Effect of Fe-metabolizing bacteria and humic substances on magnetite nanoparticle reactivity towards arsenic and chromium.

Magnetite is a magnetic, Fe(II)-Fe(III)-mineral formed through abiogenic and biogenic pathways. It constitutes an attractive material for remediation due to its reactivity, large surface-area-to-volume ratio when present as nanoparticles, and magnetic recoverability. Magnetite can be repeatedly microbially oxidized or reduced, but it is unclear how this influences the reactivity of magnetite towards toxic metal or metalloid contaminants. In this study, magnetite (both abiogenic and biogenic) was exposed to microbial Fe(II) oxidation and Fe(III) reduction, before reacted with hexavalent chromium (Cr(VI)) or pentavalent arsenic (As(V)). Results showed microbial reduction of both magnetite types improved the removal rate of Cr(VI) from solution, though surprisingly microbial Fe(II)-oxidation also showed enhanced reactivity towards Cr(VI) compared to un-treated magnetite. Synchrotron based analysis confirmed the formation of Cr(III) at the surface of the magnetite. Reactivity with As was less dramatic and showed un-treated material was able to remove As(V) from solution faster than microbially Fe(III)-reduced and Fe(II)-oxidized magnetite. The presence of humic substances was also shown to lead to a decreased reactivity of biogenic and abiogenic magnetite towards As(V) and Cr(VI). Our results imply that Fe-metabolizing bacteria influence the immobilization of contaminants and should be considered when evaluating remediation schemes, especially where Fe-metabolizing bacteria are active.

Germanium speciation using liquid chromatography-inductively coupled plasma-triple quadrupole mass spectrometry: Germanium in biological and chemical leaching solutions of fine-grained residues from copper smelting.

A new method for the speciation analysis of inorganic germanium (Ge(OH)4), monomethylgermanium (MMGe) and dimethylgermanium (DMGe) in complex acidic aqueous leachates by liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC-ICP-MS) was developed. The species are separated using anion exchange chromatography with tartrate added as complexing agent. When tartrate was added to the sample and the eluent chromatography was not affected by sulfate concentrations up to 100 mM. The He collision mode (MS/MS mode) removes polyatomic plasma- and matrix-based interferences, thus providing the selectivity in Ge speciation required for the complex samples. With LOQs of 62 ng L-1 (DMGe), 67 ng L-1 (MMGe) and 164 ng L-1 (Ge(OH)4) the method was sufficiently sensitive for the intended application. The developed method was applied to biological and chemical leachates of sulfidic flue dust from copper shale smelting (Theisen sludge). Only small amounts of methylated Ge species were determined next to inorganic Ge in these leachates.

Four Molybdenum-Dependent Steroid C-25 Hydroxylases: Heterologous Overproduction, Role in Steroid Degradation, and Application for 25-Hydroxyvitamin D3 Synthesis.

Side chain-containing steroids are ubiquitous constituents of biological membranes that are persistent to biodegradation. Aerobic, steroid-degrading bacteria employ oxygenases for isoprenoid side chain and tetracyclic steran ring cleavage. In contrast, a Mo-containing steroid C-25 dehydrogenase (S25DH) of the dimethyl sulfoxide (DMSO) reductase family catalyzes the oxygen-independent hydroxylation of tertiary C-25 in the anaerobic, cholesterol-degrading bacterium Sterolibacterium denitrificans Its genome contains eight paralogous genes encoding active site α-subunits of putative S25DH-like proteins. The difficult enrichment of labile, oxygen-sensitive S25DH from the wild-type bacteria and the inability of its active heterologous production have largely hampered the study of S25DH-like gene products. Here we established a heterologous expression platform for the three structural genes of S25DH subunits together with an essential chaperone in the denitrifying betaproteobacterium Thauera aromatica K172. Using this system, S25DH1 and three isoenzymes (S25DH2, S25DH3, and S25DH4) were overproduced in a soluble, active form allowing a straightforward purification of nontagged αßγ complexes. All S25DHs contained molybdenum, four [4Fe-4S] clusters, one [3Fe-4S] cluster, and heme B and catalyzed the specific, water-dependent C-25 hydroxylations of various 4-en-3-one forms of phytosterols and zoosterols. Crude extracts from T. aromatica expressing genes encoding S25DH1 catalyzed the hydroxylation of vitamin D3 (VD3) to the clinically relevant 25-OH-VD3 with >95% yield at a rate 6.5-fold higher than that of wild-type bacterial extracts; the specific activity of recombinant S25DH1 was twofold higher than that of wild-type enzyme. These results demonstrate the potential application of the established expression platform for 25-OH-VD3 synthesis and pave the way for the characterization of previously genetically inaccessible S25DH-like Mo enzymes of the DMSO reductase family.IMPORTANCE Steroids are ubiquitous bioactive compounds, some of which are considered an emerging class of micropollutants. Their degradation by microorganisms is the major process of steroid elimination from the environment. While oxygenase-dependent steroid degradation in aerobes has been studied for more than 40 years, initial insights into the anoxic steroid degradation have only recently been obtained. Molybdenum-dependent steroid C25 dehydrogenases (S25DHs) have been proposed to catalyze oxygen-independent side chain hydroxylations of globally abundant zoo-, phyto-, and mycosterols; however, so far, their lability has allowed only the initial characterization of a single S25DH. Here we report on a heterologous gene expression platform that allowed for easy isolation and characterization of four highly active S25DH isoenzymes. The results obtained demonstrate the key role of S25DHs during anoxic degradation of various steroids. Moreover, the platform is valuable for the efficient enzymatic hydroxylation of vitamin D3 to its clinically relevant C-25-OH form.

Location and speciation of gadolinium and yttrium in roots of Zea mays by LA-ICP-MS and ToF-SIMS.

Increasing production of rare earth elements (REE) might lead to future contamination of the environment. REE have been shown to accumulate in high concentrations in roots of plants. Plant experiments with Zea mays exposed to a nutrient solution containing gadolinium (Gd) or yttrium (Y) with 10 mg L(-1) Gd or Y were carried out to investigate this accumulation behaviour. Total concentrations of 3.17 g kg(-1) and 8.43 g kg(-1) of Gd and Y were measured in treated plant roots. Using a novel combination of laser ablation mass spectrometry and time-of-flight secondary ion mass spectrometry, imaging of location and concentration of Gd and Y was carried out in root thin sections of treated roots. Single spots of elevated REE concentration were found at the epidermis, while inside the cortex, weak signals of Gd(+) and Y(+) were aligning with the root cell structures. The composition of Gd-containing secondary ions proves an REE-oxide phase accumulated at the epidermis, limiting REE availability for further uptake.

Inositol transporters AtINT2 and AtINT4 regulate arsenic accumulation in Arabidopsis seeds.

Arsenic contamination of groundwater and soils threatens the health of tens of millions of people worldwide. Understanding the way in which arsenic is taken up by crops such as rice, which serve as a significant source of arsenic in the human diet, is therefore important. Membrane transport proteins that catalyse arsenic uptake by roots, and translocation through the xylem to shoots, have been characterized in a number of plants, including rice. The transporters responsible for loading arsenic from the xylem into the phloem and on into the seeds, however, are yet to be identified. Here, we show that transporters responsible for inositol uptake in the phloem in Arabidopsis also transport arsenic. Transformation of Saccharomyces cerevisiae with AtINT2 or AtINT4 led to increased arsenic accumulation and increased sensitivity to arsenite. Expression of AtINT2 in Xenopus laevis oocytes also induced arsenite import. Disruption of AtINT2 or AtINT4 in Arabidopsis thaliana led to a reduction in phloem, silique and seed arsenic concentrations in plants fed with arsenite through the roots, relative to wild-type plants. These plants also exhibited a large drop in silique and seed arsenic concentrations when fed with arsenite through the leaves. We conclude that in Arabidopsis, inositol transporters are responsible for arsenite loading into the phloem, the key source of arsenic in seeds.

Arsenic(V) Incorporation in Vivianite during Microbial Reduction of Arsenic(V)-Bearing Biogenic Fe(III) (Oxyhydr)oxides.

The dissolution of arsenic-bearing iron(III) (oxyhydr)oxides during combined microbial iron(III) and arsenate(V) reduction is thought to be the main mechanism responsible for arsenic mobilization in reducing environments. Besides its mobilization during bioreduction, arsenic is often resequestered by newly forming secondary iron(II)-bearing mineral phases. In phosphate-bearing environments, iron(II) inputs generally lead to vivianite precipitation. In fact, in a previous study we observed that during bioreduction of arsenate(V)-bearing biogenic iron(III) (oxyhydr)oxides in phosphate-containing growth media, arsenate(V) was immobilized by the newly forming secondary iron(II) and iron(II)/iron(III)mineral phases, including vivianite. In the present study, changes in arsenic redox state and binding environment in these experiments were analyzed. We found that arsenate(V) partly replaced phosphate in vivianite, thus forming a vivianite-symplesite solid solution identified as Fe3(PO4)1.7(AsO4)0.3·8H2O. Our data suggests that in order to predict the fate of arsenic during the bioreduction of abiogenic and biogenic iron(III) (oxyhydr)oxides in arsenic-contaminated environments, the formation of symplesite-vivianite minerals needs to be considered. Indeed, such mineral phases could contribute to a delayed and slow release of arsenic in phosphate-bearing surface and groundwater environments.

A sequential extraction procedure to evaluate the mobilization behavior of rare earth elements in soils and tailings materials.

A novel sequential extraction method for evaluation of the mobilization behavior of rare earth elements in soils and mine tailings materials is presented. The sequence consists of the following four steps: 0.05 mol L(-1) calcium nitrate (easily soluble and ion exchange fraction), 0.1 mol L(-1) citric acid (fraction mobilized by complexation and carbonate bound), 0.05 mol L(-1) hydroxylamine hydrochloride (pH = 2) (reducible fraction), 1.4 mol L(-1) nitric acid (acid soluble fraction). The procedure was optimized with a certified soil material and a mine tailings material and was applied to eight samples of a soil profile. The different results obtained by using either the developed method or the widespread used BCR-Method for comparison are discussed. There were clear advantages using the newly created sequential extraction procedure in getting more detailed information about the bioavailable fraction and a fraction addressing REE phosphates.

The influence of gadolinium and yttrium on biomass production and nutrient balance of maize plants.

Rare earth elements (REE) are expected to become pollutants by enriching in the environment due to their wide applications nowadays. The uptake and distribution of gadolinium and yttrium and its influence on biomass production and nutrient balance was investigated in hydroponic solution experiments with maize plants using increasing application doses of 0.1, 1 and 10 mg L(-1). It could be shown that concentrations of up to 1 mg L(-1) of Gd and Y did not reduce or enhance the plant growth or alter the nutrient balance. 10 mg L(-1) Gd or Y resulted in REE concentrations of up to 1.2 weight-% in the roots and severe phosphate deficiency symptoms. Transfer rates showed that there was only little transport of Gd and Y from roots to shoots. Significant correlations were found between the concentration of Gd and Y in the nutrient solution and the root tissue concentration of Ca, Mg and P.

Silicic acid competes for dimethylarsinic acid (DMA) immobilization by the iron hydroxide plaque mineral goethite.

A surface complexation modeling approach was used to extend the knowledge about processes that affect the availability of dimethylarsinic acid (DMA) in the soil rhizosphere in presence of a strong sorbent, e.g., Fe plaques on rice roots. Published spectroscopic and molecular modeling information suggest for the organoarsenical agent to form bidentate-binuclear inner-sphere surface complexes with Fe hydroxides similar to the inorganic As oxyanions. However, since also the ubiquitous silicic acid oxyanion form the same bidentate binuclear surface complexes, our hypothesis was that it may have an effect on the adsorption of DMA by Fe hydroxides in soil. Our experimental batch equilibrium data show that DMA is strongly adsorbed in the acidic pH range, with a steep adsorption edge in the circumneutral pH region between the DMA acidity constant (pKa=6.3) and the point of zero charge value of the goethite adsorbent (pHpzc=8.6). A 1-pK CD-MUSIC surface complexation model was chosen to fit the experimental adsorption vs. pH data. The same was done for silicic acid batch equilibrium data with our goethite adsorbent. Both model parameters for individual DMA and silicic acid adsorption were then merged into one CD-MUSIC model to predict the binary DMA+Si adsorption behavior. Silicic acid (500 µM) was thus predicted by the model to strongly compete for DMA with up to 60% mobilization of the latter at a pH6. This model result could be verified subsequently by experimental batch equilibrium data with zero adjustable parameters. The thus quantified antagonistic relation between DMA and silicic acid is discussed as one of factors to explain the increase of the DMA proportion in rice grains as observed upon silica fertilization of rice fields.

Investigation on stability and preservation of antimonite in iron rich water samples.

The stability of antimonite in iron rich water samples is rather poor. The aim of the study was to find a simple procedure by using preservation agents to keep the speciation information from sampling till analysis. Species analysis of antimony traces (lower µg L(-1) range) was done by HPLC-ICP-MS. Phosphoric acid, tartrate, and EDTA were tested as preservation agents in comparison to no addition. The use of EDTA as the preservation agent provided the best results. The suggested procedure is to add 20 mM EDTA as final concentration immediately during sampling and store them at dark and cool (6 °C) as usual. Using this procedure, the stability of Sb(III) as well as of Sb(V) was proven for at least 7 days, even for high iron concentrations.

Are rice (Oryza sativa L.) phosphate transporters regulated similarly by phosphate and arsenate? A comprehensive study.

Rice is one of the most important staple foods worldwide, but it often contains inorganic arsenic, which is toxic and gives rise to severe health problems. Rice plants take up arsenate As(V) via the phosphate transport pathways, though it is not known how As(V), as compared to phosphate, modifies the expression of phosphate transporters (PTs). Therefore, the impact of As(V) or phosphate (Pi) on the gene expression of PTs and several Pi signaling regulators was investigated. Rice plants were grown on medium containing different As(V) or Pi concentrations. Growth was evaluated and the expression of tested genes was quantified at different time points, using quantitative RT-PCR (qPCR). The As and P content in plants was determined using inductively coupled plasma mass spectrometry (ICP-MS). As(V) elicited diverse and opposite responses of different PTs in roots and shoots, while Pi triggered a more shallow and uniform transcriptional response in several tested genes. Only a restricted set of genes, including PT2, PT3, PT5 and PT13 and two SPX-MFS family members, was particularly responsive to As(V). Despite some common reactions, the responses of the analyzed genes were predominantly ion-specific. The possible reasons and consequences are discussed.

Fate of arsenic during microbial reduction of biogenic versus Abiogenic As-Fe(III)-mineral coprecipitates.

Fe(III) (oxyhydr)oxide minerals exhibit a high sorption affinity for arsenic (As) and the reductive dissolution of As-bearing Fe(III) (oxyhydr)oxides is considered to be the primary mechanism for As release into groundwater. To date, research has focused on the reactivity of abiogenic Fe(III) (oxyhydr)oxides, yet in nature biogenic Fe(III) (oxyhydr)oxides, precipitated by Fe(II)-oxidizing bacteria are also present. These biominerals contain cell-derived organic matter (CDOM), leading to different properties than their abiogenic counterparts. Here, we follow Fe mineralogy and As mobility during the reduction of As-loaded biogenic and abiogenic Fe(III) minerals by Shewanella oneidensis MR-1. We found that microbial reduction of As(III)-bearing biogenic Fe(III) (oxyhydr)oxides released more As than reduction of abiogenic Fe(III) (oxyhydr)oxides. In contrast, As was immobilized more effectively during reduction of As(V)-loaded biogenic than abiogenic Fe(III) (oxyhydr)oxides during secondary Fe mineral formation. During sterile incubation of minerals and after microbial Fe(III) reduction stopped, As(V) was mobilized from biogenic Fe(III) (oxyhydr)oxides probably by sorption competition with phosphate and CDOM. Our data show that the presence of CDOM significantly influences As mobility during reduction of Fe(III) minerals and we suggest that it is essential to consider both biogenic and abiogenic Fe(III) (oxyhydr)oxides to further understand the environmental fate of As.

Behaviour of metalloids and metals from highly polluted soil samples when mobilized by water--evaluation of static versus dynamic leaching.

The mobilization behaviour of metalloids and metals when leached by water from highly polluted soil/sediment samples was studied using static and dynamic approaches employing batch methodology and rotating coiled columns (RCC), respectively. Increasing the solution-to-solid ratios during batch leaching resulted in different enhanced mobilization rates, which are element-specific and matrix-specific. When dynamic leaching is employed with continuous replacement of the eluent, a higher portion is mobilized than when using batch elution with an identical solid-to-water ratio. Using RCC the time-resolved leaching of the elements was monitored to demonstrate the leaching patterns. For the majority of elements a significant decrease could be shown in the mobilized portion of the elements with ongoing leaching process. The data were discussed targeted at solid liquid partitioning coefficients of the metal(loid)s. The capabilities in application of K(d) values was demonstrated for dynamic leaching which is relevant for environmental processes.

Remobilization of pentavalent antimony and vanadium from a granular iron hydroxide material--a comparative study of different leaching systems.

The remobilization of antimony and vanadium from previously loaded commercial granular ferric-hydroxide GEH material (intended for water treatment) was examined by using a sequential extraction procedure and three different leaching systems to evaluate their physicochemical mobility and potential availability under different simulated environmental conditions. A classical batch extraction, an extraction cell (EC) and rotating-coiled columns (RCC) were used as extraction systems. For each system it could be shown that the content of ion-exchangeable antimony and vanadium in previously loaded material is negligible (<1.5%). The oxyanions were sorbed strongly and could be predominantly remobilized through reducing agents, which means through dissolution of the iron (hydr)oxide matrix. The major advantages of dynamic systems in comparison to batchwise fractionation technique are the drastically reduced extraction time and the possibility of generating information to the leaching kinetics. It is shown that the efficiency of the three leaching systems is quite different employing Wenzel's sequential fractionation protocol. Only by working with RCC, the iron (hydr)oxide matrix was completely dissolved within four steps resulting in the total mobilization of antimony and vanadium. EC seems to be less suitable for leaching studies of Sb and V sorbed on iron(hydr)oxide. The remobilizable proportion of the several fractions was lower in comparison to batch and RCC and seems to be a result of an agglomeration of the GEH in the EC device.

Biogenic Fe(III) minerals lower the efficiency of iron-mineral-based commercial filter systems for arsenic removal.

Millions of people worldwide are affected by As (arsenic) contaminated groundwater. Fe(III) (oxy)hydroxides sorb As efficiently and are therefore used in water purification filters. Commercial filters containing abiogenic Fe(III) (oxy)hydroxides (GEH) showed varying As removal, and it was unclear whether Fe(II)-oxidizing bacteria influenced filter efficiency. We found up to 10(7) Fe(II)-oxidizing bacteria/g dry-weight in GEH-filters and determined the performance of filter material in the presence and absence of Fe(II)-oxidizing bacteria. GEH-material sorbed 1.7 mmol As(V)/g Fe and was ~8 times more efficient than biogenic Fe(III) minerals that sorbed only 208.3 µmol As(V)/g Fe. This was also ~5 times more efficient than a 10:1-mixture of GEH-material and biogenic Fe(III) minerals that bound 322.6 µmol As(V)/g Fe. Coprecipitation of As(V) with biogenic Fe(III) minerals removed 343.0 µmol As(V)/g Fe, while As removal by coprecipitation with biogenic minerals in the presence of GEH-material was slightly less efficient as GEH-material only and yielded 1.5 mmol As(V)/g Fe. The present study thus suggests that the formation of biogenic Fe(III) minerals lowers rather than increases As removal efficiency of the filters probably due to the repulsion of the negatively charged arsenate by the negatively charged biogenic minerals. For this reason we recommend excluding microorganisms from filters (e.g., by activated carbon filters) to maintain their high As removal capacity.

Concentrations and speciation of arsenic in groundwater polluted by warfare agents.

Groundwater polluted with phenylarsenicals from former warfare agent deposits and their metabolites was investigated with respect to the behavior of relevant arsenic species. Depth profiles at the estimated source and at about 1km downgradient from the source zone were sampled. The source zone is characterized by high total arsenic concentrations up to 16mgL(-1) and is dominated by organic arsenic compounds. The concentrations in the downgradient region are much lower (up to 400µgL(-1)) and show a high proportion of inorganic arsenic species. Iron precipitation seems to be an effective mechanism to prevent dispersion of inorganic arsenic as well as phenylarsonic acid. Reductive conditions were observed in the deeper zone with predominant occurrence of trivalent arsenic species. The inorganic species are in redox equilibrium, whereas the phenylarsenic compounds have variable proportions. Methylphenylarsinic acid was identified in groundwater in traces which indicates microbial degradation activity.

Uptake and toxicity of hexafluoroarsenate in aquatic organisms.

The arsenic species hexafluoroarsenate has been described as a contaminant of surface waters of anthropogenic origin. Here, we undertake to identify the most sensitive biological receptor among several sentinel aquatic species used in eco-toxicological assessment and to understand toxicity in terms of internal dose. Therefore, a screening of short-term effects using different aquatic organisms (bacterium Vibrio fischeri, fish Danio rerio, crustacean Daphnia magna and green alga Desmodesmus subspicatus and Scenedesmus vacuolatus) was conducted. For most organisms tested, effects were not detectable even at very high hexafluoroarsenate concentrations (up to 9.6mM) and thus the ecotoxic potential was found to be low in comparison to other arsenic compounds. The only organisms showing a clear response were the unicellular green alga, e.g. S. vacuolatus with an EC(50) value of 1.12 mM (84 mg L(-1) As). A linear relationship between ambient and internal concentration was found for this organism with a slope of 1.63 x 10(-3). Therefore, the internal concentration which shows a significant effect, e.g. 20% of inhibition of reproduction, was found to occur at a relatively low internal dose of 0.98 microM. Moreover, no biotransformation products inside the algae could be detected using arsenic speciation analysis with HPLC-ICP-MS, thus biological effects must be attributed to the untransformed compound. We conclude that the very low uptake observed for hexafluoroarsenate may be interpreted as preventive against toxic effects for the organisms.

Natural attenuation potential of phenylarsenicals in anoxic groundwaters.

The extensive production of chemical warfare agents in the 20th century has led to serious contamination of soil and groundwater with phenyl arsenicals at former ammunition depots or warfare agent production sites worldwide. Most phenyl arsenicals are highly toxic for humans. The microbial degradation of phenylarsonic acid (PAA) and diphenylarsinic acid (DPAA) was investigated in microcosms made of anoxic groundwater/sediment mixtures taken from different depths of an anoxic, phenyl arsenical contaminated aquifer in Central Germany. DPAA was not transformed within 91 days incubation time in any of the microcosms. The removal of PAA can be described by a first order kinetics without a lag-phase (rate: 0.037 d(-1)). In sterilized microcosms, PAA concentrations always remained stable, demonstrating that PAA transformation was a biologically mediated process. PAA transformation occurred under sulfate-reducing conditions due to sulfate consumption and production of sulfide. The addition of lactate (1 mM), a typical substrate of sulfate-reducing bacteria, increased the transformation rate of PAA significantly up to 0.134 d(-1). The content of total arsenic was considerably reduced (> 75%). Intermediates of PAA transformation were detected by high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Experiments with a pure strain and sterile controls of Desulfovibrio gigas spiked with PAA showed that the elimination process is linked to the presence of sulfide formed through bacterial activity. Phenyl arsenicals were likely immobilized in the sedimentthrough sulfur substitution and a subsequent sulfur bond under the prevailing sulfate reducing condition. The results of this study indicate that PAA can undergo microbiologically mediated transformation in anoxic aquifers, leading to reduced concentrations in groundwater, which indicate a (enhancend) natural attenuation potential.

Simultaneous determination of inorganic and organic antimony species by using anion exchange phases for HPLC-ICP-MS and their application to plant extracts of Pteris vittata.

Antimony is a common contaminant at abandoned sites for non-ferrous ore mining and processing. Because of the possible risk of antimony by transfer to plants growing on contaminated sites, it is of importance to analyze antimony and its species in such biota. A method based on high performance liquid chromatographic separation and inductively coupled plasma mass spectrometric detection (HPLC-ICP-MS) was developed to determine inorganic antimony species such as Sb(III) and Sb(V) as well as possible antimony-organic metabolisation products of the antimony transferred into plant material within one chromatographic run. The separation is performed using anion chromatography on a strong anion exchange column (IonPac AS15/AG 15). Based on isocratic optimizations for the separation of Sb(III) and Sb(V) as well as Sb(V) and trimenthylated Sb(V) (TMSb(V)), a chromatographic method with an eluent gradient was developed. The suggested analytical method was applied to aqueous extracts of Chinese break fern Pteris vittata samples. The transfer of antimony from spiked soil composites into the fern, which is known as a hyperaccumulator for arsenic, was investigated under greenhouse conditions. Remarkable amounts of antimony were transferred into roots and leaves of P. vittata growing on spiked soil composites. Generally, P. vittata accumulates not only arsenic (as shown in a multiplicity of studies in the last decade), but also antimony to a lower extent. The main contaminant in the extracts was Sb(V), but also elevated concentrations of Sb(III) and TMSb(V) (all in microg L(-1) range). An unidentified Sb compound in the plant extracts was detected, which slightly differ in elution time from TMSb(V).

Adsorption mechanism of arsenate by zirconyl-functionalized activated carbon.

Arsenate [As(V)] and arsenite [As(III)] sorption at the solid-water interface of activated carbon impregnated with zirconyl nitrate (Zr-AC) was investigated using X-ray absorption spectroscopy (XAS) and surface complexation modeling. The XAS data at the Zr K-edge suggest that the structure of the zirconyl nitrate coating is built from chains of edge-sharing ZrO8 trigonal dodecahedra bound to each other through two double hydroxyl bridges. The 8-fold coordination of each Zr atom is completed by four O atoms, which share a bit less than the two theoretically possible bidentate nitrate groups. On impregnation, two of the O atoms may lose their nitrate group and be transformed to hydroxyl groups ready for binding to carboxylic or phenolic ligands at the AC surface. As K-edge XANES results showed the presence of only As(V) on adsorption regardless of the initial As oxidation state. Oxidation to As(V) is probably mediated by available carbon species on the AC surface as found by batch titration. Zr K-edge EXAFS data indicate that arsenate tetrahedra form monodentate mononuclear surface complexes with free hydroxyl groups of zirconyl dodecahedra, whereby each bidentate nitrate group is exchanged by up to two arsenate groups. The inner-sphere arsenate binding to the Zr-AC surface sites constrained with the spectroscopic results was used in the formulation of a surface complexation model to successfully describe the adsorption behavior of arsenate in the pH range between 4 and 12. The results suggest therefore that Zr-AC is an effective adsorbent for arsenic removal due to its high surface area and the presence of high affinity surface hydroxyl groups.