils.

Soils contaminated by trace elements (TEs) pose a high risk to their surrounding areas as TEs can spread by wind and water erosion or leaching. A possible option to reduce TE transfer from these sites is phytostabilisation. It is a long-term and cost-effective rehabilitation strategy which aims at immobilising TEs within the soil by vegetation cover and amendment application. One possible amendment is biochar. It is charred organic matter which has been shown to immobilise metals due to its high surface area and alkaline pH. Doubts have been expressed about the longevity of this immobilising effect as it could dissipate once the carbonates in the biochar have dissolved. Therefore, in a pot experiment, we determined plant metal uptake by ryegrass (Lolium perenne) from three TE-contaminated soils treated with two biochars, which differed only in their pH (acidic, 2.80; alkaline, 9.33) and carbonate (0.17 and 7.3 %) content. Root biomass was increased by the application of the alkaline biochar due to the decrease in TE toxicity. Zinc and Cu bioavailability and plant uptake were equally reduced by both biochars, showing that surface area plays an important role in metal immobilisation. Biochar could serve as a long-term amendment for TE immobilisation even after its alkalinity effect has dissipated.

Toward the Standardization of Biochar Analysis: The COST Action TD1107 Interlaboratory Comparison.

Biochar produced by pyrolysis of organic residues is increasingly used for soil amendment and many other applications. However, analytical methods for its physical and chemical characterization are yet far from being specifically adapted, optimized, and standardized. Therefore, COST Action TD1107 conducted an interlaboratory comparison in which 22 laboratories from 12 countries analyzed three different types of biochar for 38 physical-chemical parameters (macro- and microelements, heavy metals, polycyclic aromatic hydrocarbons, pH, electrical conductivity, and specific surface area) with their preferential methods. The data were evaluated in detail using professional interlaboratory testing software. Whereas intralaboratory repeatability was generally good or at least acceptable, interlaboratory reproducibility was mostly not (20% < mean reproducibility standard deviation < 460%). This paper contributes to better comparability of biochar data published already and provides recommendations to improve and harmonize specific methods for biochar analysis in the future.

Effects of biochar on the transformation and earthworm bioaccumulation of organic pollutants in soil.

Little is known about the effects of biochar on the fate and behavior of micropollutants in soil, especially in the presence of soil macrofauna. Using a 14C-tracer, we studied the fate of 2,4-dichlorophenol and phenanthrene, after 30 days in soil in the presence of a biochar (0-5%, dry weight) produced from China fir at 400 °C and/or the earthworm Metaphire guillelmi. Application of the biochar significantly reduced the degradation and mineralization of both pollutants and strongly increased the accumulation of their metabolites in soil. The earthworm had no significant effects on the degradation of parent molecules of the pollutants but it significantly reduced the mineralization of the pollutants independent of the presence of the biochar. Although at an application rate of <1% the biochar strongly sorbed both pollutants, it did not significantly decrease the bioaccumulation of free dichlorophenol and phenanthrene and their metabolites by the earthworm. Our results demonstrate the complex effects of biochar on the fate, transformation, and earthworm bioaccumulation of organic pollutants in soil. They show that biochar application may not be an appropriate strategy for treating soil contaminated with hydrophobic organic pollutants and underline the importance of soil-feeding earthworms in risk assessments of biochar effects on soil remediation.

Novel method to determine element concentrations in foliage of poplar and willow cuttings.

Measuring the uptake of the chemical elements by plants usually requires the destructive harvest of the plants. Analyzing individual leaves is unsatisfactory because their elemental concentration depends on their age and position on the branch or stem. We aimed to find an easy method to determine the elemental concentrations using a few suitable single leaves along the main shoot of poplar (Populus monviso) and willow (Salix viminalis) cuttings at the end of the first season. Using Ca, Cd, Mn, Fe, K, P, Pb, and Zn concentrations, measured in selected leaves along the main shoots of the cuttings, mathematical functions were derived, which described best their distribution. Elemental allocation patterns were independent of the soil characteristics and soil element concentrations. Based on these functions, three leaves from specific positions along the main shoot were selected, which could accurately describe the derived functions. The deviation of the calculated average concentration, based on the 3-leaves method, was ≤15% in approximately 65% of the cases compared to the measured concentration. This method could be used to calculate element concentrations and fluxes in phytomanagement, biomonitoring, or biomass productions projects using one-season poplar or willow cuttings.

Soil application of biochar produced from biomass grown on trace element contaminated land.

Trace element (TE) contamination of soils is a worldwide problem. However, although not considered safe anymore for food production without clean-up, many of these soils may still be used to produce biomass for non-food purposes such as biochar. Exploring the suitability of such biochar for the amendment of low-fertility soil, we investigated growth and metal accumulation of ryegrass (Lolium perenne, var. Calibra) as well as soil microbial abundance on a non-contaminated soil after amendment with biochar from birch (Betula pendula) wood produced on TE contaminated soil in comparison to a treatment with birch wood biochar originating from non-contaminated soil. Biochars were produced from both feedstocks by pyrolysis at two temperatures: 450 and 700 °C. During the pyrolysis, in contrast to Cu, Fe, Mg, K, Mn and P, the elements Cd, Pb, S and Na volatilized. The root biomass of the biochar treated plants was lower than that of the non-amended plants, while that of the shoot was higher. Plant shoot K and Zn concentrations were increased significantly by up to 7- and 3.3-fold respectively. For P, Mg, Mn, Fe and Cu no significant increase in shoot concentration could be detected. Neither the TE-contaminated biochar, nor the non-contaminated biochar had adverse effect on the bacterial community of the soil.

Metal uptake and allocation in trees grown on contaminated land: implications for biomass production.

Phytostabilization aims to reduce environmental and health risks arising from contaminated soil. To be economically attractive, plants used for phytostabilization should produce valuable biomass. This study investigated the biomass production and metal allocation to foliage and wood of willow (Salix viminalis L.), poplar (Populus monviso), birch (Betula pendula), and oak (Quercus robur) on five different soils contaminated with trace elements (TE), with varying high concentrations of Cu, Zn, Cd, and Pb as well as an uncontaminated control soil. In the treatment soils, the biomass was reduced in all species except oak. There was a significant negative correlation between biomass and foliar Cd and Zn concentrations, reaching up to 15 mg Cd kg(-1) and 2000 mg Zn kg(-1) in willow leaves. Lead was the only TE with higher wood than foliage concentrations. The highest Pb accumulation occurred in birch with up to 135 mg kg(-1) in wood and 78 mg kg(-1) in foliage. Birch could be suitable for phytostabilization of soils with high Cd and Zn but low Pb concentrations, while poplars and willows could be used to stabilise soils with high Cu and Pb and low Zn and Cd concentrations.

Colloidal properties of nanoparticular biogenic selenium govern environmental fate and bioremediation effectiveness.

Microbial selenium (Se) bioremediation is based on conversion of water soluble, toxic Se oxyanions to water insoluble, elemental Se. Formed biogenic elemental Se is of nanometer size, hampering straightforward separation from the aqueous phase. This study represents the first systematic investigation on colloidal properties of pure biogenic Se suspensions, linking electrophoretic mobility (ζ-potential) to column settling behavior. It was demonstrated that circumneutral pH, commonly applied in bioremediation, is not appropriate for gravitational separation due to the negative ζ-potential preventing agglomeration. Mono/di/trivalent counter cations and acidity (protons) were used to screen efficiently the intrinsic negative charge of biogenic Se suspensions at circumneutral pH. Fast settling was induced by La(3+) addition in the micromolar range (86.2 ± 3.5% within 0.5 h), whereas considerably higher concentrations were needed when Ca(2+) or Na(+) was used. Colloidal stability was furthermore studied in different model waters. It was demonstrated that surface waters as such represent a fragile system regarding colloidal stability of biogenic Se suspensions (ζ-potential ∼ -30 mV), whereas dissolved organic matter increases colloidal stability. In marine waters, biogenic Se is colloidally destabilized and is thus expected to settle, representing a potential sink for Se during transport in the aquatic environment.

Accumulation of Sb, Pb, Cu, Zn and Cd by various plants species on two different relocated military shooting range soils.

Annually, more than 400 t Pb and 10 t Sb enter Swiss soils at some 2000 military shooting ranges. After the decommission of military shooting ranges, heavily contaminated soils (>2000 mg kg(-1) Pb) are landfilled or processed by soil washing, whereas for soils with less contamination, alternate strategies are sought. Although the use of military shooting ranges for grazing in Switzerland is common practice, no assessment has been done about the uptake of Sb in plants and its subsequent potential intake by grazing animals. We determined the uptake of Sb, Pb, Cu, Zn and Cd in the aboveground biomass of nine plant species growing on a calcareous (Chur) and a weakly acidic (Losone) military shooting range soil in order to assess if grazing would be safe to employ on decommissioned military shooting ranges. The two soils did not differ in their total concentrations of Cu, Zn, Sb and Cd, they differed however in the total concentration of Pb. Additionally, their physical and chemical properties were significantly different. The accumulation of Zn, Cu, Cd and Pb in the shoots of all nine plant species remained below the Swiss tolerance values for fodder plants (150 mg kg(-1) Zn, 15-35 mg kg(-1) Cu, 40 mg kg(-1) Pb, and 1 mg kg(-1) Cd DW), with the only exception of Pb in Chenopodium album shoots which reached a concentration of 62 mg kg(-1) DW. Antimony concentrations were 1.5-2.6-fold higher in plants growing on the calcareous soil than on the weakly acidic soil. Considering Cu, Zn, Pb, Sb and Cd, all plants, with the exception C. album, would be suitable for grazing on similar shooting range soils.

Assessment of suitability of tree species for the production of biomass on trace element contaminated soils.

To alleviate the demand on fertile agricultural land for production of bioenergy, we investigated the possibility of producing biomass for bioenergy on trace element (TE) contaminated land. Soil samples and plant tissues (leaves, wood and bark) of adult willow (Salix sp.), poplar (Populus sp.), and birch (Betula pendula) trees were collected from five contaminated sites in France and Germany and analysed for Zn, Cd, Pb, Cu, Ca, and K. Cadmium concentration in tree leaves were correlated with tree species, whereas Zn concentration in leaves was site correlated. Birch revealed significantly lower leaf Cd concentrations (1.2-8.9 mg kg(-1)) than willow and poplar (5-80 mg kg(-1)), thus posing the lowest risk for TE contamination of surrounding areas. Birch displayed the lowest bark concentrations for Ca (2300-6200 mg kg(-1)) and K (320-1250 mg kg(-1)), indicating that it would be the most suitable tree species for fuel production, as high concentrations of K and Ca decrease the ash melting point which results in a reduced plant lifetime. Due to higher TE concentrations in bark compared to wood a small bark proportion in relation to the trunk is desirable. In general the bark proportion was reduced with the tree age. In summary, birch was amongst the investigated species the most suitable for biomass production on TE contaminated land.

A critical view of current state of phytotechnologies to remediate soils: still a promising tool?

Phytotechnologies are often shown as an emerging tool to remediate contaminated soils. Research in this field has resulted in many important findings relating to plant and soil sciences. However, there have been scant private and public investments and little commercial success with this technology. Here, we investigate the barriers to the adoption of phytotechnologies and determine whether it is still a fertile area for future research. The terminology used in phytotechnologies includes a confusing mish-mash of terms relating to concepts and processes increasing the difficulty of developing a unique commercial image. We argue that the commercial success of phytotechnologies depends on the generation of valuable biomass on contaminated land, rather than a pure remediation technique that may not compare favourably with the costs of inaction or alternative technologies. Valuable biomass includes timber, bioenergy, feedstock for pyrolosis, biofortified products, or ecologically important species.

Hydrolysed wool: a novel chelating agent for metal chelant-assisted phytoextraction from soil.

Phytoextraction has revealed great potential, however it is limited by the fact that plants need time and nutrient supply and have a limited metal uptake capacity. Although the use of synthetic chelators, such as EDTA, enhances heavy metal extraction, it also produces the negative side effects of high phytotoxicity, as well as leaching of essential metals. The aim of this research was to investigate the application of wool, in mobilising metals and in improving the phytoextraction of metals-contaminated soil. We performed column experiments with 14 d and 7 d partially hydrolysed wool as chelating agent on a silty-loamy sand agricultural soil. In the column experiment the 14 d wool hydrolysate mobilised 68% of Cu in soil, whereas in the case of Cd it mobilised 5.5%. The model plant selected for the phytoextraction experiments was tobacco (Nicotiana tabacum). The plant uptake of Cd and Cu, assisted by the application of 6.6 g kg(-1) wool hydrolysate was increased by 30% in comparison to the control plants. The application of 13.3 g kg(-1) wool hydrolysate enhanced the Cu uptake by up to 850%. Moreover, high leaching probability frequently observed when applying chelating agents, such as EDTA or ethylene diamine disuccinate (EDDS), were not detected. The use of hydrolysed wool therefore merits further investigation.

Chelate assisted phytoextraction of heavy metals from soil. Effect, mechanism, toxicity, and fate of chelating agents.

The low-cost, plant-based phytoextraction technique has often been described as a promising technique to remediate heavy metal contaminated agricultural land. The application of chelating agents has shown positive effects in increasing the solubility of heavy metals in soil and therefore in enhancing phytoextraction. This paper gives an overview of the chelating agents applied in recent studies. Various synthetic aminopolycarboxylic acids, such as ethylene diamine tetraacetic acid, and natural ones such as, ethylene diamine disuccinate and nitrilotriacetic acid, are described. Additionally, results of the application of natural low molecular weight organic acids, such as citric and tartaric acid are given. The effectiveness of these different chelating agents varies according to the plant and the heavy metals used. Furthermore, a focus is laid on the chelating agents fate after application and on its toxicity to plants and soil microorganisms, as well as it degradation. The rate of degradation is of great importance for the future of chelate assisted phytoextraction as it has a direct impact on the leaching probability. An effective prevention of leaching will be crucial for the acceptance and the economic breakthrough of enhanced phytoextraction, but a satisfactory solution to this key issue has so far not been found. Possibly further experiments in the field of enhanced phytoextraction will be able to solve this major problem, but over decades various greenhouse experiments and recently field experiments have resulted in different observations. Therefore, it is questionable if further research in this direction will lead to a promising solution. Phytoextraction has possibly reached a turning point in which it should distance itself from chelate assisted phytoextraction and focus on alternative options.

The influence of EDDS and EDTA on the uptake of heavy metals of Cd and Cu from soil with tobacco Nicotiana tabacum.

Phytoextraction, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. In order to enhance phytoextraction the use of chelating agents has been proposed. This study aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposed, as an alternative to ethylene diamine tetraacetate (EDTA). EDDS revealed a higher toxicity to tobacco (Nicotiana tabacum) in comparison to EDTA, but no toxicity to microorganisms. The uptake of Cu was increased by the addition of EDTA and EDDS, while no increase was observed in the uptake of Cd. Both chelating agents showed a very low root to shoot translocation capability and the translocation factor was lower than the one of the control. Heavy metals where significantly more phytoavailable than in the control, even after harvesting, resulting in a high heavy metal leaching possibility, probably owing to a low biodegradation rate of EDDS. New seedlings which were transplanted into the EDDS treated pots 7d after the phytoextraction experiment, showed signs of necrosis and chlorosis, which resulted in a significantly lower biomass in comparison to the control. The seedlings on the EDTA treated pots showed no toxicity signs. Contrary to previous opinions the results of this study revealed the chelating agents EDTA and EDDS as unsuitable for enhanced phytoextraction using tobacco.

Cyanide phytoremediation by water hyacinths (Eichhornia crassipes).

Although cyanide is highly toxic, it is economically attractive for extracting gold from ore bodies containing only a few grams per 1000 kg. Most of the cyanide used in industrial mining is handled without observable devastating consequences, but in informal, small-scale mining, the use is poorly regulated and the waste treatment is insufficient. Cyanide in the effluents from the latter mines could possibly be removed by the water hyacinth Eichhornia crassipes because of its high biomass production, wide distribution, and tolerance to cyanide (CN) and metals. We determined the sodium cyanide phytotoxicity and removal capacity of E. crassipes. Toxicity to 5-50 mg CN L(-1) was quantified by measuring the mean relative transpiration over 96 h. At 5 mgCNL(-1), only a slight reduction in transpiration but no morphological changes were observed. The EC(50) value was calculated by probit analysis to be 13 mgCNL(-1). Spectrophotometric analysis indicated that cyanide at 5.8 and 10 mgL(-1) was completely eliminated after 23-32 h. Metabolism of K(14)CN was measured in batch systems with leaf and root cuttings. Leaf cuttings removed about 40% of the radioactivity from solution after 28 h and 10% was converted to (14)CO(2); root cuttings converted 25% into (14)CO(2) after 48 h but only absorbed 12% in their tissues. The calculated K(m) of the leaf cuttings was 12 mgCNL(-1), and the V(max) was 35 mg CN(kg fresh weight)(-1)h(-1). Our results indicate that E. crassipes could be useful in treating cyanide effluents from small-scale gold mines.

Evaluation of the effect of small organic acids on phytoextraction of Cu and Pb from soil with tobacco Nicotiana tabacum.

Phytoremediation, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. However its use is limited by the time required for plant growth, the nutrient supply and, moreover, by the limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction, but they have also revealed several negative side-effects. The objective of this study was to investigate the use of three natural low molecular weight organic acids (NLMWOA) (citric, oxalic, and tartaric acid) as an alternative to synthetic chelators. Slurry-, column-, toxicity- and phytoextraction experiments were performed. For the phytoextraction experiment the three NLMWOA were applied to a copper- and a lead-contaminated soil respectively. A significant increase in copper uptake was visible only in the citric acid treatment (67 mg kg-1) in comparison to the EDTA treatment (42 mg kg-1). The NLMWOA application showed no enhanced effect concerning the lead phytoextraction. A possible explanation for this lack of significance could be the rate of the degradation of NLMWOA. This rate might well be too high for these heavy metals with low mobility and bioavailability such as lead. The amounts of NLMWOA applied to the soil were very high (62.5 mmol kg-1 of soil) and the effect was too little. In this respect EDTA, which was applied in very small amounts (0.125 mmol kg-1) was more efficient. Thus making NLMWOA unsuitable to enhance phytoextraction of heavy metals from soil.

The influence of humic acids on the phytoextraction of cadmium from soil.

Cadmium poses a major environmental and human health threat because of its constant release through anthropogenic activities. A need, therefore, exists for cost-effective remediation procedures. Phytoremediation, the use of plants to extract contaminants from soils and groundwater, has revealed great potential. However, it is limited by the fact that plants need time, nutrient supply and, moreover, have a limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction through phytoremediation, but they have also revealed a vast number of negative side-effects. The objective of this research was to investigate the use of humic acids as an alternative to synthetic chelators. Humic acids were applied to a cadmium-contaminated soil at various dosages, and the uptake of cadmium into Nicotiana tabacum SR-1 was determined in relation to the amounts of total and bioavailable cadmium in the soil. It was found that the theoretical bioavailability of cadmium, as determined by diethylenetriaminepentaacetic acid (DTPA) extraction, did not change, but its plant uptake was enhanced significantly, in some cases up to 65%. Humic acids added at a rate of 2 g kg(-1) soil increased the cadmium concentration in the shoots from 30.9 to 39.9 mg kg(-1). A possible reason for this enhancement is the decrease in pH, resulting in higher cadmium availability. Another possibility taken into account is that plants may take up cadmium complexes with humic acid fragments, which result from microbiological degradation or, self-dissociation.