Evaluating a drinking-water waste by-product as a novel sorbent for arsenic

Arsenic (As) carcinogenicity to humans and other living organisms has promulgated extensive research on As treatment technologies with varying levels of success; generally, the most efficient methods come with a significantly higher cost burden and they usually perform better in removing As(V) than As(III) from solution. In the reported study, a novel sorbent, a waste by-product of the drinking-water treatment process, namely, drinking-water treatment residuals (WTRs) were evaluated for their ability to adsorb both As(V) and As(III). Drinking-WTRs can be obtained free-of-charge from drinking-water treatment plants, and they have been successfully used to reduce soluble phosphorus (P) concentrations in poorly P-sorbing soils. Phosphate and arsenate molecules have the same tetrahedral geometry, and they chemically behave in a similar manner. We hypothesized that the WTRs would be effective sorbents for both As(V) and As(III) species. Two WTRs (one Fe- and one Al-based) were used in batch experiments to optimize the maximum As(V) and As(III) sorption capacities, utilizing the effects of solid:solution ratios and reaction kinetics. Results showed that both WTRs exhibited high affinities for soluble As(V) and As(III), exhibiting Freundlich type adsorption with no obvious plateau after 2-d of reaction (15000 mg kg-1). The Al-WTR was highly effective in removing both As(V) and As(III), although As(III) removal was much slower. The Fe-WTR showed greater affinity for As(III) than for As(V) and reached As(III) sorption capacity levels similar to those obtained with the Al-WTR-As(V) system (15000 mg kg-1). Arsenic sorption kinetics were biphasic, similar to what has been observed with P sorption by the WTRs. Minimal (<3%) desorption of sorbed As(III) and As(V) was observed, using phosphate as the desorbing ligand. Dissolved Fe2+ concentrations measured during As(III) sorption were significantly correlated (r2=0.74, p<0.005) with the amount of As(III) sorbed by the Fe-WTR. Lack of correlation between Fe2+ in solution and sorbed As(V) (r2=0.2) suggests reductive dissolution of the Fe-WTR mediating As(III) sorption. Results show promising potential for the WTRs in irreversibly retaining As(V) and As(III) that should be further tested in field settings.     

Bio-reduction of arsenate using a hydrogen-based membrane biofilm reactor

Arsenate (As(V)) is a carcinogen and a significant problem in groundwater in many parts of the world. Since As(III) is generally more mobile and more toxic than As(V), the reduction of As(V) to As(III) is not a conventional treatment goal. However, reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation or complexation with sulfide or by adsorption to Fe(II)-based solids. A promising approach for reducing oxidized contaminants is the H2-based membrane biofilm reactor (MBfR). In the case of arsenate, the MBfR allows bio-reduction of As(V) to As(III) and sulfate to sulfide, thereby giving the potential for As removal, such as by precipitation of As2S3(s) or formation of Fe(II)-based solids. When As(V) was added to a denitrifying MBfR, As(V) was reduced immediately to As(III). Decreasing the influent sulfate loading increased As(V) reduction for a fixed H2 pressure. A series of short-term experiments elaborated on how As(V) loading, nitrate and sulfate loadings, and H2 pressure controlled As(V) reduction. Lower nitrate loading and increased As(V) loading increased the extent of As(V) reduction, but increased H2 pressure did not increase As(V) reduction. As(V) reduction was sensitive to sulfate loading, with a maximum As(V)-removal percentage and flux with no addition of sulfate. As(III) could be precipitated with sulfide or adsorbed to Fe(II) solids, which was verified by scanning electron microscopy and energy dispersive X-ray analysis.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Behaviour of arsenic in forested catchments following a high-pollution period

Due to high availability of adsorption sites, forested catchments could be net sinks for pollutant arsenic both during the period of increasing and decreasing pollution. We tested this hypothesis along a north-south pollution gradient in spruce die-back affected areas of Central Europe. For two water years (2007-2008), we monitored As fluxes via spruce-canopy throughfall, open-area precipitation, and runoff in four headwater catchments (Czech Republic). Since 1980, atmospheric As inputs decreased 26 times in the north, and 13 times in the south. Arsenic export by runoff was similar to atmospheric inputs at three sites, resulting in a near-zero As mass balance. One site exhibited a net export of As (2.2 g ha⁻¹ yr⁻¹). In contrast, the preceding period (1995-2006) showed much higher As fluxes, and higher As export. Czech catchments do not serve as net sinks of atmospheric As. A considerable proportion of old industrial arsenic is flushed out of the soil.     

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.     

Factors influencing arsenic accumulation by Pteris vittata: a comparative field study at two sites

This study compared the factors influencing arsenic (As) accumulation by Pteris vittata at two sites, one containing As along with Au mineralization and the other containing Hg/Tl mineralization. The soils above these two sites contained high As concentrations (26.8-2955 mg kg(-1)). Although the As concentration, pH, soil cation exchange capacity and plant biomass differed significantly between the two sites, no differences were observed in the As concentrations in the fronds and roots, or the translocation factors, of P. vittata, suggesting that this species has consistent As hyperaccumulation properties in the field. The As concentration in the fronds was positively related to phosphorus (P) and potassium (K), but negatively related to calcium (Ca), at one site. This suggested that P, K and Ca influenced As accumulation by P. vittata in the field.     

Arsenic accumulation and resistance mechanism in Panax notoginseng, a traditional rare medicinal herb

Panax notoginseng, a traditional rare Chinese medicinal herb, was recently found to bring health risk to consumers, mainly because soil in its major plantation area was contaminated by arsenic (As). We investigated the effect of soil As pollution on the growth and As uptake of pot-cultured P. notoginseng, and the associated mechanisms of As stressed response. Results showed that, comparing with P. notoginseng growing in a low-As soil, the root, stem, and leaf biomasses of those growing in a high-As soil significantly reduced by 0.75, 0.09 and 0.21 g seedling⁻¹, respectively. Arsenic concentrations in roots, stems and leaves of the seedlings growing in high-As soil were 22, 15 and 3 times higher than those growing in low-As soil, respectively. Regardless of the soil As concentration, As existed in plants mainly as As(III), suggesting that the reduction of As(V) is a key step in As metabolism. Arsenic was distributed primarily in cell walls (51.7% for plants growing in the low-As soil, and 51.5% in the high-As soil), followed by cytoplasm supernatant, with cell organelles containing the least As. Compared with plants growing in the low-As soil, those in the high-As soil had increased superoxide dismutase and peroxidase activities in their roots, stems, and leaves, which would be associate with improving the resistance of P. notoginseng to As stress. The results suggest that there exists some special mechanisms of As-tolerance in P. notoginseng and the study is of significance in developing measures to reduce As in the herb.     

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.     

Trace element mobility in a contaminated soil two years after field-amendment with a greenwaste compost mulch

Application of greenwaste compost to brownfield land is increasingly common in soil and landscape restoration. Previous studies have demonstrated both beneficial and detrimental effects of this material on trace element mobility. A pot experiment with homogenised soil/compost investigated distribution and mobility of trace elements, two years after application of greenwaste compost mulch to shallow soils overlying a former alkali-works contaminated with Pb, Cu and As (∼900, 200 and 500 mg kg⁻¹, respectively). Compost mulch increased organic carbon and Fe in soil pore water, which in turn increased As and Sb mobilization; this enhanced uptake by lettuce and sunflower. A very small proportion of the total soil trace element pool was in readily-exchangeable form (<0.01% As, <0.001% other trace elements), but the effect of compost on behaviour of metals was variable and ambiguous. It is concluded that greenwaste compost should be applied with caution to multi-element contaminated soils.     

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.     

一种新型复合除砷材料的制备及其性能

将锆的水合氧化物固载于大孔螯合树脂D401上制备出一种新型除砷材料,并研究了不同实验条件下复合吸附剂D401-Zr对水溶液中As(V)的吸附性能。研究结果表明,在pH<5.2时D401-Zr对As(V)都具有较强的吸附性能;其吸附等温线与Langmuir吸附模型具有较高的吻合度;吸附动力学研究表明,D401-Zr对砷的吸附均遵循二级动力学方程;竞争吸附实验表明,与SO24-、Cl-共存时,D401-Zr对砷的去除率大于90%,而与PO34-、F-竞争离子共存时,其去除率明显下降。     

Changes in arsenic fractionation, bioaccessibility and speciation in organo-arsenical pesticide amended soils as a function of soil aging

Although organoarsenical pesticides are being phased out, sites with high concentrations of organic arsenical residues still exist due to the long-term application of these pesticides. The biotic and abiotic speciation of dimethylarsinic acid (DMA) can result in the formation of inorganic arsenic (As) species. Oxidation state, retention, and thereby persistence, varies according to temporal changes, influencing the availability and toxicity of contaminants. The current greenhouse study aimed at evaluating temporal changes in the oxidation state of As, geochemical partitioning, and bioaccessibility. Four soils with varying physiochemical properties were contaminated with DMA at two concentrations (675 and 1500 mg kg⁻¹ of As). Rice plants were grown for a 6 months period, following which, the soils were allowed to age. The operationally defined forms of As and its bioaccessibility was analyzed at 0, 6 months, 1 year, and 3 years. Changes in oxidation state of As were evaluated immediately after spiking and after 3 years of soil-pesticide equilibration. Results show that geochemical partitioning of As was affected significantly (P < 0.05) by soil type, loading rates, and equilibration time. Arsenic was bound mainly to the poorly-crystalline Fe/Al-oxyhydroxides in the soil. However, these interactions did not affect As bioaccessibility, presumably due to the dissolution of the bound fractions of As in the acidic stomach. While 74-94% of the total bioaccessible As was transformed to As(V), 4-19% was transformed to the more toxic As(III). This study indicates that although aging affected the geochemical partitioning of As in the soil, bioaccesibility was controlled by the gastric pH.     

Utilisation of chemically stabilized arsenic-contaminated soil in a landfill cover

The aim of the study was to determine if an As-contaminated soil, stabilized using zerovalent iron (Fe⁰) and its combination with gypsum waste, coal fly ash, peat, or sewage sludge, could be used as a construction material at the top layer of the landfill cover. A reproduction of 2 m thick protection/vegetation layer of a landfill cover using a column setup was used to determine the ability of the amendments to reduce As solubility and stimulate soil functionality along the soil profile. Soil amendment with Fe⁰ was highly efficient in reducing As in soil porewater reaching 99 % reduction, but only at the soil surface. In the deeper soil layers (below 0.5 m), the Fe treatment had a reverse effect, As solubility increased dramatically exceeding that of the untreated soil or any other treatment by one to two orders of magnitude. A slight bioluminescence inhibition of Vibrio fischeri was detected in the Fe⁰ treatment. Soil amendment with iron and peat showed no toxicity to bacteria and was the most efficient in reducing dissolved As in soil porewater throughout the 2 m soil profile followed by iron and gypsum treatment, most likely resulting from a low soil density and a good air diffusion to the soil. The least suitable combination of soil amendments for As immobilization was a mixture of iron with coal fly ash. An increase in all measured enzyme activities was observed in all treatments, particularly those receiving organic matter. For As to be stable in soil, a combination of amendments that can keep the soil porous and ensure the air diffusion through the entire soil layer of the landfill cover is required.     

Arsenic distribution and pathway scenarios for sediments and water in a peri-urban Mongolian small-scale coal mining area (Nalaikh District,Ulaanbaatar)

The distribution of arsenic (As) in environmental compartments is investigated in the Nalaikh Depression of N-Mongolia. In Nalaikh, lignite coal is mined by artisanal small-scale mining (ASM) approaches. Because As is often associated with sulfuric minerals in coal, it was hypothesized that enrichment of As is related to coal ASM. A second hypothesis considered coal combustion in power plants, and stoves are a key source of As in the local environment. Three mobilization and distribution scenarios were developed for potential As pathways in this semiarid environment. About 43 soil and 14 water sites were analyzed for As concentrations and meaningful parameters in soil and water. About 28 topsoil samples were analyzed in surface-subsurface pairs in order to identify potential eolian surface enrichment. Additionally, fluvial-alluvial sediments and geogenic and anthropogenic deposits were sampled. Water was sampled as surface water, groundwater, precipitation, and industrial water. Results show that As does not pose a ubiquitous risk in the Nalaikh Depression. However, locally and specifically in water, As concentrations may exceed the WHO guideline value for drinking water by up to a factor of 10. A carefully selected sampling strategy allows the evaluation of the distribution scenarios, which reveals a combination of (a) geogenic As in groundwater and distribution via surface water with (b) anthropogenic As redistribution via eolian pathways. An immediate linkage between As redistribution and coal mining is not evident. However, As distribution in fly ash from coal combustion in the local power plant and yurt settlements is the most likely As pathway. Hence, the results indicate the potential influence of diffuse, low-altitude sources on As emission to the environment. As such, this study provides a good example for As distribution under semiarid climate conditions influenced by geogenic and anthropogenic factors.

     

Occurrence of emerging organic contaminants in a tropical urban catchment in Singapore

The aim of this study was to test in a short term laboratory experiment the accumulation and physiological effects of As in the epiphytic lichen Xanthoria parietina. Arsenic content in treated samples increased progressively with increasing concentration in treatment solutions. Treatment of X. parietina thalli with 0.1, 1, 10 ppm As solutions caused significant decrease of viability, measured as intensity of respiratory activity, and damages to cell membranes, assessed by increase of electric conductivity of rinsing water and lipid peroxidation products. Soluble proteins content decreased and H₂O₂ content increased already at the lowest As concentration tested (0.01 ppm). Photosynthetic efficiency, measured in terms of F_V/F_M ratio, decreased significantly only at the highest As concentration (10 ppm). It was concluded that As exposure causes physiological stress both on the mycobiont and the photobiont and that cell membrane damage, expressed in terms of electric conductivity of rinsing water, is the parameter most affected by As treatment.     

An approach for arsenic in a contaminated soil: Speciation, fractionation, extraction and effluent decontamination

The fractionation and speciation of As in a contaminated soil were investigated, and a remediation strategy was tested. Regarding speciation, we found that As(V) prevails over As(III) whereas more than 40% of total arsenic is in organic form. The fractionation of As was investigated with two sequential extraction methods: a low mobility was found. Then we tested the possibility of using phosphoric acid to extract As from the soil and cleaning the washing effluents by sorption onto montmorillonite. The efficiency of the extraction and of the adsorption onto the clay were also investigated for Cr, Cu, Fe, Mn, Ni, Pb and Zn, whose total concentrations and fractionation in the soil are reported here. The extraction percentages for As and metals ranged from 30 to 65%; the residual proportions in the soil are presumably in very unreactive forms. Montmorillonite showed a good uptake capacity towards the investigated pollutants.     

Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO2-based adsorbent

A nanocrystalline TiO₂-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 μg L^?1 As(III), 246 μg L^?1 As(V), 151 μg L^?1 MMA, and 202 μg L^?1 DMA was continuously passed through a TiO₂ filter at an empty bed contact time of 6 min for 4 months. Approximately 11 000, 14 000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 μg L^?1. However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III).     

Partitioning of arsenic in soil-crop systems irrigated using groundwater: a case study of rice paddy soils in southwestern Taiwan

The accumulation of As in rice due to groundwater irrigation in paddy fields represents a serious health hazard in South and Southeast Asia. In Taiwan, the fate of As in long-term irrigated paddy fields is poorly understood. Groundwater, surface soil, and rice samples were collected from a paddy field that was irrigated with As-containing groundwater in southwestern Taiwan. The purpose of this study is to elucidate the source and sink of As in the paddy field by comparing the As fractions in the soils that were obtained by a sequential extraction procedure (SEP) with the As uptake of rice. The risks associated with eating rice from the field can thus be better understood. The concentration of As in groundwater varied with time throughout the growing seasons of rice, but always exceeded the permitted maximum (10 μg L⁻¹) for drinking water by the WHO. The As concentration increased with the concentration of Fe in the groundwater, supporting the claim that a large amount of As was concentrated in the Fe flocs collected from the internal wall of the groundwater pump. The results of the SEP revealed that As bound with amorphous and crystalline hydrous oxides exhibited high availability in the soils. The root of rice accumulated the largest amount of As, followed by the straw, husk, and grain. Although the As concentration in the rice grain was less than 1.0 mg kg⁻¹, the estimated intake level was close to the maximum tolerable daily intake of As, as specified by the WHO.     

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 m^2/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.