Speciation of five arsenic species (arsenite, arsenate, MMAAV, DMAAV and AsBet) in different kind of water by HPLC-ICP-MS

A method using Ion Chromatography hyphenated to an Inductively Coupled Plasma-Mass Spectrometer has been developed to accurately determine arsenite (As(III)), arsenate (As(V)), mono-methylarsonic acid (MMAA(V)), dimethylarsinic acid (DMAA(V)) and arsenobetaine (AsBet) in different water matrices. The developed method showed a high sensitivity with detection limits for each arsenic species close to 0.4pg injected. Arsenite and arsenate were the major species found in surface and well waters, but AsBet and DMAA(V) were found in some surface waters, which has never been reported before, while in some natural mineral waters located in volcanic region, the arsenic content exceeded the maximal admissible arsenic content by European legislation standards and the predominant form was As(V).     

Influence of redox potential (Eh) on the availability of arsenic species in soils and soils amended with biosolid

A study was done on the influence of redox potential on the mobility and availability of the various arsenic chemical forms in a Mollisol soil from central Chile amended with biosolid. Arsenic availability was strongly dependent on the applied redox potential. As expected, under reducing conditions (-200 mV vs Hg/Hg(2)Cl(2)) arsenic availability increased significantly, and arsenic was found mainly as arsenite. On the contrary under oxidizing conditions (200 mV vs Hg/Hg(2)Cl(2)) arsenic solubility decreased markedly and was governed by the presence of arsenate. The greatest concentration of organic arsenic species was found under reducing conditions, which would indicate that methylated species may participate in the transformation of arsenate to arsenite. In biosolid-amended soils the concentrations of methylated species increased as a function of time under reducing conditions, which can be attributed to the greater microbial activity resulting from the organic matter supply from the biosolid to soil. In all the systems, a high concentration of As(V) was found under reducing conditions, indicating that the chemical kinetics for the conversion of arsenate to arsenite is slow. Along time, the content of As(V) increased in the control soils, which may be attributed to the possible dissolution of iron oxides and hydroxides under reducing conditions.     

Arsenic uptake and speciation and the effects of phosphate nutrition in hydroponically grown kikuyu grass (Pennisetum clandestinum Hochst)

Background

This work focuses on the accumulation and mobility properties of arsenic (As) and the effects of phosphate (P) on its movement in Pennisetum clandestinum Hochst (kikuyu grass), grown hydroponically under increasing arsenate (As(V)) concentrations. The uptake of both ions and the relative kinetics show that phosphate is an efficient competitive inhibitor of As(V) uptake. The P/As uptake rate ratios in roots indicate that P is taken up preferentially by P/As transporters. An arsenite (As(III)) efflux from roots was also found, but this decreased when the arsenate concentration in the solution exceeded 5???M.

Methods

Increases in both arsenite and arsenate concentrations in roots were observed when the arsenate concentration in the solution was increased, and the highest accumulation of As(III) in roots was found when plants were grown at 5???M As(V). The low ratios of As accumulated in shoots compared to roots suggest limited mobility of the metalloid within Kikuyu plants.

Results

The results indicate that arsenic resistance in kikuyu grass in conditions of moderate exposure is mainly dependent on the following factors: 1) phosphate nutrition: P is an efficient competitive inhibitor of As(V) uptake because of the higher selectivity of membrane transporters with respect to phosphate rather than arsenate; and 2) a detoxification mechanism including a reduction in both arsenate and arsenite root efflux.

Conclusions

The As tolerance strategy of Kikuyu limits arsenate uptake and As translocation from roots to shoots; therefore, this plant cannot be considered a viable candidate for use in the phytoextraction of arsenic from contaminated soils or water.     

Uptake and biotransformation of arsenate in the lichen Hypogymnia physodes (L.) Nyl

The uptake and metabolism of arsenate, As(V), as a function of time and concentration were examined in the lichen Hypogymnia physodes (L.) Nyl. Lichen thalli were exposed to As(V) in the form of a solution. Exponential uptake of As(V) from 4 microg mL(-1) As(V) solution was accompanied by constant arsenite, As(III), excretion back into the solution. Arsenate taken up into the lichens from 0, 0.1, 1, 10 microg mL(-1) As(V) solutions was partially transformed into As(III), dimethylarsinic acid (DMA) and (mono)methylarsonic acid (MA). 48 h after exposure, the main arsenic compound in the lichens was DMA in 0.1, As(III) in 1 and As(V) in 10 microg mL(-1) treatment. The proportion of methylated arsenic compounds decreased with increasing arsenate concentration in the exposure solution. These results suggest that at least two types of As(V) detoxification exist in lichens; arsenite excretion and methylation.     

Adsorption/desorption of arsenite and arsenate on chitosan and nanochitosan

Equilibrium sorption studies of anionic species of arsenite, As(III) ions and arsenate As(V) ions onto two biosorbents, namely, chitosan and nanochitosan, have been investigated and compared. The results and trends in the sorption behavior are novel, and we have observed during the sorption process of the As(III) and As(V) on chitosan, a slow process of desorption occurred after an initial maximum adsorption capacity was achieved, before reaching a final but lower equilibrium adsorption capacity. The same desorption trend, however, is not observed on nanochitosan. The gradual desorption of As(III) and As(V) in the equilibrium sorption on chitosan is attributed to the different fractions of the dissociated forms of arsenic on the adsorbent surface and in solution and the extent of protonation of chitosan with the changing of solution pH during sorption. The change of solution pH during the sorption of arsenite ions on chitosan was also influenced by the interaction between the buffering effect of the arsenite species in the aqueous medium and the physical properties of chitosan. The final equilibrium adsorption capacity of chitosan for As(III) and As(V) was found to be around 500 and 8000 μg/g, respectively, whereas the capacities on nanochitosan are 6100 and 13,000 μg/g, respectively.

     

Uptake and accumulation behaviour of angiosperms irrigated with solutions of different arsenic species

Uptake and metabolisation of arsenic as a function of both the plant type and the chemical form of arsenic were examined. For this purpose two different plant species (Silene vulgaris and Plantago major) were selected that differed in their vitality and accumulation behaviour on arsenic-loaded substrates. The plants were cultivated on soil and irrigated with aqueous solutions of an inorganic arsenic compound (arsenious acid) and an organic compound (dimethylarsinate). The arsenic species accumulated in the parts of the plants above ground were extracted by PLE and determined using IC-ICP-MS. The concentrations and metabolisation products of arsenic found in the extracts indicate different mechanisms of arsenic uptake and transformation in both angiosperms. The arsenic species pattern showed that S. vulgaris was more arsenic--tolerable than P. major which is attributed to a low arsenate to arsenite concentration ratio in the plant compartments. S. vulgaris was also able to demethylate and reduce dimethylarsinate to form arsenite in a high extent. P. major accumulated only eight times lower concentration of arsenic, and the arsenate to arsenite concentration ratio shifted to higher values. Metabolisation products of dimethylarsinate did not occur under the present experimental conditions. The vitality of the angiosperms seems to be very dependent on the ability of the plant to reduce arsenate to arsenite.     

Impact of selected solution factors on arsenate and arsenite removal by nanoiron particles

Introduction  

The nano-scale zero-valent iron (NZVI) was used for the removal of arsenite (As(III)) and arsenate (As(V)) in aqueous solution. Batch experiments were conducted to investigate the effects of initial pH, initial arsenic concentration, dissolved oxygen (DO), and ratio of As(III)/As(V) on arsenic removal.     

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.     

Diversity and community structure of culturable arsenic-resistant bacteria across a soil arsenic gradient at an abandoned tungsten-tin mining area

We studied the bacterial diversity at a single location (the Terrubias mine; Salamanca province, Spain) with a gradient of soil As contamination to test if increasing levels of As would (1) change the preponderant groups of arsenic-resistant bacteria and (2) increase the tolerance thresholds to arsenite [As(III)] and arsenate [As(V)] of such bacteria. We studied the genetic and taxonomic diversity of culturable arsenic-resistant bacteria by PCR fingerprinting techniques and 16S rRNA gene sequencing. Then, the tolerance thresholds to As(III) and As(V) were determined for representative strains and mathematically analyzed to determine relationships between tolerances to As(III) and As(V), as well as these tolerances with the soil contamination level. The diversity of the bacterial community was, as expected, inversely related to the soil As content. The overall preponderant arsenic-resistant bacteria were Firmicutes (mainly Bacillus spp.) followed by γ-Proteobacteria (mainly Pseudomonas spp.), with increasing relative frequencies of the former as the soil arsenic concentration increased. Moreover, a strain of the species Rahnella aquatilis (γ-Proteobacteria class) exhibited strong endurance to arsenic, being described for the first time in literature such a phenotype within this bacterial species. Tolerances of the isolates to As(III) and As(V) were correlated but not with their origin (soil contamination level). Most of the strains (64%) showed relatively low tolerances to As(III) and As(V), but the second most numerous group of isolates (19%) showed increased tolerance to As(III) rather than to As(V), even though the As(V) anion is the prevalent arsenic species in soil solution at this location. To our knowledge, this is the first study to report a shift towards preponderance of Gram-positive bacteria (Firmicutes) related to high concentrations of soil arsenic. It was also shown that, under aerobic conditions, strains with relatively enhanced tolerance to As(III) predominated over the most As(V)-tolerant ones.     

Toxicity of arsenate and arsenite on germination, seedling growth and amylolytic activity of wheat

Effects of different concentrations of arsenite and arsenate (0-16 mg/l) on seed germination, relative root length and shoot height, arsenic accumulation in young seedlings, alpha-amylase, beta-amylase and total amylolytic activity in wheat were investigated in order to elucidate the toxicity of arsenic in the early developmental stage. Germination percentages of different wheat varieties had different responses to arsenic species and decreased significantly with increasing arsenic concentrations except Duokang 1. Relative root length (RRL) and relative shoot height (RSH) of wheat seedlings decreased with increasing concentrations of arsenite and arsenate. The relative root lengths were correlated with the relative shoot heights for arsenite (r2 = 0.79) and arsenate (r2 = 0.77). Arsenic uptake by seedlings increased with the increasing concentrations of arsenite or arsenate and followed the Michaelis-Menten kinetics function. The average total amylolytic activity and beta-amylase activity had no significant difference comparable to that of controls at the concentration 2 mg/l arsenite or arsenate, but decreased apparently when the concentration was higher than 2 mg/l. Whereas the alpha-amylase activity decreased with increasing concentrations of arsenite or arsenate over the whole concentration range. Arsenite decreased all the endpoints more remarkably than arsenate. In comparison, shoot height and root length were more sensitive to arsenic than other endpoints and might be used as indicators for arsenic toxicity.     

Studies on the accumulation and transformation of arsenic in freshwater organisms I. Accumulation, transformation and toxicity of arsenic compounds on the Japanese medaka, Oryzias latipes

Accumulation, transformation and toxicity of arsenic compounds to Japanese Medaka, Oryzias latipes were investigated. For sodium arsenite [As(II)] and disodium arsenate [As(V)], the mean value for 7-day lethal concentration LC50 for O. latipes were 14.6 and 30.3 mg As/l, respectively. Direct accumulation of arsenic in O. latipes increased as a function of As(III) concentration in water. A small proportion of accumulated arsenic was transformed to methylated arsenic. As much as 70% of the total arsenic accumulated in tissue was depurated. Accumulation and transformation of As(III) by O. latipes in a simple freshwater food chain were also investigated. The transformation of As(III) to As(V) by organisms was more prevalent than biomethylation of accumulated arsenic in organisms of the three steps of the food chain.     

Adsorption and removal of As(V) and As(III) using Zr-loaded lysine diacetic acid chelating resin

An adsorption process for the removal of As(V) and As(III) was evaluated under various conditions using zirconium(IV) loaded chelating resin (Zr-LDA) with lysine-Nalpha,Nalpha diacetic acid functional groups. Arsenate ions strongly adsorbed in the pH range from 2 to 5, while arsenite was adsorbed between pH 7 and 10.5. The sorption mechanism is an additional complexation between arsenate or arsenite and Zr complex of LDA. Adsorption isotherm data could be well interpreted by Langmuir equation for As(V) at pH 4 and As(III) at pH 9 with a binding constant 227.93 and 270.47 dm3 mol(-1) and capacity constant 0.656 and 1.1843 mmol g(-1), respectively. Regeneration of the resin was carried out for As(V) using 1 M NaOH. Six adsorption/desorption cycles were performed without significant decrease in the uptake performance. Column adsorption studies showed that the adsorption of As(V) is more favorable compared to As(III), due to the faster kinetics of As(V) compared to As(III). Influence of the coexisting ions on the adsorption of As(V) and As(III) was studied. The applicability of the method for practical water samples was studied.     

Removal of arsenic species from water by batch and column operations on bagasse fly ash

Bagasse fly ash (BFA, a sugar industrial waste) was used as low-cost adsorbent for the uptake of arsenate and arsenite species from water. The optimum conditions for the removal of both species of arsenic were as follows: pH 7.0, concentration 50.0 μg/L, contact time 50.0 min, adsorbent dose 3.0 g/L, and temperature 20.0 °C, with 95.0 and 89.5 % removal of arsenate and arsenite, respectively. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to analyze the results. The results of these models indicated single-layer uniform adsorption on heterogeneous surface. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 20.0 to 30.0 °C, the values of ΔG° lie in the range of ?4,722.75 to ?4,878.82 and ?4,308.80 to ?4,451.73 while the values of ΔH° and ΔS° were ?149.90 and ?121.07, and 15.61 and 14.29 for arsenate and arsenite, respectively, indicating that adsorption is spontaneous and exothermic. Pseudo-first-order kinetics was followed. In column experiments, the adsorption decreased as the flow rate increased with the maximum removal of 98.9 and 95.6 % for arsenate and arsenite, respectively. The bed depth service time and Yoon and Nelson models were used to analyze the experimental data. The adsorption capacity (N _o) of BFA on column was 3.65 and 2.98 mg/cm³ for arsenate and arsenite, respectively. The developed system for the removal of arsenate and arsenite species is economic, rapid, and capable of working under natural conditions. It may be used for the removal of arsenic species from any contaminated water resources.     

Silicon and Rhizophagus irregularis: potential candidates for ameliorating negative impacts of arsenate and arsenite stress on growth,nutrient acquisition and productivity in Cajanus cajan (L.) Millsp. genotypes

Arsenic (As) gets accumulated in plants via phosphorous transporters and water channels and interferes with nutrient and water uptake, adversely affecting growth and productivity. Although, Si and AM have been reported to combat arsenic stress, their comparative and interactive roles in ameliorating As V and As III toxicities have not been reported. Study evaluated effects of Si and Rhizophagus irregularis on growth, As uptake and yield under arsenate and arsenite stress in two pigeonpea genotypes (metal tolerant—Pusa 2002 and metal sensitive—Pusa 991). Higher As accumulation and translocation was observed in As III treated roots of Pusa 991 than those of Pusa 2002 when compared with As V. Roots were more negatively affected than shoots which led to a significant decline in nutrient uptake, leaf chlorophylls, and yield, with As III inducing more negative effects. Pusa 2002 established more effective mycorrhizal symbiosis and had higher biomass than Pusa 991. Si was more effective in inducing shoot biomass while AM inoculation significantly improved root biomass. AM enhanced Si uptake in roots and leaves in a genotype dependent manner. Combined application of Si and AM were highly beneficial in improving leaf water status, chlorophyll pigments, biomass, and productivity. Complete amelioration of negative impacts of both concentrations of As V and lower concentration of As III were recorded under +Si +AM in Pusa 2002. Results highlighted great potential of Si in improving growth and productivity of pigeonpea through R. irregularis under As V and As III stresses.

     

Accumulation, transformation, and release of inorganic arsenic by the freshwater cyanobacterium Microcystis aeruginosa

Arsenic (As) as a major hazardous metalloid was affected by phytoplankton in many aquatic environments. The toxic dominant algae Microcystis aeruginosa was exposed to different concentrations of inorganic arsenic (arsenate or arsenite) for 15 days in BG11 culture media. Arsenic accumulation, toxicity, and speciation in M. aeruginos as well as the changes of As species in media were examined. M. aeruginosa has a general well tolerance to arsenate and a definite sensitivity to arsenite. Additionally, arsenate actively elevated As methylation by the algae but arsenite definitely inhibited it. Interestingly, the uptake of arsenite was more pronounced than that of arsenate, and it was correlated to the toxicity. Arsenate was the predominant species in both cells and their growth media after 15 days of exposure to arsenate or arsenite. However, the amount of the methylated As species in cells was limited and insignificantly affected by the external As concentrations. Upon uptake of the inorganic arsenic, significant quantities of arsenate as well as small amounts of arsenite, DMA, and MMA were produced by the algae and, in turn, released back into the growth media. Bio-oxidation was the first and primary process and methylation was the minor process for arsenite exposures, while bioreduction and the subsequent methylation were the primary metabolisms for arsenate exposures. Arsenic bioaccumulation and transformation by M. aeruginosa in aquatic environment should be paid more attention during a period of eutrophication.     

Arsenic speciation and accumulation in evapoconcentrating waters of agricultural evaporation basins

To sustain agricultural productivity, evaporation basins (or ponds) have been widely used for the disposal of agricultural drainage in areas requiring subsurface drainage in the San Joaquin Valley of California, USA. The drainage water contains elevated concentration of trace elements including selenium (Se) and arsenic (As). Unlike Se, little information is available about As, a potentially high risk element. The objective of this study was to characterize the chemical behavior of As and acquire data for better understanding of biogeochemical processes and conditions affecting As fate in evaporation ponds. The study site was a 726 ha evaporation basin facility (containing 10 cells with water flowing in series) in the hydrologically closed Tulare Basin of California. We examined water chemistry, As concentration and speciation along the water flow path between cells as well as within the cells. Arsenic concentrations in the water increased linearly with Cl(-), a conservative ion from evapoconcentration. Reduced As species as arsenite [As(III)] and organic arsenic (org-As) also increased with increases in Cl(-) and salinity. Water samples with elevated EC (i.e., towards the end of flow path) had high dissolved organic matter, low dissolved oxygen, and elevated sulfide concentrations, indicating the development of reducing conditions. We hypothesize that such changes could facilitate the reduction of arsenate [As(V)] to As(III) and org-As. Elevated As in sediment profiles indicate a solid phase sink mechanism, but not significant enough to remove and reduce As concentrations in the water columns. These findings help us better define the processes that affect As in drainage facilities and contribute to our understanding of how As behaves in other regions of the world that have similar climatic and hydrogeochemical conditions.     

Photocatalytic oxidation and removal of arsenite from water using slag-iron oxide-TiO2 adsorbent

Photocatalytic oxidation of arsenite and simultaneous removal of the generated arsenate from aqueous solution were investigated. The whole process was performed using an adsorbent developed by loading iron oxide and TiO2 on municipal solid waste melted slag. The loading was carried out through chemical reactions and high-temperature process. In the removal process, arsenite was first oxidized to arsenate, and then was removed by adsorption. The oxidation of arsenite was rapid, but the adsorption of the generated arsenate was slow. A concentration of 100 mg l(-1) arsenite could be entirely oxidized to arsenate within 3 h in the presence of the adsorbent and under UV-light irradiation, but the equilibrium adsorption of the generated arsenate needed 10 h. Arsenite could also be oxidized to arsenate only by UV-light, but the reaction rate was approximately 1/3 of that of the photocatalyzed reaction. Both acidic and alkaline conditions were favorable for the oxidation reaction, and the optimum pH value for the oxidation and adsorption was proposed to be around 3. To oxidize and remove original 20 mg l(-1) or 50 mg l(-1) arsenite from aqueous solution, the necessary adsorbent amount was 2 g l(-1) or 5 g l(-1), respectively. Furthermore, the surface properties of the adsorbent were examined and the oxidation mechanism of arsenite was discussed. It is believed that the adsorbent developed in this study is efficient, cost-effective and environment-friendly for application in arsenic-contaminated wastewater treatment.     

Effect of arsenic and mercury speciation on inhibition of respiration rate in activated sludge systems

The inhibition effect of arsenite, As(III), arsenate, As(V), inorganic mercury, Hg(II) and methylmercury, MeHg, on the respiration rate of activated heterotrophic sludge microorganisms was evaluated. As(III) and MeHg were much more toxic to activated sludge than As(V) and Hg(II) respectively. The effect of various experimental parameters on the toxicity, such as sludge age, concentration of suspended solids and exposure time, was investigated. An increase of sludge age or the concentration of suspended solids reduces the observed inhibition. Longer exposure seems to dramatically increase the inhibition of As(III), MeHg and Hg(II) during the first hours of exposure, while the later inhibition increases at a slower rate. On the contrary, in the presence of As(V), 24 hours after exposure, the respiration rate was similar to that of the control biomass.     

Arsenic toxicity and accumulation in radish as affected by arsenic chemical speciation.

Arsenic (As) uptake by Rhapanus sativus L. (radish), cv. Nueva Orleans, growing in soil-less culture conditions was studied in relation to the chemical form and concentration of As. A 4 x 3 factorial experiment was conducted with treatments consisting of four As chemical forms [As(III), As(V), MMAA, DMAA] and three As concentrations (1.0, 2.0, and 5.0 mg As L-1). None of the As treatments were clearly phytotoxic to this radish cultivar. Arsenic phytoavailability was primarily determined by the As chemical form present in the nutrient solution and followed the trend DMAA < or = As(V) < or = As(III) < MMAA. Root and shoot As concentrations significantly increased with increasing As application rates. Monomethyl arsonic acid treatments caused the highest As accumulation in both roots and shoots, and this organic arsenical showed a higher uptake rate than the other As compounds. Inner root As concentrations were, in general, within the normal range for As contents in food crops but root skin As levels were close or above the maximum threshold set for As content in edible fruit, crops and vegetables. The statement that toxicity limits plant As uptake to safe levels was not confirmed in our study. If radish plants are exposed to a large pulse of As, as growth on contaminated nutrient solutions, they may accumulate residues which are unacceptable for animal and human consumption without exhibiting symptoms of phytotoxicity.     

TiO2-catalyzed photooxidation of arsenite to arsenate in aqueous samples

The TiO2-catalyzed photooxidation of arsenite (As(III)) to arsenate (As(V)) was studied in aqueous TiO2 suspensions using a solar simulator which emitted ultraviolet and visible radiations. The concentration of As(III) was varied between 50 microg l(-1) and 10 mg l(-1), and the concentration of TiO2 between 1 mg l(-1) and 50 mg l(-1). Total oxidation of As(III) to As(V) occurred within minutes. The concentration of As(III) declined exponentially which indicates first-order kinetics. In the pH range between 5 and 9 there was no significant influence of the pH of the suspension on the reaction rate. Batch experiments without irradiation showed that part of the arsenic was adsorbed on the TiO2 surface. When using 100 microg l(-1) As and between 1 mg l(-1) and 50 mg l(-1) TiO2, 8-39% of As(III) and up to 73% of As(V) were adsorbed by TiO2. As(III) was also oxidized by UV radiation in the absence of TiO2, but the reaction was slower than in the presence of TiO2 resulting in an irradiation time too long for practical use. In addition, oxidation of As(III) in the presence of TiO2 was also observed under solar irradiation within a few minutes.