Studies on the accumulation and transformation of arsenic in freshwater organisms II. Accumulation and transformation of arsenic compounds by Tilapia mossambica

Bioaccumulation and biotransformation of arsenic (As) compounds in freshwater Tilapia mossambica was investigated. The direct accumulation of As by T mossambica was proportional to the concentration of arsenicals in water. Small amounts of accumulated As were transformed to methylated As, including trimethylarsenic (TMA) species. Accumulation and transformation of As(III) by T. mossambica via freshwater food chain results in the transformation of As(III) to As(V) with little biomethylation of accumulated As. Approximately 90% of accumulated As was depurated to water.     

Removal of arsenic from water by electrocoagulation

In the present study electrocoagulation (EC) has been evaluated as a treatment technology for arsenite [As(III)] and arsenate [As(V)] removal from water. Laboratory scale experiments were conducted with three electrode materials namely, iron, aluminum and titanium to assess their efficiency. Arsenic removal obtained was highest with iron electrodes. EC was able to bring down aqueous phase arsenic concentration to less than 10 microgl(-1) with iron electrodes. Current density was varied from 0.65 to 1.53 mAcm(-2) and it was observed that higher current density achieved rapid arsenic removal. Experimental results at different current densities indicated that arsenic removal was normalized with respect to total charge passed and therefore charge density has been used to compare the results. Effect of pH on arsenic removal was not significant in the pH range 6-8. Comparative evaluation of As(III) and As(V) removal by chemical coagulation (with ferric chloride) and electrocoagulation has been done. The comparison revealed that EC has better removal efficiency for As(III), whereas As(V) removal by both processes was nearly same. The removal mechanism of As(III) by EC seems to be oxidation of As(III) to As(V) and subsequent removal by adsorption/complexation with metal hydroxides generated in the process.     

Removal of arsenic from groundwater by granular titanium dioxide adsorbent

A novel granular titanium dioxide (TiO2) was evaluated for the removal of arsenic from groundwater. Laboratory experiments were carried out to investigate the adsorption capacity of the adsorbent and the effect of anions on arsenic removal. Batch experimental results showed that more arsenate [As(V)] was adsorbed on TiO2 than arsenite [As(III)] in US groundwater at pH 7.0. The adsorption capacities for As(V) and As(III) were 41.4 and 32.4 mgg(-1) TiO2, respectively. However, the adsorbent had a similar adsorption capacity for As(V) and As(III) (approximately 40 mgg(-1)) when simulated Bangladesh groundwater was used. Silica (20 mgl(-1)) and phosphate (5.8 mgl(-1)) had no obvious effect on the removal of As(V) and As(III) by TiO2 at neutral pH. Point-of-entry (POE) filters containing 3 l of the granular adsorbent were tested for the removal of arsenic from groundwater in central New Jersey, USA. Groundwater was continuously passed through the filters at an empty bed contact time (EBCT) of 3 min. Approximately 45,000 bed volumes of groundwater containing an average of 39 microgl(-1) of As(V) was treated by the POE filter before the effluent arsenic concentration increased to 10 microgl(-1). The total treated water volumes per weight of adsorbent were about 60,000 l per 1 kg of adsorbent. The field filtration results demonstrated that the granular TiO2 adsorbent was very effective for the removal of arsenic in groundwater.     

Distribution of soil arsenic species, lead and arsenic bound to humic acid molar mass fractions in a contaminated apple orchard

Excessive application of lead arsenate pesticides in apple orchards during the early 1900s has led to the accumulation of lead and arsenic in these soils. Lead and arsenic bound to soil humic acids (HA) and soil arsenic species in a western Massachusetts apple orchard was investigated. The metal-humate binding profiles of Pb and As were analyzed with size exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS). It was observed that both Pb and As bind "tightly" to soil HA molar mass fractions. The surface soils of the apple orchard contained a ratio of about 14:1 of water soluble As (V) to As (III), while mono-methyl (MMA) and di-methyl arsenic (DMA) were not detectable. The control soil contained comparatively very low levels of As (III) and As (V). The analysis of soil core samples demonstrated that As (III) and As (V) species are confined to the top 20 cm of the soil.     

Investigation of arsenic removal in batch wise water treatments by means of sequential hydride generation flow injection analysis

Arsenic water pollution is a big issue worldwide. Determination of inorganic arsenic in each oxidation state is important because As(III) is much more toxic than As(V). An automated arsenic measurement system was developed based on complete vaporization of As by a sequential procedure and collection/preconcentration of the vaporized AsH(3), which was subsequently measured by a flow analysis. The automated sensitive method was applied to monitoring As(III) and As(V) concentrations in contaminated water standing overnight. Behaviors of arsenics were investigated in different conditions, and unique time dependence profiles were obtained. For example, in the standing of anaerobic water samples, the As(III) concentration immediately began decreasing whereas dead time was observed in the removal of As(V). In normal groundwater conditions, most arsenic was removed from the water simply by standing overnight. To obtain more effective removal, the addition of oxidants and use of steel wools were investigated. Simple batch wise treatments of arsenic contaminated water were demonstrated, and detail of the transitional changes in As(III) and As(V) were investigated.     

Speciation and uptake of arsenic accumulated by corn seedlings using XAS and DRC-ICP-MS

ICP-MS was used to investigate the uptake of As(III) and As(V) from hydroponics growth media by corn seedlings. It was found that arsenic uptake by the plant roots for the arsenic(V) and arsenic(III) treatments were 95 and 112 ppm, respectively. However, in the shoots of the arsenic (V) treatments had 18 ppm whereas arsenic(III) treatments had 12 ppm. XANES studies showed that As for both treatments arsenic was present as a mixture of an As(III) sulfur complex and an As(V) oxygen complex. The XANES data was corroborated by the EXAFS studies showing the presence of both oxygen and sulfur ligands coordinated to the arsenic. Iron concentrations were found to increase by 4 fold in the As(V) contaminated growth media and 7 fold in the As(III) treatment compared to the control iron concentration of 500 ppm. Whereas, the total iron concentration in the shoots was found to decrease by approximately the same amount for both treatments from 360 ppm in the control to approximately 125 ppm in both arsenic treatments. Phosphorus concentrations were found to decrease in both the roots and shoots compared to the control plants. The total sulfur in the roots was found to increase in the arsenic(III) and arsenic(V) treatments to 560 ppm and 800 ppm, respectively, compared to the control plants 358 ppm. In addition, the total sulfur in shoots of the plants was found to remain relatively constant at approximately 1080 ppm. The potassium concentrations in the plants were found to increase in the roots and decrease in the shoots.     

Retention of arsenic on hydrous ferric oxides generated by electrochemical peroxidation

Electrochemical peroxidation (ECP), an emerging remediation technology, with direct electric current applied to steel electrode and small addition of H2O2, was used to remove As(III) from contaminated aqueous solutions. Bench scale experiments were conducted to evaluate the sorption and distribution of arsenic between the soluble and solid state hydrous ferric oxides (HFO) formed as part of the ECP process. ECP was effective in removing arsenic from the aqueous solution, with >98% of the applied As(III) adsorbed on HFO. Removal was complete within 3 min of ECP treatment and apparently independent of the initial pH of the water (3.5-9.5). In the absence of H2O2 more As(III) was adsorbed by solid state iron at pH 9.5 than at 3.5 (2600 vs. 1750 microg l(-1)). Thus H2O2 was crucial to oxidize As(III) to As(V) which is more strongly retained by HFO. Removal of As was not significantly affected by the concentration of H2O2 or by current processing time. The optimal operating conditions were pH < 6.5, H2O2 concentration of 10 mg l(-1) and current process time not exceeding 3 min. X-ray diffraction (XRD), diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy and transmission electron microscopy (TEM) were applied to study the HFO deposits. The XRD data indicated the prevalence of poorly ordered Fe minerals in the suspended ECP solids with a dominance of 5 line ferrihydrite in the absence of H2O2. At pH 3.5 and with 100 mg H2O2 l(-1), akaganeite was formed, whereas an incipient hematitic phase, reflection at 0.39 nm, occurred at pH 6.5. DRIFT data indicate that both As(III) and As(V) were specifically adsorbed onto HFO at acid and neutral pH. TEM observations indicated the presence of spherical shape ferrihydrite and provided evidence for possible formation of subrounded hematite and acicular shape goethite.     

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.     

The oxidation states of arsenic in well-water from a chronic arsenicism area of northern Mexico

Aquifers in the Región Lagunera in northern Mexico are heavily contaminated with arsenic. The range of total arsenic concentrations in 128 water samples analyzed was 0.008 to 0.624 mg litre(-1), and concentrations greater than 0.05 mg litre(-1) were found in 50% of them. Approximately 400 000 people living in rural areas were exposed to high As concentrations. Most of the As was in inorganic form and pentavalent arsenic [As(V)] was the predominant species in 93% of the samples. In 36% of the samples, however, variable percentages (20-50) of trivalent As [As(III)] were found. Organic arsenicals were present in very small amounts. Since As(III) is several times more toxic than As(V), we suggest that periodic studies be performed on the As(III)/As(V) ratio in wells whose total As concentrations are above 0.05 mg litre(-1), in combination with epidemiological studies to evaluate possible differences in health effects produced by different As species.     

Speciation of arsenic and chromium metal ions by reversed phase high performance liquid chromatography

The speciation of arsenic [As(III) and As(V)] and chromium [Cr(III) and Cr(VI)] was carried out by high performance liquid chromatography. The column used was Econosil C18 (250 x 4.6 mm i.d., particle size 10 microm). The mobile phases consisted of water-acetonitrile (80:20, v/v) for arsenic and 10 mM ammonium acetate buffer (6.0 pH)-acetonitrile (10:90, v/v) for chromium speciation separately and respectively. The detection was carried out by UV-Vis at 410 nm and atomic absorption spectrometer (AAS) respectively and separately. The values of alpha and Rs of As(III) and As(V) species were 1.4 and 1.5 respectively while the values of alpha and Rs for Cr(III) and Cr(VI) were 1.35 and 0.2 respectively. The effect of the acetonitrile percentages was also carried out on the speciation of arsenic only. The relative standard deviation and limit of detection were in the range of 0.01-0.02 and 0.4-1.0 microg/ml respectively.     

Soil calcium significantly promotes uptake of inorganic arsenic by garland chrysanthemum (ChrysanthemumL coronarium) fertilized with chicken manure bearing roxarsone and its metabolites

Roxarsone (ROX), a widely used feed organoarsenic additive, occurs as itself and its metabolites in animal manure that is commonly land used as fertilizer. Soil property impacts arsenic (As) speciation and bioavailability. Fourteen soils across China were used to conduct culture experiments to investigate As uptake by garland chrysanthemum (ChrysanthemumL coronarium), with the soils fertilized with chicken manure bearing ROX and its metabolites. The results show As(III) was the sole As form in garland chrysanthemum shoots, and As(III) and As(V) occurred in roots. Only inorganic As was detected in all soils when the plants were harvested. Stepwise regression analysis shows soil-exchangeable Ca predominated shoot As(III) concentration (shoot As(III) = 1.60030 soil Ca, R ² = 0.8832***). Therefore, ROX is transferred into the human food chain finally as inorganic As in plants. Application of animal manure bearing ROX and its metabolites is not recommended in Ca-rich soils to avoid excess inorganic As dietary exposure.

     

Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.     

Effects of oxalate and phosphate on the release of arsenic from contaminated soils and arsenic accumulation in wheat

Oxalate is exuded by plants in the rhizosphere and plays an important role in the soil/root interactions. Phosphate fertilizer is widely used all over the world and may influence the behavior of arsenic (As) in soils. In this study oxalate and phosphate were used as extractants to investigate their effects on the release of As from three As-contaminated soils and the chemical speciation of As. Concentrations of arsenite (As(III)) and arsenate (As(V)) released progressively increased by increasing the concentrations of oxalate or phosphate. The released As(V) content was higher than that of As(III) and the differences between As(V) and As(III) released by oxalate was more obvious than by phosphate. Greenhouse experiment was conducted to evaluate the effects of oxalate and phosphate on As uptake by wheat (Triticum vulgare L.). Addition of oxalate or phosphate resulted in the increase of As accumulation in both wheat root and shoot and the effect of phosphate was more obvious than that of oxalate.     

Distribution of inorganic arsenic species in mine tailings of abandoned mines from Korea

The main objective of the present study is to determine arsenic species in mine tailings by applying an ion exchange method. Three abandoned mines, Jingok, Cheonbo and Sino mines in Korea, which had produced mainly gold, were selected for the collection and analysis of the tailings. It was found that the arsenic speciation using an ion exchange method was effective to separate As(III) and As(V) in leachate of mine tailings. The concentration of As(V) was found to be 63-99% in the leachate, indicating that As(V) would be the major arsenic species in the mine tailings and the tailings were under oxic conditions. The total concentrations of arsenic and metal elements in the mine tailings were up to 62,350 mg/kg As, 40 wt.% Fe, 21,400 mg/kg Mn, and 7,850 mg/kg Al. Sulfate was the dominant anion throughout the leachate, reaching a maximum dissolved concentration of 734 mg/l. The results of XRD and SEM in the mine tailings showed that main arsenic-containing minerals were pyrite (FeS2) and arsenopyrite (FeAsS) which would be the source of arsenic contamination in the study area.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

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).     

Effects of compost and phosphate amendments on arsenic mobility in soils and arsenic uptake by the hyperaccumulator,Pteris vittata L

Chinese brake fern (Pteris vittata L.), an arsenic (As) hyperaccumulator, has shown the potential to remediate As-contaminated soils. This study investigated the effects of soil amendments on the leachability of As from soils and As uptake by Chinese brake fern. The ferns were grown for 12 weeks in a chromated-copper-arsenate (CCA) contaminated soil or in As spiked contaminated (ASC) soil. Soils were treated with phosphate rock, municipal solid waste, or biosolid compost. Phosphate amendments significantly enhanced plant As uptake from the two tested soils with frond As concentrations increasing up to 265% relative to the control. After 12 weeks, plants grown in phosphate-amended soil removed >8% of soil As. Replacement of As by P from the soil binding sites was responsible for the enhanced mobility of As and subsequent increased plant uptake. Compost additions facilitated As uptake from the CCA soil, but decreased As uptake from the ASC soil. Elevated As uptake in the compost-treated CCA soil was related to the increase of soil water-soluble As and As(V) transformation into As(III). Reduced As uptake in the ASC soil may be attributed to As adsorption to the compost. Chinese brake fern took up As mainly from the iron-bound fraction in the CCA soil and from the water-soluble/exchangeable As in the ASC soil. Without ferns for As adsorption, compost and phosphate amendments increased As leaching from the CCA soil, but had decreased leaching with ferns when compared to the control. For the ASC soil, treatments reduced As leaching regardless of fern presence. This study suggest that growing Chinese brake fern in conjunction with phosphate amendments increases the effectiveness of remediating As-contaminated soils, by increasing As uptake and decreasing As leaching.     

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.     

Iron oxide-loaded slag for arsenic removal from aqueous system

An effective adsorbent for arsenic removal from aqueous system was synthesized by loading iron(III) oxide on municipal solid waste incinerator melted slag. The loading was accomplished via chemical processes and thermal coating technique. The key point of the technique was the simultaneous generation of amorphous FeOOH sol and silica sol in-situ and eventually led to the formation of Fe-Si surface complexes which combined the iron oxide with the melted slag tightly. The surface morphology of the iron oxide-loaded slag was examined and the loading mechanisms were discussed in detail. The adsorbent was effective for both arsenate and arsenite removal and its removal capabilities for As(V) and As(III) were 2.5 and 3 times of those of FeOOH, respectively. Both affinity adsorption and chemical reactions contributed to arsenic removal. The effects of solution pH, contact time, arsenic concentration and adsorbent dosage on arsenic removal were examined and the optimum removal conditions were established. Furthermore, leaching of hazardous elements such as Cr(VI), As, Se, Cd and Pb from the adsorbent at a pH range of 2.5-12.5 was below the regulation values. Accordingly, it is believed that the iron oxide-loaded slag developed in this study is environmentally acceptable and industrially applicable for wastewater treatment.     

Determination of total arsenic content in water by atomic absorption spectroscopy (AAS) using vapour generation assembly (VGA)

Analysis of arsenic in water is important in view of contamination of ground water with arsenic in some parts of the world including West Bengal in India and neighboring country Bangladesh. WHO has fixed the threshold for arsenic in drinking water to 10ppb (microg/l) level, hence the methodology for determination of arsenic is required to be sensitive at ppb level. Atomic absorption spectrophotometry with vapour generation assembly (AAS-VGA) is well known technique for the trace analysis of arsenic. However, total arsenic analysis [As(III)+As(V)] is very crucial and it requires reduction of As(V) to As(III) for correct analysis. As(III) is reduced to AsH3 vapours and finally to free As atoms, which are responsible for absorption signal in AAS. To accomplish this the vapour generation assembly attached to AAS has acid channel filled with 10 M HCl and the reduction channel with sodium borohydride. Further sample can be reduced either before aspiration for analysis, using potassium iodide (KI) or the sample can be introduced in the instrument directly and KI can be added in the reduction channel along with the sodium borohydride. The present work shows that samples prepared in 3 M HCl can be reduced with KI for 30 min before introduction in the instrument. Alternatively samples can be prepared in 6 M HCl and directly aspirated in AAS using KI in VGA reduction channel. The latter methodology is more useful when the sample size is large and time cycle is difficult to maintain. It is observed that the acid concentration of the sample in both the situations plays an important role. Further reduction in acid concentration and analysis time is achieved for the arsenic analysis by using modified method. Analysis in both the methods is sensitive at ppb level.