Search

Despite the centrality of staple grains for human well-being, both as a source of nutrients and of toxic ions, there is little understanding of where and how elements vary, and if there are particular elements that correlate. Here, for shop bought polished (white) rice, we comprehensively characterized trace (arsenic species, cadmium, copper, iron, manganese, molybdenum, rubidium and zinc) and macro-nutrients (calcium, chlorine, potassium, phosphorus and sulphur) for grain purchased in 18 countries, across four continents, a total of 1045 samples. This was to investigate if there were any major differences between geographic location and elemental content, and to observe if there were any patterns in elemental distribution. Greatest variation in the median was observed for the non-essential rubidium (15-fold) and arsenic species (fivefold). Rubidium was the highest in the Americas, lowest in Europe, while inorganic arsenic (iAs) and dimethylarsonic acid (DMA) were low for Africa and high in the South American and European continents. The highest concentrations of cadmium were found in Asian samples, and lowest in South America, with variation within these regions. At the extremes of individual counties, China had fivefold higher concentrations than the global median, while Tanzania was fourfold lower than this value. Calcium, potassium, molybdenum and phosphorus were the highest in European and lowest in African grain, though the fold-differences were relatively low, ~ 0.2, while iron was the highest in African grain and lowest in European, Asian and South American grain, with a ~ twofold difference. Selenium was also higher in Africa versus other regions, and copper, manganese and zinc were the highest in American grain. Factor analysis showed that copper, cadmium, molybdenum, rubidium and selenium were strongly associated together, and these element’s factor loadings were diametrically opposed to less tightly associated calcium, chlorine, manganese, potassium, phosphorus and sulphur. Stepwise additions linear region analysis was performed on log-transformed concentrations to investigate cadmium associations in more detail. Selenium was the greatest predictor of cadmium concentration, followed by molybdenum, accounting for over 50% of the contribution to the adjusted R2. Arsenic species were only weakly correlated with other elements. The implications for these findings with respect to dietary nutrition are discussed. Vietnamese rice was notable in being deficient in macro- and micro-nutrients while also being elevated in cadmium at a median of 0.02 mg/kg, with China though still having a median that is ~ 2.5-fold this concentration. These Chinese concentrations are of particular concern as the 75th percentile for China is 0.1 mg/kg, a value that triggers regulatory action for rice products.

Green, Andy J. et al., One of cadmium’s major exposure routes to humans is through rice consumption. The concentrations of cadmium in the global polished (white), market rice supply-chain were assessed in 2270 samples, purchased from retailers across 32 countries, encompassing 6 continents. It was found on a global basis that East Africa had the lowest cadmium with a median for both Malawi and Tanzania at 4.9 μg/kg, an order of magnitude lower than the highest country, China with a median at 69.3 μg/ kg. The Americas were typically low in cadmium, but the Indian sub-continent was universally elevated. In particular certain regions of Bangladesh had high cadmium, that when combined with the high daily consumption rate of rice of that country, leads to high cadmium exposures. Concentrations of cadmium were compared to the European Standard for polished rice of 200 μg/kg and 5% of the global supply-chain exceeded this threshold. For the stricter standard of 40 μg/kg for processed infant foods, for which rice can comprise up to 100% by composition (such as rice porridges, puffed rice cereal and cakes), 25% of rice would not be suitable for making pure rice baby foods. Given that rice is also elevated in inorganic arsenic, the only region of the world where both inorganic arsenic and cadmium were low in grain was East Africa.

Despite the centrality of staple grains for human well-being, both as a source of nutrients and of toxic ions, there is little understanding of where and how elements vary, and if there are particular elements that correlate. Here, for shop bought polished (white) rice we comprehensively characterize trace (arsenic species, cadmium, copper, iron, manganese, molybdenum, rubidium and zinc) and macro-nutrients (calcium, chlorine, potassium, phosphorus and sulphur) for grain purchased in 18 countries, across 4 continents, a total of 1045 samples, to investigate if there were any major differences between geographic location and elemental content, and to observe if there were any patterns in elemental distribution. Greatest variation in the median was observed for the non-essential rubidium (15-fold) and arsenic species (5-fold). Rubidium was highest in the Americas, lowest in Europe, while inorganic arsenic and dimethylarsonic acid (DMA) were low for Africa and high in the South American and European continents. Cadmium had the highest concentration in Asian samples and lowest in South America. Calcium, potassium, molybdenum and phosphorus, were highest in European and lowest in African grain, though the fold-differences were relatively low, ~ 0.2, while iron was highest in African grain and low in European, Asian and South American grain, with a ~ 2-fold difference. Selenium was also higher in Africa versus other regions, and copper, manganese and zinc where highest in American grain. Factor analysis showed that copper, cadmium, molybdenum, rubidium and selenium were strongly associated together, and these element’s factor loadings were diametrically opposed to less tightly associated calcium, chlorine, manganese, potassium, phosphorus and sulphur. Stepwise additions linear region analysis was performed on log transformed concentrations to investigate cadmium associations in more detail. Selenium was the greatest predictor of cadmium concentration, followed by molybdenum, accounting for over 50% of the contribution to the adjusted R2. Arsenic species were only weakly correlated with other elements. The implications for these findings with respect to dietary nutrition are discussed.

The application of pyrogenic materials in immobilization processes of metalloids represents a burning issue in environmental and waste applications and management. The main objective of this study was to characterize the effect of biomass pretreatment by Cu, Fe and Mg blending and pyrolysis temperature on As sorption efficiency as a model of anionic metalloids from model solutions and As immobilization in old mine soil by pyrogenic materials. The physico-chemical characterization of engineered materials produced in slow pyrolysis process at 400 and 700°C from metal-blended hard wood chips (30% w/w) showed increasing of surface areas (1.4–1.8-fold), changes in pH, and more than 50% decrease in total C content. The batch sorption processes of As ions by Cu-modified pyrogenic materials (CuPM), Fe-modified pyrogenic materials (FePM), and Mg-modified pyrogenic materials (MgPM) showed increasing uptake in order CuPM700 (Qmax 2.56 mg g−1) 3.2 times and MgPM400 > 5 times compared to control. Promising pyrogenic material MgPM400 showed immobilization effect also on additional heavy metals (Cd, Cu, Fe, Mn, Pb, Sr, Zn) present in studied soil.

BACKGROUND: Nowadays a significant amount of land contaminated with toxic elements is being used for agriculture, posing a serious risk of crop contamination and toxicity. Several methodologies are being used to remediate soil contamination, including the use of amendments such as biochar. This work evaluated the effects of biochar combined with different fertirrigations (water, a conventional fertilizer solution, or a fertilizer solution with a commercial biostimulant derived from leonardite) on the availability of toxic elements and nutrients for pepper cultivated in a soil contaminated with As, Cd, Pb, and Zn. RESULTS: Irrigation with fertilizer solutions improved plant growth regardless of the biochar amendment. Biochar decreased the bioavailability of Cu and Pb in soil and the Cu content in pepper leaves. Combined with fertilization, biochar also decreased plant As and Pb content. Biochar combined with biostimulant decreased the bioavailable content of Cd in soil and its uptake by pepper plants. CONCLUSION: The use of biochar and biostimulant presented advantages for plant production in a non-suitable scenario of nutrient scarcity and contamination, We thank the agronomic technicians Manuel Campos Macossay and Carlos Rodriguez Orta for the location of the soil and supply of materials. This article is the result of a research project ‘Compar ison of agronomic efficiency between Huma Gro® products and mineral conventional fertilizers’ funded by Bio Huma Netics Inc. (Gilbert, Arizona, USA). Bio Huma Netics Inc. did not participate in the experimental procedures or in the evaluation of the results

High concentrations of arsenic (As) in groundwater threaten the environment and public health. Geogenically, groundwater As contamination predominantly occurs via its mobilization from underground As-rich sediments. In an aquatic ecosystem, As is typically driven by several underlying processes, such as redox transitions, microbially driven reduction of iron (Fe) oxide minerals, and release of associated As. Notably, dissolved As mobilized from soils and sediments exhibits high affinity for dissolved organic matter (DOM). Thus, high DOM concentrations can increase As mobility. Therefore, it is crucial to understand the complex interactions and biogeochemical cycling of As, DOM, and Fe oxides. This review collates knowledge regarding the fate of As in multicomponent As-DOM-Fe systems, including ternary complexes involving both Fe and DOM. Additionally, the release mechanisms of As from sediments into groundwater in the presence of both Fe and DOM have been discussed. The mechanisms of As mobilization/sorption at the solid-water interface can be affected by negatively charged DOM competing for sorption sites with As on Fe (oxy)(hydr)oxides and may be further modified by other anionic ubiquitous species such as phosphate, silicic acid, or sulfur. This review emphasizes the need for a comprehensive understanding of the impact of DOM, Fe oxides, and related biogeochemical processes on As mobilization to aquifers. The review identifies important knowledge gaps that may aid in developing applicable practices for preventing the spread of As contamination in aquatic resources and traditional soil management practices.

The biogeochemical cycling of multiple soil elements is fundamental for life on Earth. Here, we conducted a global field survey across 16 chronosequences from contrasting biomes with soil ages ranging from centuries to millions of years. For this, we collected and analysed 435 topsoil samples (0-10 cm) from 87 locations. We showed that high levels of topsoil element coupling, defined as the average correlation among nineteen soil elements, are maintained over geological timescales globally. Cross-biome changes in plant biodiversity, soil microbial structure, weathering, soil pH and texture, and mineral-free unprotected organic matter content largely controlled multi-element coupling. Moreover, elements with heavier atomic mass were naturally more decoupled and unpredictable in space than those with lighter mass. Only the coupling of carbon, nitrogen and phosphorus, which are essential to life on Earth, deviated from this predictable pattern, suggesting that this anomaly may be an undeniable fingerprint of life in terrestrial soils.

High concentrations of heavy metal[loid]s in soils, spoils, vegetation and waters in the proximity of former metalliferous mining areas may pose a risk to the environment if dispersed. Several amendments were compared for their abilities to reduce the phyto-toxicity of a contaminated mine spoil (≤ 10,000 mg kg − 1 As, Bi, Cd, Cu, Hg, Pb and Zn). Iron and phosphorus based amendments or compost were mixed into mine soil [spoil] and ryegrass was germinated on the mixtures in a 90-day pot trial. Metal[loid] concentrations in pore waters and ryegrass tissues were measured to compare the effects of each amendment on 1) metal[loid]s in solution, 2) their uptake to plant tissue and 3) plant biomass production. The data were evaluated in terms of environmental risk and practical application to mine site remediation. Iron based amendments significantly reduced As, Cd and Cu concentrations in pore water > 2 fold compared to the untreated mine spoil. Compost and Fe(II) + CaCO 3 resulted in the lowest concentrations of metal[loid]s in ryegrass tissue and a significant increase in biomass, matching that achieved in a control, non-contaminated soil. Phosphorus based amendments generally had no significant impact on, or increased metal[loid]s in pore water whilst also failing to improve ryegrass biomass yields significantly, suggesting that factors other than nutrient deficiency, for example phyto-toxicity, hindered vegetation growth. Given that compost induced the particularly displeasing effect of considerable solubilisation of As (> 300 μg l − 1 in pore water) when added to the mine soil [spoil], Fe based amendments can be adjudged as the most suitable to deploy for the remediation of metal[loid] affected areas at this mine site. This is especially the case for Fe(II) + CaCO 3 due to its more favourable effects on pH and ryegrass yield than Fe oxide alone.

The availability of metallic nutrients in dryland soils, many of which are essential for the metabolism of soil organisms and vascular plants, may be altered due to climate change-driven increases in aridity. Biocrusts, soil surface communities dominated by lichens, bryophytes and cyanobacteria, are ecosystem engineers known to exert critical functions in dryland ecosystems. However, their role in regulating metallic nutrient availability under climate change is uncertain. Here, we evaluated whether well-developed biocrusts modulate metallic nutrient availability in response to 7 years of experimental warming and rainfall reduction in a Mediterranean dryland located in southeastern Spain. We found increases in the availability of K, Mg, Zn and Na under warming and rainfall exclusion. However, the presence of a well-developed biocrust cover buffered these effects, most likely because its constituents can uptake significant quantities of available metallic nutrients. Our findings suggest that biocrusts, a biotic community prevalent in drylands, exert an important role in preserving and protecting metallic nutrients in dryland soils from leaching and erosion. Therefore, we highlight the need to protect them to mitigate undesired effects of soil degradation driven by climate change in this globally expanding biome., Eduardo Moreno-Jiménez et al. experimentally manipulate rainfall and temperature in a Mediterranean dryland to explore the association of biocrusts with essential metallic nutrients. They find that biocrusts—communities of lichens, bryophytes and cyanobacteria on the soil surface—can buffer against the effects of warming and reduced rainfall on metallic nutrient availability.

© The Author(s)., Current intensive agricultural practices, although highly successful in terms of production, have been found to be environmentally unsustainable. One of the crucial approaches to increase agricultural sustainability is the recycling of organic wastes, since these materials often contain many beneficial nutrients for soil and agriculture. Recently, pyrolytic conversion of biodegradable waste into charred material has gained global attention as an amendment to recycle nutrients while improving soil health. Increasing interest in the beneficial applications of pyrolyzed biomass has expanded multidisciplinary areas for science and engineering. The fertilizers used in this study were prepared by pyrolyzing mixtures of two abundant residues in Mediterranean areas: grape seeds and sewage sludge, in different proportions (100% GS, 75% GS-25% SS, 50% GS-50% SS, 25% GS-75% SS, 100% SS). In addition, fresh sludge was mixed with pyrolyzed grape seeds and included as an additional treatment. In this study, the positives and negatives of the application of biochars on agronomic potential and environmental risk have been addressed, taking into account P, Zn, Cu, Fe, As and Cd. In order to choose the best mixture, it is necessary to find a compromise between maximizing the beneficial elements that are translocated to the plant crop, as well as reducing the elements that are leached. Results of a 6-week greenhouse study indicated that the unpyrolyzed sludge mixture contained the largest amount of available nutrients Fe, Cu and P. In agreement, this treatment mixed with a Chromic Luvisol soil (40 ton/ha) increased the uptake of these elements in corn (Zea mays L.—LG ambitious). The yield also increased by 60% in this treatment. However, this mixture also contained more contaminants (As, Cd) which were extracted with Ammonium Bicarbonate-DTPA. According to our results, the treatments where grape seeds and sewage sludge were mixed at 50% and then pyrolyzed exhibited the optimal compromise between efficiency (nutrients uptake) and tolerable levels of potentially toxic elements in leachates., The authors thank the Project UAM-Santander 2017/ASIA/07 “Applications of modified biochars for agro-environmental management” for funding this research.

Stabilized cementitious aggregates AG were produced from wood ashes containing ∼10,000 mg kg−1 As, Cr and Cu, then amended to two agricultural pasture soils. Metal(loid) leaching (column tests), mobility (pore water extracts) and uptake to ryegrass was determined, comparing raw ashes with aggregates. Risk modeling was applied to selected data to inform wider discussion of the experimental results. Under rapid leaching (7 h) AG 2 (pre-strengthened with CO2) outperformed AG 1 in suppressing soluble metal(loid) removal. During prolonged leaching (12d) both aggregates were susceptible to mild dissolution/release of metal(loid)s upon acidification. Pore water sampled from the pot test indicated that Cr was generally most mobile, As least so, reduced furthest by AG 2. Risk modelling, based on pot experimental data, demonstrated soil specific accumulation of As in beef muscle and milk, being furthest reduced (compared to the raw ash addition) by AG 2 in soil A, but increased in soil B by the same treatment. The results of this study indicate that a reduction in soluble As, Cr and Cu can be achieved through cementitious aggregation of wood ashes, though the extent is metal(loid) specific when amended to soils. Pre-testing under local soil conditions before field application would be required to ensure that metal(loid) mobility remained suppressed.

An outdoor macrocosm experiment using Fe-based and organic amendments over 2 years was set up to evaluate the effectiveness of aided-phytostabilisation. For that, a soil contaminated with As- and Cu-rich waste material (∼13000 mg As kg−1 and ∼500 mg Cu kg−1) was treated with combinations of iron sulphate (Fe) with lime, paper mill sludge (PS), holm-oak biochar (BC), olive mill waste compost (OMWC) or green waste compost (GWC). Rye (Secale cereale L.) was grown in the treated and non-treated soils 16 months after addition of the amendments. Arsenic and Cu dynamics in soil were assessed throughout the experiment and soil quality parameters (soil nutrients, organic matter and soil biology) were measured almost two years after addition of the amendments. All treatments resulted in a reduction of soluble and extractable Cu during the experiment and, despite the increase in soil pH (from 5 to 68) and DOC (from 10 up to 50 mg DOC L−1) provoked by the amendments, As was not significantly mobilised in the treated soils. Treatments combining Fe sulphate with the organic materials, especially biochar and both composts, resulted in an increase in soil available nutrients and enhanced rye growth. In this semi-field scale experiment, the combination of Fe sulphate with holm-oak biochar showed the most promising results in terms of soil fertility (nutrient availability), plant As and Cu uptake and soil C sequestration. Further research should focus on monitoring long-term effects of the soil amendments on crops, following repeated applications.

Drylands cover more than 40% of terrestrial surface, and their global extent and socio-ecological importance will increase in the future due to the forecasted increases in aridity driven by climate change. Despite the essential role of metallic micronutrients in life chemistry and ecosystem functioning, it is virtually unknown how their bioavailability changes along aridity gradients at the global scale. Here we analysed soil total and available Cu, Fe, Mn, and Zn in 143 drylands from all continents, except Antarctica, covering a broad range of aridity and soil conditions. We found that total and available micronutrient concentrations in dryland soils were low compared to averages commonly found in soils of natural and agricultural ecosystems globally. Aridity negatively affected the availability of all micronutrients evaluated, mainly indirectly by increasing soil pH and decreasing soil organic matter. Remarkably, the available Fe:Zn ratio decreased exponentially as aridity increased, pointing to stoichiometric alterations. Our findings suggest that increased aridity conditions due to climate change will limit the availability of essential micronutrients for organisms, particularly that of Fe and Zn, which together with other adverse effects (e.g., reduced water availability) may pose serious threats to key ecological processes and services, such as food production, in drylands worldwide.

Soil pollution with trace elements is a concerning issue worldwide. Monitoring of soil pollution and remediation protocols need still from valid complementary analytical approaches able to detect changes in speciation and lability of metals in soils (e.g. stabilization or mobility). In this work, we compare three different analytical approaches to assess potential changes in environmental availability of Cu, As and Zn in a Mediterranean polluted soil that was amended with different combinations of iron sulphate and alkaline paper sludge waste. The studied methods were: (i) a standard large-bore flow-through column system (macrocolumn), (ii) an automatic dynamic flow-through microcolumn extraction system, and (iii) the diffusive gradients in thin gels technique (DGT). The three analytical approaches tested showed immobilization of Zn and Cu in contaminated mine soils after co-application of paper sludge and iron sulphate, but they differ quantitatively in terms of As mobility. Interconversion between oxidation states of inorganic As is observed to occur to a larger extent in macrocolumn. Because this may only occur in very specific Mediterranean scenarios (i.e. organic matter application to intermittently flooded mine soils), macrocolumn extraction procedures might not appropriately mimic the environmental availability of As in soils with organic amendments (e.g., paper sludge waste). Microcolumn leaching is the fastest screening tool to ascertain the efficiency of chemical amendments, but DGT is a good alternative with less technical demands.

The efficiency of combining iron sulfate and organic amendments (paper mill sludge, olive mill waste compost and olive tree pruning biochar) for the remediation of an As- and Cu-contaminated soil was evaluated. Changes in As and Cu fractionation and solubility due to the application of the amendments was explored by leachate analysis, single and sequential extractions. Also, the effects on Arrhenatherum elatius growth, germination of Lactuca sativa and toxicity to the bacteria Vibrio fischeri were assessed. The combination of iron sulfate and the organic amendments efficiently reduced As solubility and availability through the formation of amorphous iron oxides, while organic matter did not seem to mobilize As. At the same time, copper fractionation was strongly affected by soil pH and organic matter addition. The soil pH significantly influenced both As and Cu mobility. Within all the amendments tested, FeSO4 in combination with compost showed to be the most suitable treatment for the overall remediation process, as it reduced As and Cu availability andenhanced soil nutrient concentrations and plant growth. In sipte of contradictory trends between chemical analyses and ecotoxicity tests, we can still conclude that the application of organic amendments in combination with reactive iron salts is a suitable approach for the remediation of soils contaminated by Cu and As.

The utilization of carbonaceous materials in separation processes of radionuclides, heavy metals and metalloids represents a burning issue in environmental and waste management. The main objective of this study was to characterize the effect of chemical modification of corncob-derived biochar by Fe-impregnations on sorption efficiency of Eu and As as a model compounds of cationic lanthanides and anionic metalloids. The biochar sample produced in slow pyrolysis process at 500 °C before (BC) and after (IBC) impregnation process was characterized by elemental, FTIR, SEM-EDX analysis to confirm the effectiveness of Fe-impregnation process. The basic physico-chemical properties showed differences in surface area and pH values of BC- and IBC-derived sorbents. Sorption processes of Eu and As by BC and IBC were characterized as a time- and initial concentration of sorbate-dependent processes. The sorption equilibrium was reached for both sorbates in 24 h of contact time. Batch equilibrium experiments revealed the increased maximum sorption capacities (Q max) of IBC for As about more than 20 times (Q max BC 0.11 and Q max IBC 2.26 mg g−1). Our study confirmed negligible effect of Fe-impregnation on sorption capacity of biochar for Eu (Q max BC 0.89 and Q max IBC 0.98 mg g−1). The iron-impregnation of biochar-derived sorbents can be utilized as a valuable treatment method to produce stable and more effective sorption materials for various xenobiotics separation from liquid wastes and aqueous solutions.

Heavy metal(loid) rich ash (≤10,000 mg kg-1 total As, Cr, Cu and Zn) originating from the combustion of contaminated wood was subjected to several experimental procedures involving its incorporation into an upland pasture soil. Ash was added to soil that had been prior amended with local cattle manure, replicating practices employed at the farm scale. Metal(loid) concentrations were measured in soil pore water and ryegrass grown on soil/manure plus ash mixtures (0.1-3.0% vol. ash) in a pot experiment; toxicity evaluation was performed on the same pore water samples by means of a bacterial luminescence biosensor assay. Thereafter a sequential extraction procedure was carried out on selected soil, manure and ash mixtures to elucidate the geochemical association of ash derived metal(loid)s with soil constituents. Predictive modelling was applied to selected data from the pot experiment to determine the risk of transfer of As to meat and milk products in cattle grazing pasture amended with ash. The inclusion of manure to soils receiving ash reduced phyto-toxicity and increased ryegrass biomass yields, compared to soil with ash, but without manure. Elevated As and Cu concentrations in pore water and ryegrass tissue resulting from ash additions were reduced furthest by the inclusion of manure due to an increase in their geochemical association with organic matter. Zinc was the only measured metal(loid) to remain uniformly soluble and bioavailable regardless of the addition of ash and manure. Risk modelling on pot experimental data highlighted that an ash addition of >1% (vol.) to this pasture soil could result in As concentrations in milk and meat products exceeding acceptable limits. The results of this study therefore suggest that even singular low doses of ash applied to soil increase the risk of leaching of metal(loid)s and intensify the risk of As transfer in the food chain.

Background: Translocating plants for conservation purposes can be a useful tool to enhance existing populations, restore lost populations or create new ones, but has rarely been done for bryophytes, especially liverworts.Aims: Here, the leafy liverwort Herbertus hutchinsiae, a representative species of oceanic-montane liverwort-rich heath, was translocated to unoccupied habitat within its current range, to establish whether its restricted distribution is due to habitat or dispersal limitation.Methods: Feasibility of establishing new populations outside the current distribution range was assessed, to test the suitability of the species for assisted colonisation. Furthermore, transplants were grown at degraded sites where the species had declined to assess potential for restoration.Results: Although maximal growth rates occurred within-range, transplants grew at all sites, indicating that the species could be dispersal limited; a conclusion supported by distribution modelling.Conclusions: Assisted colonisat...

The contamination of soils and waters with organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), affect a large number of sites worldwide that need remediation. In this context soils amendments can be used to immobilise PAHs while maintaining soil functioning, with biochar being a promising amendment. In this experiment, phenantrene (Phe) was used as a frequent PAH contaminating soils and we studied the effect of three biochars at 1% applications to three different substrates, two agricultural topsoils and pure sand. We evaluated the changes in soil properties, sorption-desorption of Phe, and mineralisation of Phe in all treatments. Phe in pure sand was effectively sorbed to olive pruning (OBC) and rice husk (RBC) biochars, but pine biochar (PBC) was not as effective. In the soils, OBC and RBC only increased sorption of Phe in the silty soil. Desorption was affected by biochar application, RBC and OBC decreased water soluble Phe independently of the soil, which may be useful in preventing leaching of Phe into natural waters. Contrastingly, OBC and RBC slightly decreased the mineralisation of Phe in the soils, thus indicating lower bioavailability of the contaminant. Overall, biochar effects in the two tested soils were low, most likely due to the rather high soil organic C (SOC) contents of 2.2 and 2.8% with Koc values in the same range as those of the biochars. However, OBC and RBC additions can substantially increase adsorption of Phe in soils poor in SOC., This work was partly supported by Spanish MINECO, project number CTM2013-48697- C2-2-R. COST Action TD1107 funded Eduardo Moreno Jiménez during his experiments in Germany.

An aided phytostabilisation strategy consisting of several composite amendments of iron sulphate and organic materials combined with Lupinus albus L. (white lupin) was evaluated for remediation of an As- and Cu-contaminated soil. Iron sulphate was combined with lime, paper mill sludge (PS), olive mill waste compost (OMWC) or holm oak biochar (BC) and applied to a slightly acidic soil with high concentration of As (∼2200 mg kg −1 ) and Cu (∼150 mg kg −1 ). White lupin was grown for 48 days in pots containing amended and non-amended soils and the effect of soil treatments on soluble and extractable trace elements, soil fertility and plant growth and composition was evaluated. The addition of the amendments raised soil pH and reduced soluble As (50–93%) and extractable As and Cu (50–89%). Despite the reduction of As- and Cu-extractable fractions, plant As and Cu uptake was not greatly affected by the amendments. Variations in soil pH and P-Olsen seemed to have influenced As dynamics in the treated soils, although they did not provoke its mobilisation with respect to the non-amended soil. Our results suggest that the freshly formed iron oxides resulting from addition of iron sulphate controlled As dynamics in the treated soils, avoiding its mobilisation due to application of organic materials. The combination of iron sulphate with OMWC and BC is shown as appropriate for aided phytostabilisation of metal(loid)s contaminated soils, as it improved soil fertility and plant nutrition while reduced As and Cu mobility.

Biochar can be used as a sorbent to remove inorganic pollutants from water but the efficiency of sorption can be improved by activation or modification. This review evaluates various methods to increase the sorption efficiency of biochar including activation with steam, acids and bases and the production of biochar-based composites with metal oxides, carbonaceous materials, clays, organic compounds, and biofilms. We describe the approaches, and explain how each modification alters the sorption capacity. Physical and chemical activation enhances the surface area or functionality of biochar, whereas modification to produce biochar-based composites uses the biochar as a scaffold to embed new materials to create surfaces with novel surface properties upon which inorganic pollutants can sorb. Many of these approaches enhanced the retention of a wide range of inorganic pollutants in waters, but here we provide a comparative assessment for Cd2+, Cu2+, Hg2+, Pb2+, Zn2+, NH4+, NO3-, PO43-, CrO42- and AsO43-.

Biochar has been proposed as a tool to enhance phytostabilisation of contaminated soils but little data are available to illustrate the direct effect on roots in contaminated soils. This work aimed to investigate specific root traits and to assess the effect of biochar amendment on contaminant availability. Amendment with two different types of biochar, pine woodchip and olive tree pruning, was assessed in a rhizobox experiment with maize planted in a soil contaminated with significant levels of copper and arsenic. Amendment was found to significantly improve root traits compared to the control soil, particularly root mass density and root length density. Copper uptake to plants and ammonium sulphate extractable copper was significantly less in the biochar amended soils. Arsenic uptake and extractability varied with type of biochar used but was not considered to be the limiting factor affecting root and shoot development. Root establishment in contaminated soils can be enhanced by biochar amendment but choice of biochar is key to maximising soil improvement and controlling contaminant availability.

The arsenic (As) resistance of Silene vulgaris is studied on two Mediterranean soils, spiked with As and grown under semicontrolled conditions. The results showed that this species accumulates high amounts of As in roots, but both transfer and translocation factors were far from the values found in the As hyperaccumulator species. Arsenic availability in both tested soils is related to soil parameters as follows: Phosphorus (P) > iron oxides > pH. Silene plants studied did not show visual symptoms of As toxicity except for growth reductions at the greater As doses and in the soil with greater P availability; this would indicate the As resistance ability of this plant population.

This is an Accepted Manuscript of an article published by Taylor & Francis Group in Plant Biosystems on 01/01/2014, available online: http://www.tandfonline.com/10.1080/11263504.2012.758188, Mercury tolerance in wild vascular plants has hardly been studied and a tolerant ecotype is not known. In order to confirm the tolerance to Hg of Rumex induratus naturally growing in the biggest Hg mine in the world (Almadén population), the population was compared in a hydroponic experiment with another population from a non-Hg-contaminated area (Colmenar). The plants were exposed to different doses of Hg and a dose of As to establish whether the tolerance to Hg coincides with tolerance to other trace elements. Plants from Colmenar reached up to 1322 μg Hg g-1 in roots and 65 μg Hg g-1 in shoots and showed a significant decrease in biomass due to Hg exposure, whilst Almadén accumulated only 812 μg Hg g-1 and 56 μg Hg g-1 in roots and shoots, respectively. The Almadén population showed a higher tolerance to intense exposure to Hg, but not to As. Plants from Almadén exposed to Hg showed higher capacity to synthesise thiols in the root and to control oxidative stress and Zn starvation. Our findings suggest that R. induratus could be used to enhance understanding of the mechanisms of Hg tolerance in plants, This study was supported by Spanish Ministry of Education and Science, Project CGL 2009-13171-C03-02 and by Comunidad de Madrid, Project EIADES (S2009 AMB-1474)

Arsenic and Cu mobility was investigated in the rhizosphere of Lupinus albus L. grown in an iron-amended contaminated soil. White lupin was grown in rhizobags in contaminated soil either left untreated or amended with iron sulphate plus lime (Fe + lime) or biochar (Fe + BC). Porewater was monitored in rhizosphere and bulk soil throughout the experiment and the extractable fraction of several elements and As and Cu plant uptake was analysed after 48 days. The distribution of As, Cu, P and Fe in the lupin rhizosphere was evaluated with chemical images obtained by laser ablation-ICP-MS analysis of diffusive gradients in thin films (DGT) gels. The treatments effectively reduced the soluble and extractable As and Cu fractions in the bulk soil, but they did not affect plant uptake. In all cases, soluble As was slightly enhanced in the rhizosphere. This difference was more pronounced in the Fe + lime-treated rhizosphere soil, where an increase of pH as well as extractable As and Fe concentrations were also observed. Chemical imaging of the lupin rhizosphere also showed slightly higher As- and Fe-DGT fluxes around lupin roots grown in the non-amended soil. Our findings indicate As and Fe co-solubilisation by lupin root exudates, likely as a response to P deficiency. Arsenic mobilisation occurred only in the rhizosphere and was not decreased by the amendments.

Arsenic is a non-threshold carcinogenic metalloid. Thus, human exposure should be minimised, e.g. by chemically stabilizing As in soil. Since iron is a potential As immobiliser, it was investigated whether root iron plaque, formed under aerobic conditions, affects As uptake, metabolism and distribution in Lupinus albus plants. White lupin plants were cultivated in a continuously aerated hydroponic culture containing Fe/EDDHA or FeSO4 and exposed to arsenate (5 or 20 μM). Only FeSO4 induced surficial iron plaque in roots. LA-ICP-MS analysis accomplished on root sections corroborated the association of As to this surficial Fe. Additionally, As(V) was the predominant species in FeSO4-treated roots, suggesting less efficient As uptake in the presence of iron plaque. Fe/EDDHA-exposed roots neither showed such surficial FeAs co-localisation nor As(V) accumulation; in contrast As(III) was the predominant species in root tissue. Furthermore, FeSO4-treated plants showed reduced shoot-to-root As ratios, which were >10-fold lower compared to Fe/EDDHA treatment. Our results highlight the role of an iron plaque formed in roots of white lupin under aerobic conditions on As immobilisation. These findings, to our knowledge, have not been addressed before for this plant and have potential implications on soil remediation (phytostabilisation) and food security (minimising As in crops).

Phytoremediation can be a suitable option to manage derelict mine soils. A pot experiment was carried out under semi-controlled conditions with a mine-impacted soil. A further contamination event was mimicked by applying 5% of pyritic sludge. Four species were planted in pots (Myrtus communis, Retama sphaerocarpa, Rosmarinus officinalis and Tamarix gallica), and some pots remained unplanted as a control. The substrates were moderately to highly contaminated, mainly with arsenic and zinc. The strong acidification induced by the pyritic sludge was buffered with lime and plants survived in all the pots. Liming provoked an effective immobilisation of metals and arsenic. Plant establishment decreased labile As in the substrate by 50%, mainly M. communis, although the levels of extractable metals were not affected by the plants. R. sphaerocarpa and M. communis increased the levels of C and N in the soil by 23% and 34% respectively, and also enhanced enzymatic activities and microbial respiration to the double in some cases. The low transfer of trace elements to shoots limited the phytoextraction rate. Our results support the use of phytostabilisation in Mediterranean mine soils and show how plants of R. sphaerocarpa and M. communis may increase soil health and quality during revegetation.

Chloride salinity has been strongly related to enhanced cadmium (Cd) uptake by plants due to increased solubility in the soil solution, even in agricultural soil with very low levels of cadmium. This finding is relevant because the cadmium content of food crops is an important concern for human health. Therefore, the aim of this study was to predict and discuss the chlorine-enhanced uptake of cadmium by two common crops: maize and tobacco under “non-saline” (1 mM) and “very strongly saline” (200 mM) scenarios using a modified ‘biotic ligand model’ and datasets from a set of soil and hydroponic experiments. Results indicated that predicted cadmium uptake rates (expressed as cadmium in plant μmol m−2 root) by maize and tobacco plants were consistently higher (54 and 15%, respectively) assuming conditions of ‘very strong salinity’ soil compared to the simulated ‘non-saline’ soil. In the light of the results of the present research, valuable information is given on modeled cadmium phytoavailability as an indication of the potential risk due to increased cadmium uptake by crops under saline conditions, especially as the enhancement of cadmium uptake in the presence of Cl− salinity may be a general trend that occurs in many edible crops. The biotic ligand model parameterization applied in the present study attempted to simulate conditions commonly found in natural cadmium and salt-affected soils. However, caution is needed to extrapolate results obtained from these models to real soil conditions.

Monitoring soil pollution is a key aspect in sustainable management of contaminated land but there is often debate over what should be monitored to assess ecological risk. Soil pore water, containing the most labile pollutant fraction in soils, can be easily collected in situ offering a routine way to monitor this risk. We present a compilation of data on concentration of trace elements (As, Cd, Cu, Pb, and Zn) in soil pore water collected in field conditions from a range of polluted and non-polluted soils in Spain and the UK during single and repeated monitoring, and propose a simple eco-toxicity test using this media. Sufficient pore water could be extracted for analysis both under semi-arid and temperate conditions, and eco-toxicity comparisons could be effectively made between polluted and non-polluted soils. We propose that in-situ pore water extraction could enhance the realism of risk assessment at some contaminated sites.

Green waste compost and biochar amendments were assessed for their assistance in regulating the mobility of copper (Cu) and lead (Pb) and the resultant uptake of these metals into vegetation. The amendments were mixed with a heavily Cu and Pb contaminated soil (600 and 21,000 mg kg −1 , respectively) from a former copper mine in Cheshire (UK), on a volume basis both singly and in combination in greenhouse pot trials. Ryegrass ( Lolium perenne L. var. Cadix) was grown for the following 4 months during which biomass, metals in soil pore water and plant uptake were measured in three consecutive harvests. Very high Pb concentrations in pore water from untreated soil (>80 mg l −1 ) were reduced furthest by compost amendment ( −1 ) whereas biochar was the more effective treatment at reducing pore water Cu concentrations. Duly, ryegrass shoot Cu levels were reduced and large, significant reductions in shoot Pb levels were observed after biochar and compost amendments, respectively during successive harvests. However, because green waste compost singly and in combination with biochar vividly enhanced biomass yields, harvestable amounts of Pb were only significantly reduced by the compost amendment which had reduced shoot Pb levels furthest. The low biomass of ryegrass with biochar amendment meant that this was the only amendment which did not significantly increase harvestable amounts of Cu. Therefore the two amendments have opposing metal specific suitability for treating this contaminated soil regarding whether it is a maximum reduction in plant tissue metal concentration or a maximum reduction in harvestable amount of metal that is required.

The utilization of carbon-rich pyrolysis materials in the separation processes of metalloids plays a crucial role in analytes pre-concentration techniques and opens a burning issue in new sorbents development. This study characterized the effect of physical and chemical activation with subsequent iron impregnation of grape seed-derived biochar on sorption removal of As from model aqueous solutions. Sorbents that were produced in slow pyrolysis process at 600 &deg, C were characterized by SEM, elemental, and specific surface area analysis. Sorption separation of As by the studied materials was characterized as on contact time and an initial concentration dependent process reaching sorption equilibrium in 1440 min. Air activated biochar (A1GSBC) showed about 7.7 times and HNO3 activated biochar (A2GSBC) about 6.8 times higher values of Qmax as compared to control (GSBC). A1GSBC and A2GSBC can be easily and effectively regenerated by alkali agent in several cycles. All of these results showed the practical use of the activation process to produce effective sorption materials with increased surface area and improved sorption potential for anionic forms separation from liquid wastes.

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.

Hg and As resistance and bioaccumulation were studied in hydroponically grown Pistacia lentiscus and Tamarix gallica plants. Both elements caused growth inhibition in roots and shoots, with mercury showing greater phytotoxicity than arsenic. Accumulation of both elements by plants increased in response to element supply, with the greatest uptake found in T. gallica. Both elements affected P and Mn status in plants, reduced chlorophyll a concentration and increased MDA and thiol levels. These stress indices showed good correlations with As and Hg concentration in plant tissues, especially in the roots. Toxic responses to mercury were more evident than for arsenic, especially in shoot tissues. T. gallica showed higher resistance to both Hg and As than P. lentiscus, as well accumulating more As and Hg.

The final publication is available at Springer via http://dx.doi.org/10.1007/s11368-009-0099-4, Background, aim, and scope The mobility of arsenic in soils and its transfer to other environmental components present significant environmental risks. The management of polluted land is determined by the availability, mobility, and transfer of inorganic pollutants to different ecosystem compartments. In this paper, the fate of arsenic at this mining site has been evaluated to determine future management practises to minimise such risk. Materials and methods In a field study carried out in the area adjacent to a mining site at Bustarviejo (North Madrid, Spain), samples of soils, plants, and water were collected from areas adjacent to the core of the former mining activity. The following parameters were investigated in soil samples: pH, organic matter, pseudo-total As, P, and Fe, and labile As and P, and a sequential extraction procedure was performed to investigate As speciation in soil. Plant materials were analysed for both As and P. Arsenic concentrations in water samples (surface and soil pore water collected in the field) were also measured. Results are considered in tandem with previous data on metal concentrations in soils and plants from this site. Results Despite high As concentrations in soils impacted by former mining activities (spoil accumulation and drainage from spoil heaps resulted in concentrations of up to 3,000 mg kg-1), it was not present in a labile form. Sequential extraction revealed that arsenic was mainly retained by Al- and Fe-(oxihydr)oxides (up to 80%). Therefore, only a small proportion of the total soil pool was potentially available for plant uptake (0.3% and 7% extracted by (NH4)2SO4 and NH4H2PO4, respectively). There was very limited transfer of arsenic from soil to plants, and concentrations of arsenic in shoot tissues were relatively low (, This study was supported by the Spanish Ministry of Education and Science, project CTM 2007-66401-CO2/TECNO, and by Comunidad de Madrid, project S-0505/AMB/0296. The authors are grateful to the Excmo. Ayuntamiento de Bustarviejo, for admittance to the mine zone and the facilities offered and to Dr. R. Gamarra for his assistance with plant identification. Authors are grateful to L. Beesley for his comments and language corrections.

This study investigated total arsenic and arsenic speciation in rice using ion chromatography with mass spectrometric detection (IC-ICP-MS), covering the main rice-growing regions of the Iberian Peninsula in Europe. The main arsenic species found were inorganic and dimethylarsinic acid. Samples surveyed were soil, shoots and field-collected rice grain. From this information soil to plant arsenic transfer was investigated plus the distribution of arsenic in rice across the geographical regions of Spain and Portugal. Commercial polished rice was also obtained from each region and tested for arsenic speciation, showing a positive correlation with field-obtained rice grain. Commercial polished rice had the lowest i-As content in Andalucia, Murcia and Valencia while Extremadura had the highest concentrations. About 26% of commercial rice samples exceeded the permissible concentration for infant food production as governed by the European Commission. Some cadmium data is also presented, available with ICP-MS analyses, and show low concentration in rice samples.

Plants of Rumex induratus and Marrubium vulgare, collected in the mining area of Almaden, were transferred to pots and grown for 2 months using perlite as substrate and treated with soluble mercury (Hg) in the applied nutrient solution. Mercury resistance, Hg bioaccumulation, and some stress biomarkers were investigated in both plant species. Mercury concentration increased in both plant species in response to Hg supply, but R. induratus was more effective in Hg accumulation. Rumex induratus and M. vulgare showed higher [Hg]shoot-to-[Hg]root ratios than other plant species. Mercury in the growth medium perlite was also investigated, distinguishing soluble, available, and total amounts of Hg in the medium. At the lower doses, one half of the applied Hg was retained by perlite. Rumex induratus decreased the available Hg fraction in perlite more than M. vulgare. The bioaccumulation factor ([Hg] plant /[Hg] available ) was similar in both species and similar as found in previous field studies. Plant growth, water content, and chlorophyll concentration, and nutrient translocation were reduced in both plant species by the Hg. Rumex induratus showed higher resistance and Hg-accumulation capacity than M. vulgare, due to the accumulation of thiols in roots and the absence of a lipid oxidative response.

A new post-treatment method was applied for improving the sorption efficiency of biochar-based sorbents for anionic forms of phosphorus. The Fe-impregnation through direct hydrolysis of Fe(NO3)3 was used to produce impregnated corn cob- (IBC A), garden wood waste- (IBC B), and wood chip-derived biochars (IBC C). The qualitative and quantitative effects of impregnation process on biochars were confirmed by SEM-EDX, FTIR, and ICP-MS. The analyses revealed increased concentrations of N and thus potential NO3 − participation in the phosphate sorption process. Biochar surface area showed a significant decrease after the impregnation process due to the filling of micro- and mesopores with Fe maximum sorption capacity (Q max) increased by a factor of 12–50. The sorption processes of phosphates by IBC A, IBC B, and IBC C were dependent on pH, initial concentration, and time. Speciation analysis and pH-study confirmed the range of pH 4.5–5.5 as optimum values at which most of phosphorus is present in form of mononuclear H2PO4 −. Batch sorption experiments showed a significant increase in the sorption capacity for phosphates by Fe impregnation of biochar as well as effectiveness and stability of this treatment. These findings indicate an option for utilizing engineered biochars as tools for the recovery of phosphorus from the aquatic environment.

Research into the use of biochar for the remediation of contaminated soils has expanded rapidly over the past 5 yr. We review recent developments in the field and present the findings emanating from small-scale batch sorption experiments, through soil incubations and bioassays, to large-scale field experiments. We discuss the evidence that these experiments have contributed toward a mechanistic understanding of how biochar is capable of remediating soils contaminated with both organic and inorganic contaminants. The effects of biochar pyrolysis temperature, biochar source material, soil type, and contaminant type on the performance of biochars for remediation are identified. The risks associated with applying biochar to uncontaminated agricultural soils are discussed. Knowledge gaps and questions are identified which, if addressed, will considerably advance the application of biochar as a soil remediation tool in the future.

Heavy metals accumulation in soils poses a potential threat to ecosystems, which, in turn, threat human health through food chains. Therefore, remediating polluted sites is important to environment and humanity. In this investigation, statice (L. sinuatum) was exposed to Cd (0, 15, 30, 60 mg kg(-1) soil) or Pb (0, 100, 150, 300 mg kg(-1) soil) in a pot experiment to assess its tolerance to each metal and study its phytoaccumulation capability. The benefits of mycorrhization (mixture of Glomus mosseae and G. intraradices) were also studied simultaneously. Single exposure to Cd or Pb reduced the plant growth, but statice was still relatively tolerant to both metals. The plants accumulated both metals in their roots; little was translocated to the shoots. Total Pb and total Cd accumulated by the roots was approximately 2 and 3 times higher in mycorrhizal than non-mycorrhizal plants (49 versus 147 and 595 versus 956 μg plant(-1)) respectively; however, mycorrhization alleviated metal phytotoxicity. The results suggest that statice is a potential candidate to be used as an ornamental plant in lead and cadmium polluted sites, mainly inoculated with arbuscular mycorrhizae. Besides that, it would be useful as a Pb or Cd controlling agent by means of phytostabilization.

An automatic in-vitro bioaccessibility test based upon dynamic microcolumn extraction in a programmable flow setup is herein proposed as a screening tool to evaluate bio-char based remediation of mine soils contaminated with trace elements as a compelling alternative to conventional phyto-availability tests. The feasibility of the proposed system was evaluated by extracting the readily bioaccessible pools of As, Pb and Zn in two contaminated mine soils before and after the addition of two biochars (9% (w:w)) of diverse source origin (pine and olive). Bioaccessible fractions under worst-case scenarios were measured using 0.001 mol L(-1) CaCl2 as extractant for mimicking plant uptake, and analysis of the extracts by inductively coupled optical emission spectrometry. The t-test of comparison of means revealed an efficient metal (mostly Pb and Zn) immobilization by the action of olive pruning-based biochar against the bare (control) soil at the 0.05 significance level. In-vitro flow-through bioaccessibility tests are compared for the first time with in-vivo phyto-toxicity assays in a microcosm soil study. By assessing seed germination and shoot elongation of Lolium perenne in contaminated soils with and without biochar amendments the dynamic flow-based bioaccessibility data proved to be in good agreement with the phyto-availability tests. Experimental results indicate that the dynamic extraction method is a viable and economical in-vitro tool in risk assessment explorations to evaluate the feasibility of a given biochar amendment for revegetation and remediation of metal contaminated soils in a mere 10 min against 4 days in case of phyto-toxicity assays.

Unfortunately, the address of Barbora Michalekova-Richveisova is wrong in the published article. The correct address is given below as number 6.

Previous studies have demonstrated that rice cultivated under flooded conditions has higher concentrations of arsenic (As) but lower cadmium (Cd) compared to rice grown in unsaturated soils. To validate such effects over long terms under Mediterranean conditions a field experiment, conducted over 7 successive years was established in SW Spain. The impact of water management on rice production and grain arsenic (As) and cadmium (Cd) was measured, and As speciation was determined to inform toxicity evaluation. Sprinkler irrigation was compared to traditional flooding. Both irrigation techniques resulted in similar grain yields (~3000 kg grain ha(-1)). Successive sprinkler irrigation over 7 years decreased grain total As to one-sixth its initial concentration in the flooded system (0.55 to 0.09 mg As kg(-1)), while one cycle of sprinkler irrigation also reduced grain total As by one-third (0.20 mg kg(-1)). Grain inorganic As concentration increased up to 2 folds under flooded conditions compared to sprinkler irrigated fields while organic As was also lower in sprinkler system treatments, but to a lesser extent. This suggests that methylation is favored under water logging. However, sprinkler irrigation increased Cd transfer to grain by a factor of 10, reaching 0.05 mg Cd kg(-1) in 7 years. Sprinkler systems in paddy fields seem particularly suited for Mediterranean climates and are able to mitigate against excessive As accumulation, but our evidence shows that an increased Cd load in rice grain may result.

Amending contaminated soils with organic wastes can influence trace element mobility and toxicity. Soluble concentrations of metals and arsenic were measured in pore water and aqueous soil extracts following the amendment of a heavily contaminated mine soil with compost and biochar (10% v:v) in a pot experiment. Speciation modelling and toxicity assays (Vibrio fischeri luminescence inhibition and Lolium perenne germination) were performed to discriminate mechanisms controlling metal mobility and assess toxicity risk thereafter. Biochar reduced free metal concentrations furthest but dissolved organic carbon primarily controlled metal mobility after compost amendment. Individually, both amendments induced considerable solubilisation of arsenic to pore water (>2500 μg l(-1)) related to pH and soluble phosphate but combining amendments most effectively reduced toxicity due to simultaneous reductions in extractable metals and increases in soluble nutrients (P). Thus the measure-monitor-model approach taken determined that combining the amendments was most effective at mitigating attendant toxicity risk.

There is a legacy of polluted soils worldwide, contaminated with a variety of different chemicals from a wide range of industrial (e.g., electricity generation, oil refi ning, mining), agricultural (e.g., pesticide application) and urban (e.g., waste disposal, motor vehicle discharges) sources. Soils are considered polluted when they have an excess of an element or compound which, through direct or indirect exposure, causes a toxic response to biota resulting in unacceptable risks to the environment or human health (Adriano 2001, Abrahams 2002, Vangronsveld et al. 2009). This is a cause for concern in many countries such as the U.S where over 100,000 contaminated sites have been identifi ed (Connell 2005), or the E.U. member states thathave reported 250,000 polluted sites that need urgent remediation (Mench et al. 2010). The remediation of contaminated soils is therefore receiving increasing attention from governments, legislators, industries and the general population. Due to the wide range and dispersive nature of many contaminant sources, soil contamination is often too widespread for ex situ remediation options (e.g., excavating and burying polluted soils in landfi ll sites) to be practically, environmentally or fi nancially viable. This has resulted in the development of more sustainable, in situ remediation treatments that, in many cases, involve the application of amendments directly to contaminated soils. For soils contaminated with inorganic pollutants like heavy metals, these amendments include clay minerals, zeolites, lime or composts (Simon 2000, Mench et al. 2003, Vangronsveld et al. 2009), whereas for organic contaminants like polycyclic aromatic hydrocarbons (PAHs), or polychlorinated biphenyls (PCBs), activated carbons have been favored (Brandli et al. 2008, Ghosh et al. 2011). The application of this kind of in situ amendments does not remove the contaminants from the soil, so their success is based on a reduction in the bioavailability and/or mobility of the contaminants in question. This reduction is achieved by altering the physico-chemical and biological characteristics of the soil, ultimately reducing the risk of contaminant uptake by fauna and fl ora, or leaching into waters. Biochars have received interest recently as an amendment for soil remediation purposes due to their potential to reduce the bioavailability of organic contaminants (Gomez-Eyles et al. 2011, Hale et al. 2011), inorganic contaminants (Beesley and Marmiroli 2011), and both organic and inorganic contaminants simultaneously (Cao et al. 2009, Beesley et al. 2010b). This is demonstrated by a rapid increase in the number of studies published featuring, within their title, the words ‘biochar’, ‘soil’, and ‘contaminated’ or ‘polluted’ from just 1 in 2007 to almost 30 in 2011 (Fig. 1).

The bioavailability of soil arsenic (As) is determined by its speciation in soil solution, i.e., arsenite [As(III)] or arsenate [As(V)]. Soil bioavailability studies require suitable methods to cope with small volumes of soil solution that can be speciated directly after sampling, and thereby minimise any As speciation change during sample collection. In this study, we tested a self-made microcartridge to separate both As species and compared it to a commercially available cartridge. In addition, the diffusive gradient in thin films technique (DGT), in combination with the microcartridges, was applied to synthetic solutions and to a soil spiked with As. This combination was used to improve the assessment of available inorganic As species with ferrihydrite(FH)-DGT, in order to validate the technique for environmental analysis, mainly in soils. The self-made microcartridge was effective in separating As(III) from As(V) in solution with detection by inductively coupled plasma optical emission spectrometry (ICP-OES) in volumes of only 3 ml. The DGT study also showed that the FH-based binding gels are effective for As(III) and As(V) assessment, in solutions with As and P concentrations and ionic strength commonly found in soils. The FH-DGT was tested on flooded and unflooded As spiked soils and recoveries of As(III) and As(V) were 85-104% of the total dissolved As. This study shows that the DGT with FH-based binding gel is robust for assessing inorganic species of As in soils.

Organic matter amendments are applied to contaminated soil to provide a better habitat for re-vegetation and remediation, and olive mill waste compost (OMWC) has been described as a promising material for this aim. We report here the results of an incubation experiment carried out in flooded conditions to study its influence in As and metal solubility in a trace elements contaminated soil. NPK fertilisation and especially organic amendment application resulted in increased As, Se and Cu concentrations in pore water. Independent of the amendment, dimethylarsenic acid (DMA) was the most abundant As species in solution. The application of OMWC increased pore water dissolved organic-carbon (DOC) concentrations, which may explain the observed mobilisation of As, Cu and Se; phosphate added in NPK could also be in part responsible of the mobilisation caused in As. Therefore, the application of soil amendments in mine soils may be particularly problematic in flooded systems.

Arsenic is a natural trace element found in the environment. In some cases and places, human activities have increased the soil concentration of As to levels that exceed hazard thresholds. Amongst the main contributing sources of As contamination of soil and water are the following: geologic origin, pyriticmining, agriculture, and coal burning. Arsenic speciation in soils occurs and is relatively complex. Soils contain both organic and inorganic arsenic species. Inorganic As species include arsenite and arsenate, which are the most abundant forms found in the environment. The majority of As in aerated soils exists as H₂AsO₄- (acid soils) or HAsO₄²- (neutral species and basic). However, HA₃sO₃ is the predomiant anaerobic soils, where arsenic availability is higher and As(III) is more weakly retained in the soil matrix than is As(V). The availability of As in soils is usually driven by multiple factors. Among these factors is the presence of Fe-oxides and/or phosphorus, (co)precipitation in salts, pH, organic matter, clay content, rainfall amount, etc. The available and most labile As fraction can potentially be taken up by plant roots, although the concentration of this fraction is usually low. Arsenic has no known biological function in plants. Once inside root cells, As(V) is quickly reduced to As(III), and, in many plant species, becomes complexed. Phosphorus nutrition influences As(V) uptake and toxicity in plants, whilst silicon has similar influences on As(III). Plants cope with As contamination in their tissues by possessing detoxification mechanisms. Such mechanisms include complexation and compartmentalization. However, once these mechanisms are saturated, symptoms of phytotoxicity appear. Phytotoxic effects commonly observed from As exposure includes growth inhibition, chlorophyll degradation, nutrient depletion and oxidative stress. Plants vary in their ability to accumulate and tolerate As (from tolerant hyperaccumulators to sensitive excluders), and some plants are useful for soil reclamation and in sustainable agriculture, The status of current scientific knowledge allows us to manage As contamination in the soil-plant system and to mitigate arsenic's effects. Phytoremediation is an emerging technology suitable for reclaiming As-contaminated soils and waters. Phytoextraction has been used to clean As-contaminated soils, although its applicability has not yet reached maturity. Phytostabilization has been employed to reduce environmental risk by confining As as an inert form in soils and has shown success in both laboratory experiments and in field trials. Phytofiltration has been used to treat As-enriched waters. Such treatment removes As when it is accumulated in plants grown in or on water. In agricultural food production, appropriate soil management and plant variety/species selection can minimize As-associated human dis- eases and the transfer of As within the food chain. Selecting suitable plants for use on As-contaminated soils may also enhance alternative land use, such as for energy or raw material production.

Biochars are biological residues combusted under low oxygen conditions, resulting in a porous, low density carbon rich material. Their large surface areas and cation exchange capacities, determined to a large extent by source materials and pyrolysis temperatures, enables enhanced sorption of both organic and inorganic contaminants to their surfaces, reducing pollutant mobility when amending contaminated soils. Liming effects or release of carbon into soil solution may increase arsenic mobility, whilst low capital but enhanced retention of plant nutrients can restrict revegetation on degraded soils amended only with biochars; the combination of composts, manures and other amendments with biochars could be their most effective deployment to soils requiring stabilisation by revegetation. Specific mechanisms of contaminant-biochar retention and release over time and the environmental impact of biochar amendments on soil organisms remain somewhat unclear but must be investigated to ensure that the management of environmental pollution coincides with ecological sustainability.

7 Pags., 4 Tabls., 4 Figs., Re-vegetation is the main aim of ecological restoration projects, and in Mediterranean environments native plants are desirable to achieve successful restoration. In 1998, the burst of a tailings dam flooded the Guadiamar river valley downstream from Aznalcóllar (Southern Spain) with sludges that contained elevated concentrations of metals and metalloids, polluting soils and waters. A phytoremediation experiment to assess the potential use of native shrub species for the restoration of soils affected by the spillage was performed from 2005 to 2007, with soils divided into two groups: pH < 5 and pH > 5. Four native shrubs (Myrtus communis, Retama sphaerocarpa, Rosmarinus officinalis and Tamarix gallica) were planted and left to grow without intervention. Trace element concentrations in soils and plants, their extractability in soils, transfer factors and plant survival were used to identify the most-interesting species for phytoremediation. Total As was higher in soils with pH < 5. Ammonium sulphate-extractable zinc, copper, cadmium and aluminium concentrations were higher in very-acid soils, but arsenic was extracted more efficiently when soil pH was >5. Unlike As, which was either fixed by Fe oxides or retained as sulphide, the extractable metals showed significant relationships with the corresponding total soil metal concentration and inverse relationships with soil pH. T. gallica, R. officinalis and R. sphaerocarpa survived better in soils with pH > 5, while M. communis had better survival at pH < 5. R. sphaerocarpa showed the highest survival (30%) in all soils. Trace element transfer from soil to harvestable parts was low for all species and elements, and some species may have been able to decrease trace element availability in the soil. Our results suggest that R. sphaerocarpa is an adequate plant species for phytostabilising these soils, although more research is needed to address the self-sustainability of this remediation technique and the associated environmental changes., The authors acknowledge financial support from the Spanish Ministry of Science and Innovation (projects: CTM 2007-66401-CO2-02/TECNO and CTM 2004-06715-CO2-01) and from the Comunidad de Madrid (project EIADES S2009/AMB-1478).