Arsenic triggered nano-sized uranyl arsenate precipitation on the surface of Kocuria rosea.

Arsenic (As) and uranium (U) frequently occur together naturally and, in consequence, transform into cocontaminants at sites of uranium mining and processing, yet the simultaneous interaction process of arsenic and uranium has not been well documented. In the present contribution, the influence of arsenate on the removal and reduction of uranyl by the indigenous microorganism Kocuria rosea was characterized using batch experiments combined with species distribution calculation, SEM-EDS, FTIR, XRD and XPS. The results showed that the coexistence of arsenic plays an active role in Kocuria rosea growth and the removal of uranium under neutral and slightly acidic conditions. U-As complex species of UO2HAsO4 (aq) had a positive effect on uranium removal, while Kocuria rosea cells appeared to have a large specific surface area serving as attachment sites. Furthermore, a large number of nano-sized flaky precipitates, constituted by uranium and arsenic, attached to the surface of Kocuria rosea cells at pH 5 through P=O, COO-, and C=O groups in phospholipids, polysaccharides, and proteins. The biological reduction of U(VI) and As(V) took place in a successive way, and the formation of a chadwickite-like uranyl arsenate precipitate further inhibited U(VI) reduction. The results will help to design more effective bioremediation strategies for arsenic-uranium cocontamination.

Arsenosugar standards extracted from algae: Isolation, characterization and use for identification and quantification purposes.

Sulfate (SO4-sug) and sulfonate (SO3-sug) arsenosugar standard solutions were obtained using preparative liquid chromatography. Several commercial algae samples were characterized (total contents and speciation) to select the most appropriate in relation to their arsenosugar contents. Water extracts from the selected sample (Fucus vesiculosus) were fractionated using a Hamilton PRP-X100 preparative column, and the presence of arsenic species in the isolated fractions was ascertained by IC-ICP-MS. Two of the fractions successfully presented only one arsenic species corresponding to sulfate and sulfonate arsenosugars at suitable concentrations. To unequivocally confirm the presence of both compounds, high-resolution mass spectrometry (ESI-TOF/MS) was used and the exact mass determined with errors lower than 0.5 ppm. The standard solutions obtained were successfully used to identify and quantify SO4-sug and SO3-sug in several edible algae samples purchased in local market. Total arsenic content for analyzed samples ranged from 34 to 57 mg kg-1, concentration values found for SO3-sug ranged from 5 to 36 mg As kg-1 and SO4-sug was only found in fucus with a concentration of 9.3 mg As kg-1.

Competitive adsorption and desorption of arsenate, vanadate, and molybdate onto the low-cost adsorbent materials alum water treatment sludge and bauxite.

When low-cost adsorbents are being used to remove contaminant ions (e.g. arsenate, vanadate, and molybdate) from wastewater, competitive adsorption/desorption are central processes determining their removal efficiency. Competitive adsorption of As, V, and Mo was investigated using equimolar oxyanion concentrations in single, binary, and tertiary combinations in adsorption isotherm and pH envelope studies while desorption of previously adsorbed oxyanions was examined in solutions containing single and binary oxyanion combinations. The low-cost adsorbent materials used were alum water treatment sludge (amorphous hydroxy-Al) and bauxite ore (crystalline Al oxides). Adsorption isotherm and pH envelope studies showed that Mo had only a small effect in decreasing adsorption of As and V but V and As had substantial and similar effects in reducing adsorption of the other. As had a greater effect than V in reducing adsorption of Mo and it was concluded that the affinity of oxyanions for the surfaces of water treatment sludge and bauxite followed the order As > V >> Mo. In 0.3 M NaCl electrolyte, desorption of previously adsorbed oxyanions amounted to 0.3-3.4% for V and As, and 11-20% for Mo. As had approximately four times greater effect than Mo in increasing desorption of V while V had about three times the effect of Mo in increasing desorption of As. Thus, the order of oxyanions in inducing desorption of the other oxyanions (i.e. As on V and As) was the same as that for adsorption selectivity: As > V >> Mo. Water treatment sludge was a more effective adsorbent than bauxite because it had a greater adsorption capacity for all three anions and, in addition, they were held more strongly so desorption in the background electrolyte was proportionately less. It was concluded that at similar molar concentrations, arsenate would tend to reduce adsorption of vanadate as well as displace vanadate already held on adsorbent surfaces while both anions will compete effectively with molybdate. The limiting factor for simultaneous removal of As, V, and Mo from multielement solutions by adsorption will therefore be the removal of Mo.

Treatment of a mixed wood preservative leachate by a hybrid constructed wetland and a willow planted filter.

The performance and removal mechanisms of a hybrid constructed wetland (HCW) followed by a willow planted filter (WPF) were evaluated for the treatment of a leachate contaminated by wood pole preservatives (pentachlorophenol (PCP) and chromated copper arsenate) to reach the storm sewer discharge limits. The HCW aimed to dechlorinate the PCP and polychlorodibenzo-p-dioxins/polychlorodibenzofuran (PCDD/F) and to remove metals by adsorption and precipitation. The HCW was efficient in removing PCP (>98.6%), oil, arsenic (99.4%), chromium (>99.2%), copper (>99.6%%) and iron (29%) to under their discharge limits, but it was unable to reach those of Mn and PCDD/F, with residual concentrations of 0.11 mg Mn/L and 0.32 pg TEQ/L. Iron and manganese could be removed but were subsequently released by the HCW due to low redox conditions. No dechlorination of PCDD/F was observed since its chlorination profile remained the same in the different sections of the HCW. Adsorption was the most probable removal mechanism of PCDD/F. The WPF was able to remove some residual contamination, but it released Mn at a gradually decreasing rate. Total evapotranspiration of the leachate by a larger fertilized WPF and the construction of an underground retention basin are proposed to prevent any discharge of PCDD/F traces in the environment.

Removal of arsenic(III,V) by a granular Mn-oxide-doped Al oxide adsorbent: surface characterization and performance.

In order to remove arsenic (As) from contaminated water, granular Mn-oxide-doped Al oxide (GMAO) was fabricated using the compression method with the addition of organic binder. The analysis results of XRD, SEM, and BET indicated that GMAO was microporous with a large specific surface area of 54.26 m2/g, and it was formed through the aggregation of massive Al/Mn oxide nanoparticles with an amorphous pattern. EDX, mapping, FTIR, and XPS results showed the uniform distribution of Al/Mn elements and numerous hydroxyl groups on the adsorbent surface. Compression tests indicated a satisfactory mechanical strength of GMAO. Batch adsorption results showed that As(V) adsorption achieved equilibrium faster than As(III), whereas the maximum adsorption capacity of As(III) estimated from the Langmuir isotherm at 25 °C (48.52 mg/g) was greater than that of As(V) (37.94 mg/g). The As removal efficiency could be maintained in a wide pH range of 3~8. The presence of phosphate posed a significant adverse effect on As adsorption due to the competition mechanisms. In contrast, Ca2+ and Mg2+ could favor As adsorption via cation-bridge involvement. A regeneration method was developed by using sodium hydroxide solution for As elution from saturated adsorbents, which permitted GMAO to keep over 75% of its As adsorption capacity even after five adsorption-regeneration cycles. Column experiments showed that the breakthrough volumes for the treatment of As(III)-spiked and As(V)-spiked water (As concentration = 100 µg/L) were 2224 and 1952, respectively. Overall, GMAO is a potential adsorbent for effectively removing As from As-contaminated groundwater in filter application.

Macroscopic and microscopic investigation of adsorption and precipitation of Zn on γ-alumina in the absence and presence of As.

Contaminants zinc (Zn) and arsenate (As) often coexist in soils. However, little is known concerning the impacts of coexisting As on Zn adsorption and precipitation on soil minerals. In the present study, adsorption and precipitation of Zn on γ-alumina in the absence and presence of arsenate was investigated employing batch experiments and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Results indicated that Zn formed edge-sharing tetrahedral surface complexes at pH 5.5 and Zn-Al LDH-like (layered double hydroxide) precipitates at pH 7.0 on the surface of γ-alumina. The presence of arsenate significantly enhanced Zn sorption densities, and remarkably changed its bonding environment. At pH 5.5, SR-XRD (Synchrotron Radiation-based X-ray Diffraction) and EXAFS showed that koettigite-like precipitate were formed in the cosorption of Zn and As on γ-alumina regardless of the addition sequence of As and Zn. At pH 7.0, when Zn was preequilibrated with γ-alumina prior to the As introduction, mixed Zn-Al LDH-like and amorphous adamite-like precipitates formed. However, when Zn and As were added simultaneously, only amorphous adamite-like precipitate was observed. Zn inner-sphere complexes and surface ternary complexes γ-alumina-As-Zn were the main outcome when As was preequilibrated firstly. Zn-arsenate precipitates could significantly decrease the concentration of Zn in aqueous solution and decrease the bioavailability and mobilization of Zn in soils.

Phosphate reclaim from simulated and real eutrophic water by magnetic biochar derived from water hyacinth.

In this study, the efficiency and mechanism of aqueous phosphate removal by magnetic biochar derived from water hyacinth (MW) were investigated. The MW pyrolyzed at 450 °C (MW450) exhibited the most prominent phosphate sorption capacity, which was estimated to be 5.07 mg g-1 based on Langmuir-Freundlich model. At an initial phosphorus (P) concentration of 1 mg l-1, >90% P removal was achieved over pH 3-9, but the efficiency decreased sharply at pH > 10. The presence of arsenate and carbonate could remarkably decrease P sorption, while the inhibition effects of antimonate, nitrate and sulfate were less significant. In further application of MW450 to reclaim P from eutrophic lake waters (0.71-0.94 mg l-1 total P), ∼96% P removals were attained in the batch studies and the effluent P concentrations in the column tests were reduced to <0.05 mg l-1 within 509-1019 empty bed volumes. As indicated by XRD, MW450 surface was dominated by Fe3O4 and Fe2O3, resulting in a good ferromagnetic property of this composite (saturation magnetization 45.8 emu g-1). Based on XPS, P sorption onto MW450 occurred mainly by surface complexation with the hydroxyl via ligand exchange. These results highlighted that MW derived from highly damaging water hyacinth could provide a promising alternative for P removal from most eutrophic waters.

Simultaneous reduction of arsenic(V) and uranium(VI) by mackinawite: role of uranyl arsenate precipitate formation.

Uranium (U) and arsenic (As) often occur together naturally and, as a result, can be co-contaminants at sites of uranium mining and processing, yet few studies have examined the simultaneous redox dynamics of U and As. This study examines the influence of arsenate (As(V)) on the reduction of uranyl (U(VI)) by the redox-active mineral mackinawite (FeS). As(V) was added to systems containing 47 or 470 µM U(VI) at concentrations ranging from 0 to 640 µM. In the absence of As(V), U was completely removed from solution and fully reduced to nano-uraninite (nano-UO2). While the addition of As(V) did not reduce U uptake, at As(V) concentrations above 320 µM, the reduction of U(VI) was limited due to the formation of a trögerite-like uranyl arsenate precipitate. The presence of U also significantly inhibited As(V) reduction. While less U(VI) reduction to nano-UO2 may take place in systems with high As(V) concentrations, formation of trögerite-like mineral phases may be an acceptable reclamation end point due to their high stability under oxic conditions.

Sequential enrichment with titania-coated magnetic mesoporous hollow silica microspheres and zirconium arsenate-modified magnetic nanoparticles for the study of phosphoproteome of HL60 cells.

As one of the most important types of post-translational modifications, reversible phosphorylation of proteins plays crucial roles in a large number of biological processes. However, owing to the relatively low abundance and dynamic nature of phosphorylation and the presence of the unphosphorylated peptides in large excess, phosphopeptide enrichment is indispensable in large-scale phosphoproteomic analysis. Metal oxides including titanium dioxide have become prominent affinity materials to enrich phosphopeptides prior to their analysis using liquid chromatography-mass spectrometry (LC-MS). In the current study, we established a novel strategy, which encompassed strong cation exchange chromatography, sequential enrichment of phosphopeptides using titania-coated magnetic mesoporous hollow silica microspheres (TiO2/MHMSS) and zirconium arsenate-modified magnetic nanoparticles (ZrAs-Fe3O4@SiO2), and LC-MS/MS analysis, for the proteome-wide identification of phosphosites of proteins in HL60 cells. In total, we were able to identify 11,579 unique phosphorylation sites in 3432 unique proteins. Additionally, our results suggested that TiO2/MHMSS and ZrAs-Fe3O4@SiO2 are complementary in phosphopeptide enrichment, where the two types of materials displayed preferential binding of peptides carrying multiple and single phosphorylation sites, respectively.

Loop flow analysis of dissolved reactive phosphorus in aqueous samples.

The current flow based method for the determination of dissolved reactive phosphorus (DRP) suffers interference from salinity (e.g. index refractive difference) and the incidentally formed bubbles, which can be a problem for optical detection. Here we reported a simple and robust loop flow analysis (LFA) method for accurate measurement of DRP in different aqueous samples. The chemistry is based on the classic phosphomolybdenum blue (PMB) reaction and the PMB formed in a novel cross-shaped flow cell was detected at 700 nm using a miniature spectrophotometer. The effects of reagents on the kinetic formation of PMB were evaluated. The detection limit was 32 nM with an optical pathlength of 1cm and the relative standard deviations for repetitive determinations of 1, 2 and 8 µM phosphate solutions were 1.8% (n=113, without any stoppage during repeating analysis for >7h), 1.0% (n=49) and 0.39% (n=9), respectively. The analysis time was 4 min sample(-1). The effects of salinity and interfering ions (silicate and arsenate) were evaluated and showed no interference under the proposed protocol for DRP analysis. Using the LFA method, different aqueous samples with a salinity range of 0-34 were analyzed and the results showed excellent agreement with the reference method (slope 0.9982±0.0063, R(2)=0.9987, n=34). Recoveries for spiked samples varied from 95.4% to 103.7%. The proposed method showed insignificant interference from salinity, silicate and arsenate, higher reproducibility, easier operation and was free of the bubble problem.

Phosphorus-arsenic interactions in variable-charge soils in relation to arsenic mobility and bioavailability.

Phosphorus (P) influences arsenic (As) mobility and bioavailability which depends on the charge components of soil. The objective of this study was to examine P-As interaction in variable-charge allophanic soils in relation to P-induced As mobilization and bioavailability. In this work, the effect of P on arsenate [As(V)] adsorption and desorption was examined using a number of allophanic and non-allophanic soils which vary in their anion adsorption capacity. The effect of P on As uptake by Indian mustard (Brassica juncea L.) plants was examined using a solution culture, and a soil plant growth experiment involving two As-spiked allophanic and non-allophanic soils which vary in their anion adsorption capacity, and a field As-contaminated sheep dip soil. Arsenate adsorption increased with an increase in the anion adsorption capacity of soils. The addition of P resulted in an increase in As desorption, and the effect was more pronounced in the case of allophanic soil. In the case of both As-spiked soils and field contaminated sheep-dip soil, application of P increased the desorption of As, thereby increasing its bioavailability. The effect of P on As uptake was more pronounced in the high anion adsorbing allophanic than low adsorbing non-allophanic soil. In the case of solution culture, As phytoavailability decreased with increasing concentration of P which is attributed to the competition of P for As uptake by roots. While increasing P concentration in solution decreased the uptake of As, it facilitated the translocation of As from root to shoot. The net effect of P on As phytoavailability in soils depends on the extent of P-induced As mobilization in soils and P-induced competition for As uptake by roots. The P-induced mobilization of As could be employed in the phytoremediation of As-contaminated sites. However, care must be taken to minimize the leaching of As mobilized through the P-induced desorption, thereby resulting in groundwater and off site contamination.

Absence of detectable arsenate in DNA from arsenate-grown GFAJ-1 cells.

A strain of Halomonas bacteria, GFAJ-1, has been claimed to be able to use arsenate as a nutrient when phosphate is limiting and to specifically incorporate arsenic into its DNA in place of phosphorus. However, we have found that arsenate does not contribute to growth of GFAJ-1 when phosphate is limiting and that DNA purified from cells grown with limiting phosphate and abundant arsenate does not exhibit the spontaneous hydrolysis expected of arsenate ester bonds. Furthermore, mass spectrometry showed that this DNA contains only trace amounts of free arsenate and no detectable covalently bound arsenate.

Removing heavy metals in water: the interaction of cactus mucilage and arsenate (As (V)).

High concentrations of arsenic in groundwater continue to present health threats to millions of consumers worldwide. Particularly, affected communities in the developing world need accessible technologies for arsenic removal from drinking water. We explore the application of cactus mucilage, pectic polysaccharide extracts from Opuntia ficus-indica for arsenic removal. Synthetic arsenate (As (V)) solutions were treated with two extracts, a gelling extract (GE) and a nongelling extract (NE) in batch trials. The arsenic concentration at the air-water interface was measured after equilibration. The GE and NE treated solutions showed on average 14% and 9% increases in arsenic concentration at the air-water interface respectively indicating that the mucilage bonded and transported the arsenic to the air-water interface. FTIR studies showed that the -CO groups (carboxyl and carbonyl groups) and -OH (hydroxyl) functional groups of the mucilage were involved in the interaction with the arsenate. Mucilage activity was greater in weakly basic (pH 9) and weakly acidic (pH 5.5) pH. This interaction can be optimized and harnessed for the removal of arsenic from drinking water. This work breaks the ground for the application of natural pectic materials to the removal of anionic metallic species from water.

EXAFS and DFT investigations of uranyl arsenate complexes in aqueous solution.

Uranium and arsenic often co-occur in nature, for example, in acid mine drainage waters. Interaction with arsenic is thus important to understand uranium mobility in aqueous solutions. For the present study, EXAFS spectroscopy was used to investigate the formation and identify the structure of aqueous uranyl arsenate species at pH 2. The nearest U-As distance of 3.39 Å, observed in shock-frozen liquid samples, was significantly shorter than that observed in solid uranyl arsenate minerals. The shorter bond length indicated that the solution contained a bidentate-coordinated species, in contrast to the monodentate coordination in solid uranyl arsenate minerals. The U-As coordination number of 1.6 implied that two uranyl arsenate species with U:As ratios of 1:1 and 1:2 formed in nearly equal proportions and that the hydrated uranyl ion was present only as a minor component. The two uranyl arsenate species could not be differentiated spectroscopically, since their U-As distances were equal. A comparison based on DFT modeling indicated for both the 1:1 and the 1:2 species, that the bidentate arsenates were bound to uranium with one of the binding oxygen atoms being protonated. Based on the present spectroscopic study, the two species that will have to be considered in acidic uranium-arsenic-rich solutions are thus UO(2)H(2)AsO(4)(+), and UO(2)(H(2)AsO(4))(2)(0).

Differential pair distribution function study of the structure of arsenate adsorbed on nanocrystalline γ-alumina.

Structural information is important for understanding surface adsorption mechanisms of contaminants on metal (hydr)oxides. In this work, a novel technique was employed to study the interfacial structure of arsenate oxyanions adsorbed on γ-alumina nanoparticles, namely, differential pair distribution function (d-PDF) analysis of synchrotron X-ray total scattering. The d-PDF is the difference of properly normalized PDFs obtained for samples with and without arsenate adsorbed, otherwise identically prepared. The real space pattern contains information on atomic pair correlations between adsorbed arsenate and the atoms on γ-alumina surface (Al, O, etc.). PDF results on the arsenate adsorption sample on γ-alumina prepared at 1 mM As concentration and pH 5 revealed two peaks at 1.66 Å and 3.09 Å, corresponding to As-O and As-Al atomic pair correlations. This observation is consistent with those measured by extended X-ray absorption fine structure (EXAFS) spectroscopy, which suggests a first shell of As-O at 1.69 ± 0.01 Å with a coordination number of ~4 and a second shell of As-Al at ~3.13 ± 0.04 Å with a coordination number of ~2. These results are in agreement with a bidentate binuclear coordination environment to the octahedral Al of γ-alumina as predicted by density functional theory (DFT) calculation.

Applicability of poorly crystalline aluminum oxide for adsorption of arsenate.

This study examined the characteristics of arsenate adsorption on poorly crystalline oxide (PCAO) which was obtained from recycling of dry sanding powders (DSP) produced during sanding and sawing process in a decorative interior company. After calcinating DSP at 550°C, poorly crystalline oxide (PCAO) was obtained as an adsorbent. From the batch adsorption experiments, arsenate was completely removed up to the concentration of 10 mg/L by PCAO. The stability of PCAO as an adsorbent was evaluated at pH 7 and found that the arsenate adsorbed on PCAO was stable for 24 h. The predominant interaction between arsenate and PCAO was thought to be a strong chemical bond by spectroscopic analysis. The arsenate adsorption behavior onto PCAO was satisfactorily simulated with MINEQL+, suggesting that arsenate formed inner-sphere complexes with the surface of PCAO by chemisorption. Meanwhile, the presence of competitive anions such as PO(4) (3-), SO(4) (2-) and CO(3) (2-) decreased somewhat the removal efficiency of arsenate and the effects of competing anions on the adsorption of arsenate were in the order of PO(4) (3-) > SO(4) (2-) > CO(3) (2-) under pH 6. The application of PCAO to the real mine drainage was also carried out. Although the adsorption of arsenic on the PCAO was slightly decreased rather than that removed from synthetic wastewater due to competitive sorption by multiple ions, it was possible to meet the national discharge standard limit with increasing adsorbent concentration.

Influence of arsenate adsorption to ferrihydrite, goethite, and boehmite on the kinetics of arsenate reduction by Shewanella putrefaciens strain CN-32.

The kinetics of As(V) reduction by Shewanella putrefaciens strain CN-32 was investigated in suspensions of 0.2, 2, or 20 g L(-1) ferrihydrite, goethite, or boehmite at low As (10 µM) and lactate (25 µM) concentrations. Experimental data were compared with model predictions based on independently determined sorption isotherms and rates of As(V) desorption, As(III) adsorption, and microbial reduction of dissolved As(V), respectively. The low lactate concentration was chosen to prevent significant Fe(III) reduction, but still allowing complete As(V) reduction. Reduction of dissolved As(V) followed first-order kinetics with a 3 h half-life of As(V). Addition of mineral sorbents resulted in pronounced decreases in reduction rates (32-1540 h As(V) half-life). The magnitude of this effect increased with increasing sorbent concentration and sorption capacity (goethite < boehmite < ferrihydrite). The model consistently underestimated the concentrations of dissolved As(V) and the rates of microbial As(V) reduction after addition of S. putrefaciens (∼5 × 10(9) cells mL(-1)), suggesting that attachment of S. putrefaciens cells to oxide mineral surfaces promoted As(V) desorption and thereby facilitated As(V) reduction. The interplay between As(V) sorption to mineral surfaces and bacterially induced desorption may thus be critical in controlling the kinetics of As reduction and release in reducing soils and sediments.

Effects of adsorbed arsenate on the rate of transformation of 2-line ferrihydrite at pH 10.

2-Line ferrihydrite, a form of iron in uranium mine tailings, is a dominant adsorbent for elements of concern (EOC), such as arsenic. As ferrihydrite is unstable under oxic conditions and can undergo dissolution and subsequent transformation to hematite and goethite over time, the impact of transformation on the long-term stability of EOC within tailings is of importance from an environmental standpoint. Here, studies were undertaken to assess the rate of 2-line ferrihydrite transformation at varying As/Fe ratios (0.500-0.010) to simulate tailings conditions at the Deilmann Tailings Management Facility of Cameco Corporation, Canada. Kinetics were evaluated under relevant physical (~1 °C) and chemical conditions (pH ~10). As the As/Fe ratio increased from 0.010 to 0.018, the rate of ferrihydrite transformation decreased by 2 orders of magnitude. No transformation of ferrihydrite was observed at higher As/Fe ratios (0.050, 0.100, and 0.500). Arsenic was found to retard ferrihydrite dissolution and transformation as well as goethite formation.

Comment on "A bacterium that can grow by using arsenic instead of phosphorus".

Wolfe-Simon et al. (Research Articles, 3 June 2011, p. 1163; published online 2 December 2010) argued that the bacterial strain GFAJ-1 can vary the elemental composition of its biomolecules by substituting arsenic for phosphorus. Although their data show that GFAJ-1 is an extraordinary extremophile, consideration of arsenate redox chemistry undermines the suggestion that arsenate can replace the physiologic functions of phosphate.

Comment on "A bacterium that can grow by using arsenic instead of phosphorus".

Wolfe-Simon et al. (Research Articles, 3 June 2011, p. 1163; published online 2 December 2010) reported that bacterium GFAJ-1 can substitute arsenic for phosphorus in its macromolecules, including DNA and proteins. If such arseno-DNA exists, then much of the past century of work with arsenate and phosphate chemistry, as well as much of what we think we know about metabolism, will need rewriting.