Phytoextraction efficiency of Arabidopsis halleri is driven by the plant and not by soil metal concentration.

The hyperaccumulation trait allows some plant species to allocate remarkable amounts of trace metal elements (TME) to their foliage without suffering from toxicity. Utilizing hyperaccumulating plants to remediate TME contaminated sites could provide a sustainable alternative to industrial approaches. A major hurdle that currently hampers this approach is the complexity of the plant-soil relationship. To better anticipate the outcome of future phytoremediation efforts, we evaluated the potential for soil metal-bioavailability to predict TME accumulation in two non-metallicolous and two metallicolous populations of the Zn/Cd hyperaccumulator Arabidopsis halleri. We also examined the relationship between a population's habitat and its phytoextraction efficiency. Total Zn and Cd concentrations were quantified in soil and plant material, and bioavailable fractions in soil were quantified via Diffusive Gradients in Thin-films (DGT). We found that shoot TME accumulation varied independent from both total and bioavailable soil TME concentrations in metallicolous individuals. In fact, hyperaccumulation patterns appear more plant- and less soil-driven: one non-metallicolous population proved to be as efficient in accumulating Zn on non-polluted soil as the metallicolous populations in their highly contaminated environment. Our findings demonstrate that in-situ information on plant phytoextraction efficiency is indispensable to optimize site-specific phytoremediation measures. If successful, hyperaccumulating plant biomass may provide valuable source material for application in the emerging field of green chemistry.

Long-term organic matter application reduces cadmium but not zinc concentrations in wheat.

Wheat is a staple food crop and a major source of both the essential micronutrient zinc (Zn) and the toxic heavy metal cadmium (Cd) for humans. Since Zn and Cd are chemically similar, increasing Zn concentrations in wheat grains (biofortification), while preventing Cd accumulation, is an agronomic challenge. We used two Swiss agricultural long-term field trials, the "Dynamic-Organic-Conventional System Comparison Trial" (DOK) and the "Zurich Organic Fertilization Experiment" (ZOFE), to investigate the impact of long-term organic, mineral and combined fertilizer inputs on total and phytoavailable concentrations of soil Zn and Cd and their accumulation in winter wheat (Triticum aestivum L.). "Diffusive gradients in thin films" (DGT) and diethylene-triamine-pentaacetic acid (DTPA) extraction were used as proxies for plant available soil metals. Compared to unfertilized controls, long-term organic fertilization with composted manure or green waste compost led to higher soil organic carbon, cation exchange capacity and pH, while DGT-available Zn and Cd concentrations were reduced. The DGT method was a strong predictor of shoot and grain Cd, but not Zn concentrations. Shoot and grain Zn concentrations correlated with DTPA-extractable and total soil Zn concentrations in the ZOFE, but not the DOK trial. Long-term compost fertilization led to lower accumulation of Cd in wheat grains, but did not affect grain Zn. Therefore, Zn/Cd ratios in the grains increased. High Zn and Cd inputs with organic fertilizers and high Cd inputs with phosphate fertilizers led to positive Zn and Cd mass balances when taking into account atmospheric deposition and fertilizer inputs. On the other hand, mineral fertilization led to the depletion of soil Zn due to higher yields and thus higher Zn exports than under organic management. The study supports the use of organic fertilizers for reducing Cd concentrations of wheat grains in the long-term, given that the quality of the fertilizers is guaranteed.

Uptake and Transformation of Methylated and Inorganic Antimony in Plants.

Used as a hardening agent in lead bullets, antimony (Sb) has become a major contaminant in shooting range soils of some countries including Switzerland. Soil contamination by Sb is also an environmental problem in countries with Sb-mining activities such as China and Bolivia. Because of its toxicity and relatively high mobility, there is concern over the risk of Sb transfer from contaminated soils into plants, and thus into the food chain. In particular there is very little information on the environmental behavior of methylated antimony, which can be produced by microbial biomethylation of inorganic Sb in contaminated soils. Using a new extraction and high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) method, we investigated antimony speciation in roots and shoots of wheat, fescue, rye, and ryegrass plants exposed to trimethyl antimony(V) (TMSb), antimonite (Sb(III)), and antimonate (Sb(V)) in hydroponics. The total root Sb concentrations followed the order Sb(III) treatment > Sb(V) treatment > TMSb treatment, except for fescue. Shoot Sb concentrations, however, did not differ among the three treatments. In the Sb(V) treatment small quantities of TMSb were found in the roots, whereas no TMSb was detected in the roots of Sb(III)-treated plants. In contrast, similar concentrations of TMSb were found in the shoots in both inorganic Sb treatments. The results indicate that biomethylation of Sb may occur in plants. In the TMSb treatment TMSb was the major Sb species, but the two inorganic Sb species were also found both in shoots and roots along with some unknown Sb species, suggesting that also TMSb demethylation may occur within plant tissues. The results furthermore indicate that methylated Sb is more mobile in plants than inorganic Sb species. Knowledge about this is important in risk assessments of Sb-contaminated sites, as methylation may render Sb more toxic than inorganic Sb, as it is known for arsenic (As).

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

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

Antimony mobility during prolonged waterlogging and reoxidation of shooting range soil: A field experiment.

Due to its increasing anthropogenic use, antimony (Sb) soil pollution is of growing concern. Many soils experience fluctuating hydrological conditions, yet very little is known about how this affects the mobility of this toxic element under field conditions. In this study, we performed an outdoor lysimeter experiment to compare Sb leaching from a calcareous shooting range soil under drained and prolonged waterlogged conditions (1.5-2.75years), followed by a 1.5-year period of soil reoxidation. Waterlogging reduced Sb leachate concentrations significantly compared to drained conditions and soil solution concentrations decreased with depth due to the increased reducing conditions. This was attributed to the reduction of Sb(V) to Sb(III) and the more effective sorption of the latter to metal (hydr)oxides. However, reductive dissolution of iron (hydr)oxides released Sb into solution, although Sb concentrations never exceeded those in the drained lysimeters. On reoxidation of the soil, Sb was remobilized, but even after 1.5years under reoxidised conditions, Sb leachate and soil solution concentrations still remained below those of the drained lysimeters. Our results demonstrate that prolonged waterlogging may have an irreversible effect on Sb leachate and soil solution concentrations.

Fate and chemical speciation of antimony (Sb) during uptake, translocation and storage by rye grass using XANES spectroscopy.

Antimony (Sb) is a contaminant of increased prevalence in the environment, but there is little knowledge about the mechanisms of its uptake and translocation within plants. Here, we applied for the synchrotron based X-ray absorption near-edge structure (XANES) spectroscopy to analyze the speciation of Sb in roots and shoots of rye grass (Lolium perenne L. Calibra). Seedlings were grown in nutrient solutions to which either antimonite (Sb(III)), antimonate (Sb(V)) or trimethyl-Sb(V) (TMSb) were added. While exposure to Sb(III) led to around 100 times higher Sb accumulation in the roots than the other two treatments, there was no difference in total Sb in the shoots. Antimony taken up in the Sb(III) treatment was mainly found as Sb-thiol complexes (roots: >76% and shoots: 60%), suggesting detoxification reactions with compounds such as glutathione and phytochelatins. No reduction of accumulated Sb(V) was found in the roots, but half of the translocated Sb was reduced to Sb(III) in the Sb(V) treatment. Antimony accumulated in the TMSb treatment remained in the methylated form in the roots. By synchrotron based XANES spectroscopy, we were able to distinguish the major Sb compounds in plant tissue under different Sb treatments. The results help to understand the translocation and transformation of different Sb species in plants after uptake and provide information for risk assessment of plant growth in Sb contaminated soils.

Green manure and long-term fertilization effects on soil zinc and cadmium availability and uptake by wheat (Triticum aestivum L.) at different growth stages.

Zinc (Zn) deficiency in human populations depending on cereals as a main source of Zn is a global malnutrition problem. In this field study, we investigated the potential of green manure application to increase soil Zn availability and wheat grain Zn concentrations (biofortification) on a Luvisol with different long-term fertilizer management. We also studied cadmium (Cd), as wheat is a major contributor of this undesired non-essential element to human diets. Clover (Trifolium alexandrinum L.), mustard (Sinapis alba L.) or no green manure was grown on field plots which had been managed with farmyard manure or mineral fertilizers for 65years in Switzerland. After green manure incorporation into the soil, spring wheat (Triticum aestivum L.) was grown on all plots. The "diffusive gradients in thin films" (DGT) method and DTPA extraction were used to compare soil Zn and Cd availability among the treatments. In contrast to mustard, clover increased soil mineral nitrogen concentrations and wheat biomass; however, neither increased grain Zn concentrations. DGT-available Zn and Cd increased temporarily after both farmyard manure and mineral nitrogen fertilizer application. Higher DTPA-extractable soil Zn and Cd, lower wheat grain yields, but higher grain Zn concentrations were obtained with farmyard manure compared to mineral fertilizers, independent of the green manure treatment. Farmyard manure added Zn, Cd and organic matter that increased the soil binding capacity for Zn and Cd. The decomposition of clover residues caused higher wheat grain yields, but only marginally lower grain Zn concentrations. The absence of a stronger dilution of grain Zn was probably due to organic acid and nitrogen release from decomposing clover, which facilitated Zn uptake by wheat. The study revealed that both long- and short-term field management with organic matter alters soil Zn and Cd concentrations but that the long-term effects dominate their uptake by wheat, in Zn sufficient soil.

Use of soil amendments to immobilize antimony and lead in moderately contaminated shooting range soils.

Shooting ranges are a source of environmental concern around the world as they are a source of toxic antimony (Sb) and lead (Pb). In-situ chemical stabilization is a strategy to reduce metal(loid) leaching and bioavailability. However it is difficult to find the right treatment due to the fact that Pb is a cation and Sb an anion, under oxidised conditions and they often show the opposite mobility in soil, on the application of amendments. A batch experiment was set up with two soils (slightly acidic and alkaline), two red mud based amendments (ViroSoil™ 1 and 2) alone and in combination with two reducing agents (zero valent iron and iron sulphate), to assess the effect of the treatments on metal(loid) leaching and compare it to unamended soil and soil amended with goethite, a known Sb adsorbent. Iron sulphate was effective at reducing Sb leaching due to the reduction of SbV to SbIII which bound more strongly to iron (hyr)oxides in soil. However it had an adverse effect on the leaching of Pb due to its acidifying effect and reductive dissolution of manganese (hyd)roxides. Combining ViroSoil™ amendments with FeSO4 still reduced Sb leaching but also Pb leaching and proved a suitable treatment.

Antimony retention and release from drained and waterlogged shooting range soil under field conditions.

Many soils polluted by antimony (Sb) are subject to fluctuating waterlogging conditions; yet, little is known about how these affect the mobility of this toxic element under field conditions. Here, we compared Sb leaching from a calcareous shooting range soil under drained and waterlogged conditions using four large outdoor lysimeters. After monitoring the leachate samples taken at bi-weekly intervals for >1.5 years under drained conditions, two of the lysimeters were subjected to waterlogging with a water table fluctuating according to natural rainfall water infiltration. Antimony leachate concentrations under drained conditions showed a strong seasonal fluctuation between 110 µg L(-1) in summer and <40 µg L(-1) in winter, which closely correlated with fluctuations in dissolved organic carbon (DOC) concentrations. With the development of anaerobic conditions upon waterlogging, Sb in leachate decreased to 2-5 µg L(-1) Sb and remained stable at this level. Antimony speciation measurements in soil solution indicated that this decrease in Sb(V) concentrations was attributable to the reduction of Sb(V) to Sb(III) and the stronger sorption affinity of the latter to iron (Fe) (hydr)oxide phases. Our results demonstrate the importance of considering seasonal and waterlogging effects in the assessment of the risks from Sb-contaminated sites.

Release of antimony from contaminated soil induced by redox changes.

Soil contamination by toxic antimony (Sb) released from corroding ammunition has become an issue of public concern in various countries. Many of these soils are at least occasionally subject to waterlogging; yet mechanisms controlling Sb mobility under anaerobic conditions are still poorly understood. We investigated Sb concentration and speciation dynamics in a calcareous shooting range soil in terms of changing redox conditions using microcosm experiments. The transition to reducing conditions invoked by indigenous microbial activity at first led to the immobilization of Sb, as Sb(V) was converted to Sb(III), which binds more extensively to iron (hydr)oxides. When reducing conditions continued, the previously sorbed Sb(III) was gradually released into solution due to reductive dissolution of the iron (hydr)oxides. Speciation measurements in the solid phase by Sb K-edge XANES spectroscopy and in the soil solution by liquid chromatography ICP-MS provided the first evidence that Sb(III) predominated at low redox conditions (Eh <0.05 V) in both phases. The results show that Sb(V) is less stable in reducing environments than commonly assumed. Given that Sb(III) is generally more toxic than Sb(V), the mobilization of Sb(III) under Fe-reducing conditions may significantly increase (eco)toxicological risks arising from Sb-contaminated soils that are prone to flooding or waterlogging.

Availability of zinc and the ligands citrate and histidine to wheat: does uptake of entire complexes play a role?

Organic ligands in soils affect the availability of trace metals such as Zn to plants. This study investigated the effects of two of these ligands, citrate and histidine, on Zn uptake by wheat under hydroponic conditions. Uptake of (65)Zn in the presence of these ligands was compared to uptake in the presence of EDTA at the same free Zn concentration (Zn(2+) ~ 50 nM). In the presence of citrate Zn root uptake was enhanced ~3.5 times and in the presence of histidine, by a factor of ~9, compared to the EDTA treatments. Citrate uptake was slightly reduced in the treatment containing ligands and Zn compared to the treatment containing the same ligand concentration but no Zn. In addition, a higher uptake of Zn than of citrate was observed. This suggests that the enhanced Zn uptake was primarily due to increased supply of Zn(2+) by diffusion and dissociation of Zn-citrate complexes at the root surface. Histidine uptake was much higher than citrate uptake and not influenced by the presence of Zn. As histidine forms stronger complexes with Zn than citrate, the results suggest that the enhancement of Zn uptake in the presence of histidine was in part due to the uptake of undissociated Zn-histidine complexes.

Changes in Sb speciation with waterlogging of shooting range soils and impacts on plant uptake.

A pot experiment was conducted to investigate the solubility and redox species of antimony (Sb) in a relocated shooting range soil and its uptake by Lolium perenne L. and Holcus lanatus L. under different water regimes. After 1-week waterlogging, the total Sb concentration in soil solution decreased from ∼110 µg L(-1) to <20 µg L(-1), and slowly increased over the following 4 weeks, with the dissolution of Fe and Mn (hydr)oxides. In this process, half of the Sb in soil solution was reduced to Sb(III), which greatly affected the plant uptake of Sb. Waterlogging increased shoot Sb concentrations of L. perenne by ∼10 fold but decreased uptake in H. lanatus by 80%. Results indicate that Sb might primarily be taken up as Sb(III) by L. perenne and as Sb(V) by H. lanatus. Temporary waterlogging of soil may increase the risk of trace elements entering the food chain.

Internal Zn allocation influences Zn deficiency tolerance and grain Zn loading in rice (Oryza sativa L.).

One of the important factors that influences Zn deficiency tolerance and grain Zn loading in crops is the within-plant allocation of Zn. Three independent experiments were carried out to understand the internal Zn distribution patterns in rice genotypes grown in Zn-sufficient and Zn-deficient agar nutrient solution (ANS). In one of the experiments, two rice genotypes (IR55179 and KP) contrasting in Zn deficiency tolerance were leaf-labeled with (65)Zn. In the other two experiments, two Zn biofortification breeding lines (IR69428 and SWHOO) were either root- or leaf-labeled with (65)Zn. Rice genotype IR55179 showed significantly higher Zn deficiency tolerance than KP at 21 and 42 days after planting. When KP was Zn-deficient, it failed to translocate (65)Zn from the labeled leaf to newly emerging leaves. Similarly, the root-to-shoot translocation of unlabeled Zn was lower in KP than in IR55179. These results suggest that some Zn-efficient rice genotypes have greater ability to translocate Zn from older to actively growing tissues than genotypes sensitive to Zn deficiency. Among the two Zn biofortication breeding lines that were leaf-labeled with (65)Zn at 10 days before panicle initiation stage, (65)Zn distribution in the grains at maturity was similar between both genotypes in Zn-sufficient conditions. However, under Zn-deficient conditions, SWHOO accumulated significantly higher (65)Zn in grains than IR69428, indicating that SWHOO is a better remobilizer than IR69428. When the roots of these two Zn biofortication breeding lines were exposed to (65)Zn solution at 10 days after flowering, IR69428 showed higher root uptake of (65)Zn than SWHOO in Zn-sufficient conditions, but (65)Zn allocation in the aerial parts of the plant was similar between both genotypes.

Applicability of diffusive gradients in thin films for measuring Mn in soils and freshwater sediments.

Manganese (Mn) is an essential plant nutrient, receiving increased attention due to significant deficiency problems in modern crop production. In aquatic sediments, Mn plays an important role in controlling the mobility of other elements due to its high redox sensitivity. Diffusive gradients in thin films (DGT) is recognized as one of the most promising techniques to assess plant availability of nutrients in soils and mobility in sediments. However, the appropriate conditions where DGT can be used to measure Mn in soils and sediments have not been thoroughly investigated. We deployed DGTs in soil, sediment, and solution to investigate the effect of pH and competition from Ca and Fe ions. We found that by using DGT it is possible to accurately measure Mn in soils at pH levels and Ca and Fe concentrations resembling those of normal and fertile agricultural soils. However, in acid soils at pH below 5.5, Mn measurements might be biased due to potential competition effects caused by Ca. Soil deployments showed that changes in soil redox conditions were closely reflected by the DGT based Mn measurements. This might enable a novel approach of using DGT to predict Mn mobility and plant availability in soils. In reducing aquatic sediments, high concentrations of ferrous ions can displace Mn from the resin-gel of the DGT device. We found this to be a significant problem with longer deployment times.

FT-IR as an alternative method for measuring chemical properties during composting.

Chemical properties have been used as a way of following the composting process and compost maturity, however, their analysis is very time consuming as each must be separately determined. By developing a more rapid method to predict these properties, time and cost would be saved. This study investigates the use of Fourier Transform mid-Infrared Spectroscopy (FT-IR) for this purpose. FT-IR spectra and measured values of several chemical properties from a variety of compost mixtures were used to produce calibrated models using partial least-squares regression analysis which predicted the known chemical properties. These models displayed a range of accuracies that for most properties was more than sufficient to follow at least broad dynamic changes associated with maturation. The best calibrations were achieved for total C, total N, LOI, lignin, and cellulose with r(2) values within the range 56-77%. Some degree of calibration was achieved for available-P and NH(4)(+)-N, with r(2) values of between 40% and 57%. No useful calibration could be achieved for NO(3)(-) or pH.

Remediation of metal polluted mine soil with compost: co-composting versus incorporation.

Trace element contamination of post-industrial sites represents a major environmental problem and sustainable management options for remediating them are required. This study compared two strategies for immobilizing trace elements (Cu, Pb, Zn, and As) in mine spoil: (1) co-composting contaminated soil with organic wastes and (2) conventional incorporation of mature compost into contaminated soil. Sequential chemical extraction of the soil was performed to determine temporal changes in trace element fractionation and bioavailability during composting and plant growth. We show that mine spoil can be co-composted successfully and this action causes significant shifts in metal availability. However, co-composting did not lead to significant differences in metal partitioning in soil or in plant metal uptake compared with simply mixing mine spoil with mature compost. Both treatments promoted plant growth and reduced metal accumulation in plants. We conclude that co-composting provides little additional benefit for remediating trace-element-polluted soil compared with incorporation of compost.

Uptake of metals during chelant-assisted phytoextraction with EDDS related to the solubilized metal concentration.

The use of chelants to enhance phytoextraction is one method being tested to make phytoextraction efficient enough to be used as a remediation technique for heavy metal pollution in the field. We performed pot experiments with sunflowers in order to investigate the use of the biodegradable chelating agent SS-EDDS for this purpose. We used singly and combined contaminated soils (Cu, Zn) and multimetal contaminated field soils (Cu, Zn, Cd, Pb). EDDS (10 mmol kg(-10 soil) increased soil solution metals greatly for Cu (factor 840-4260) and Pb (factor 100-315), and to a lesser extent for Zn (factor 23-50). It was found that Zn (when present as the sole metal), Cu, and Pb uptake by sunflowers was increased by EDDS, butin multimetal contaminated soil Zn and Cd were not. EDDS was observed in the sunflower roots and shoots at concentrations equal to metal uptake. The different metal uptake in the various soils can be related to a linear relationship between Cu and Zn in soil solution in the presence of EDDS and plant uptake, indicating the great importance of measuring and reporting soil solution metal concentrations in phytoextraction studies.

The influence of EDDS on the uptake of heavy metals in hydroponically grown sunflowers.

Phytoextraction is an environmentally friendly in situ technique for cleaning up metal contaminated land. Unfortunately, efficient metal uptake by remediation plants is often limited by low phytoavailability of the targeted metals. Chelant assisted phytoextraction has been proposed to improve the efficiency of phytoextraction. Phytoremediation involves several subsequent steps: transfer of metals from the bulk soil to the root surfaces, uptake into the roots and translocation to the shoots. Nutrient solution experiments address the latter two steps. In this context we investigated the influence of the biodegradable chelating agent SS-EDDS on uptake of essential (Cu and Zn) and non-essential (Pb) metals by sunflowers from nutrient solution. EDDS was detected in shoots and xylem sap for the first time, proving that it is taken up into the above ground biomass of plants. The essential metals Cu and Zn were decreased in shoots in the presence of EDDS whereas uptake of the non-essential Pb was enhanced. We suggest that in the presence of EDDS all three metals were taken up by the non-selective apoplastic pathway as the EDDS complexes, whereas in the absence of EDDS essential metal uptake was primarily selective along the symplastic pathway. This shows that synthetic chelating agents do not necessarily increase uptake of heavy metals, when soluble concentrations are equal in the presence and absence of chelates.

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing.

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.