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Abstract: Since the world economy has been confronted with an increasing risk of supply shortages of critical raw materials (CRMs), there has been a major interest in identifying alternative secondary sources of CRMs. Bauxite residues from alumina production are available at a multi‐million tonnes scale worldwide. So far, attempts have been made to find alternative re‐use applications for bauxite residues, for instance in cement / pig iron production. However, bauxite residues also constitute an untapped secondary source of CRMs. Depending on their geological origin and processing protocol, bauxite residues can contain considerable amounts of valuable elements. The obvious primary consideration for CRM recovery from such residues is the economic value of the materials contained. However, there are further benefits from re‐use of bauxite residues in general, and from CRM recovery in particular. These go beyond monetary values (e.g. reduced investment / operational costs resulting from savings in disposal). For instance, benefits for the environment and health can be achieved by abatement of tailing storage as well as by reduction of emissions from conventional primary mining. Whereas certain tools (e.g. life‐cycle analysis) can be used to quantify the latter, other benefits (in particular sustained social and technological development) are harder to quantify. This review evaluates strategies of bauxite residue re‐use / recycling and identifies associated benefits beyond elemental recovery. Furthermore, methodologies to translate risks and benefits into quantifiable data are discussed. Ultimately, such quantitative data are a prerequisite for facilitating decision‐making regarding bauxite residue re‐use / recycling and a stepping stone towards developing a zero‐waste alumina production process. © 2018 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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.

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., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

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.

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., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2012 Elsevier B.V. All rights reserved.)

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.

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.

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.

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.

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.

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.