Evolution model of δ³⁴S and δ¹⁸O in dissolved sulfate in volcanic fan aquifers from recharge to coastal zone and through the Jakarta urban area, Indonesia

The sources of sulfate in an aquifer system, and its formation/degradation via biogeochemical reactions, were investigated by determining sulfate isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) in dissolved sulfate in groundwater from the Jakarta Basin. The groundwater flow paths, water ages, and geochemical features are well known from previous studies, providing a framework for the groundwater chemical and isotopic data, which is supplemented with data for spring water, river water, hot spring water, seawater, detergents, and fertilizers within the basin. The sulfate isotope composition of groundwater samples varied widely from − 2.9‰ to + 33.4‰ for δ³⁴S_SO4 and + 4.9‰ to + 17.8‰ for δ¹⁸O_SO4 and changed systematically along its flow direction from the mountains north to the coastal area. The groundwater samples were classified into three groups showing (1) relatively low and narrow δ³⁴S_SO4 (+ 2.3‰ to + 7.6‰) with low and varied δ¹⁸O_SO4 (+ 4.9‰ to + 12.9‰) compositions, (2) high and varied δ³⁴S_SO4 (+ 10.2‰ to + 33.4‰) with high δ¹⁸O_SO4 (+ 12.4‰ to + 17.3‰) compositions, and (3) low δ³⁴S_SO4 (<+6.1‰) with high δ¹⁸O_SO4 (up to + 17.8‰) compositions. These three types of groundwater were observed in the terrestrial unconfined aquifer, the coastal unconfined and confined aquifers, and the terrestrial confined aquifer, respectively. A combination of field measurements, concentrations, and previously determined δ¹⁵N_NO3 data, showed that the observed isotopic heterogeneity was mainly the result of contributions of pollutants from domestic sewage in the rural area, mixing of seawater sulfate that had experienced previous bacterial sulfate reduction in the coastal area, and isotopic fractionation during the formation of sulfate through bacterial disproportionation of elemental sulfur. Our results clearly support the hypothesis that human impacts are important factors in understanding the sulfur cycle in present-day subsurface environments. A general model of sulfate isotopic evolution along with groundwater flow has rarely been proposed, due to the complicated hydrogeological research setting that causes varied isotope ratios, although its understanding has recently received great attention. This pioneer study on a simple volcanic fan aquifer system with a well-understood groundwater flow mechanism provides a useful model for future studies.     

In situ treatment of arsenic contaminated groundwater

Groundwater in a sand and gravel aquifer was contaminated by arsenic compounds. The extent and the As concentration of the polluted groundwater plume decreased from 1971 to 1975, whereas the content of free dissolved oxygen increased. High As concentrations (> 1 mg/1) occured in groundwater with typical characteristics of a “reduced” water with negative Eh values and high concentrations of dissolved iron (up to 140 mg/1 in 1971). When plotted into an As stability field diagram, the higher values (> 1 mg As/1) coincided with the fields of trivalent As species, whereas the lower values (< 0.1 mg As/1) fitted to the fields of the pentavalent arsenic species. Therefore it was concluded that an improvement of the oxygen supply should accelerate the natural precipitation processes. By injection of 29,000 kg KMnO₄ into 17 wells and piezometers the soluble As (III) species were oxidized to As (V) species, which were precipitated as FeAsO₄ or Mn₃(AsO₄)₂ or co-precipitated with Mn- and Fe-hydroxides.     

Occurrence of arsenic in core sediments and groundwater in the Chapai-Nawabganj District, northwestern Bangladesh

Groundwater and core sediments of two boreholes (to a depth of 50 m) from the Chapai-Nawabganj area in northwestern Bangladesh were collected for arsenic concentration and geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10-40 m of depth) range from 2.8 μg L⁻¹ to 462.3 μg L⁻¹. Groundwater geochemical conditions change from oxidized to successively more reduced, higher As concentration with depth. Higher sediment arsenic levels (55 mg kg⁻¹) were found within the upper 40 m of the drilled core samples. X-ray absorption near-edge structure spectroscopy was employed to elucidate the arsenic speciation of sediments collected from two boreholes. Environmental scanning electron microscopy and transmission X-ray microscopy were used to investigate the characteristics of FeOOH in sediments which adsorb arsenic. In addition, a pH-Eh diagram was drawn using the Geochemist's Workbench (GWB) software to elucidate the arsenic speciation in groundwater. The dominant groundwater type is Ca-HCO₃ with high concentrations of As, Fe and Mn but low levels of NO₃⁻ and SO₄²⁻. Sequential extraction analysis reveals that Mn and Fe hydroxides and organic matter are the major leachable solids carrying As. High levels of arsenic concentration in aquifers are associated with fine-grained sediments. Fluorescent intensities of humic substances indicate that both groundwater and sediments in this arsenic hotspot area contain less organic matter compared to other parts of Bengal basin. Statistical analysis clearly shows that As is closely associated with Fe and Mn in sediments while As is better correlated with Mn in groundwater. These correlations along with results of sequential leaching experiments suggest that reductive dissolution of MnOOH and FeOOH mediated by anaerobic bacteria represents an important mechanism for releasing arsenic into the groundwater.     

Preparation and evaluation of iron–chitosan composites for removal of As(III) and As(V) from arsenic contaminated real life groundwater

A study on the removal of arsenic from real life groundwater using iron–chitosan composites is presented. Removal of arsenic(III) and arsenic(V) was studied through adsorption at pH 7.0 under equilibrium and dynamic conditions. The equilibrium data were fitted to Langmuir adsorption models and the various model parameters were evaluated. The monolayer adsorption capacity from the Langmuir model for iron chitosan flakes (ICF) (22.47 ± 0.56 mg/g for As(V) and 16.15 ± 0.32 mg/g for As(III)) was found to be considerably higher than that obtained for iron chitosan granules (ICB) (2.24 ± 0.04 mg/g for As(V); 2.32 ± 0.05 mg/g for As(III)). Anions including sulfate, phosphate and silicate at the levels present in groundwater did not cause serious interference in the adsorption behavior of arsenate/arsenite. The column regeneration studies were carried out for two sorption–desorption cycles for both As(III) and As(V) using ICF and ICB as sorbents. One hundred and forty-seven bed volumes of As(III) and 112 bed volumes of As(V) spiked groundwater were treated in column experiments using ICB, reducing arsenic concentration from 500 to <10 μg/l. The eluent used for the regeneration of the spent sorbent was 0.1 M NaOH. The adsorbent was also successfully applied for the removal of total inorganic arsenic down to <10 μg/l from real life arsenic contaminated groundwater samples.     

Microbial transformations of arsenic: mobilization from glauconitic sediments to water

In the Inner Coastal Plain of New Jersey, arsenic (As) is released from glauconitic sediment to carbon- and nutrient-rich shallow groundwater. This As-rich groundwater discharges to a major area stream. We hypothesize that microbes play an active role in the mobilization of As from glauconitic subsurface sediments into groundwater in the Inner Coastal Plain of New Jersey. We have examined the potential impact of microbial activity on the mobilization of arsenic from subsurface sediments into the groundwater at a site on Crosswicks Creek in southern New Jersey. The As contents of sediments 33-90 cm below the streambed were found to range from 15 to 26.4 mg/kg, with siderite forming at depth. Groundwater beneath the streambed contains As at concentrations up to 89 μg/L. Microcosms developed from site sediments released 23 μg/L of As, and active microbial reduction of As(V) was observed in microcosms developed from site groundwater. DNA extracted from site sediments was amplified with primers for the 16S rRNA gene and the arsenate respiratory reductase gene, arrA, and indicated the presence of a diverse anaerobic microbial community, as well as the presence of potential arsenic-reducing bacteria. In addition, high iron (Fe) concentrations in groundwater and the presence of iron-reducing microbial genera suggests that Fe reduction in minerals may provide an additional mechanism for release of associated As, while arsenic-reducing microorganisms may serve to enhance the mobility of As in groundwater at this site.     

Mobilization of arsenic and other naturally occurring contaminants in groundwater of the Main Ethiopian Rift aquifers

This study investigates the mechanisms of arsenic (As) and other naturally occurring contaminants (F⁻, U, V, B, and Mo) mobilization from Quaternary sedimentary aquifers of the Main Ethiopian Rift (MER) and their enrichment in the local groundwater. The study is based on systematic measurements of major and trace elements as well as stable oxygen and hydrogen isotopes in groundwater, coupled with geochemical and mineralogical analyses of the aquifer rocks. The Rift Valley aquifer is composed of rhyolitic volcanics and Quaternary lacustrine sediments. X-ray fluorescence (XRF) results revealed that MER rhyolites (ash, tuff, pumice and ignimbrite) and sediments contain on average 72 wt. % and 65 wt. % SiO₂, respectively. Petrographic studies of the rhyolites indicate predominance of volcanic glass, sanidine, pyroxene, Fe-oxides and plagioclase. The As content in the lacustrine sediments (mean = 6.6 mg/kg) was higher than that of the rhyolites (mean: 2.5 mg/kg). The lacustrine aquifers of the Ziway-Shala basin in the northern part of MER were identified as high As risk zones, where mean As concentration in groundwater was 22.4 ± 33.5 (range of 0.60–190 μg/L) and 54% of samples had As above the WHO drinking water guideline value of 10 μg/L. Field As speciation measurements showed that most of the groundwater samples contain predominantly (∼80%) arsenate-As(V) over arsenite-As(III) species. The As speciation together with field data of redox potential (mean Eh = +73 ± 65 mV) and dissolved-O₂ (6.6 ± 2.2 mg/L) suggest that the aquifer is predominantly oxidative. Water-rock interactions, including the dissolution of volcanic glass produces groundwater with near-neutral to alkaline pH (range 6.9–8.9), predominance of Na–HCO₃ ions, and high concentration of SiO₂ (mean: 85.8 ± 11.3 mg/L). The groundwater data show high positive correlation of As with Na, HCO₃¯, U, B, V, and Mo (R² > 0.5; p < 0.001). Chemical modeling of the groundwater indicates that Fe-oxides and oxyhydroxides minerals were saturated in the groundwater, suggesting that the As reactivity is controlled by adsorption/desorption processes with these minerals. The data show that As and other oxyanion-forming elements such as U, B, Mo, and V had typically higher concentrations at pH > ∼8, reflecting the pH-dependence of their mobilization. Based on the geochemical and stable isotope variations we have established a conceptual model for the occurrence of naturally occurring contaminants in MER groundwater: 1) regional groundwater recharge from the Highland, along the Rift margins, followed by lateral flow and water–rock interactions with the aquifer rocks resulted in a gradual increase of the salinity and naturally occurring contaminants towards the center of the valley; and (2) local δ¹⁸O-rich lake water recharge into adjacent shallow aquifers, followed by additional mobilization of As and other oxyanion-forming elements from the aquifer rocks. We posit that the combined physical-chemical conditions of the aquifers such as oxidizing state, Na–HCO₃ composition, and pH>∼8 lead to enhanced mobilization of oxyanion-forming elements from Fe-oxides and consequently contamination of local groundwater. These geochemical conditions characterize groundwater resources along the Eastern African Rift and thus constitute a potential threat to the quality of groundwater in larger areas of Eastern Africa.     

Sources and controls for the mobility of arsenic in oxidizing groundwaters from loess-type sediments in arid/semi-arid dry climates - evidence from the Chaco-Pampean plain (Argentina)

In oxidizing aquifers, arsenic (As) mobilization from sediments into groundwater is controlled by pH-dependent As desorption from and dissolution of mineral phases. If climate is dry, then the process of evaporative concentration contributes further to the total concentration of dissolved As. In this paper the principal As mobility controls under these conditions have been demonstrated for Salí River alluvial basin in NW Argentina (Tucumán Province; 7000 km²), which is representative for other basins or areas of the predominantly semi-arid Chaco-Pampean plain (1,000,000 km²) which is one of the world’s largest regions affected by high As concentrations in groundwater. Detailed hydrogeochemical studies have been performed in the Salí River basin where 85 groundwater samples from shallow aquifers (42 samples), deep samples (26 samples) and artesian aquifers (17 samples) have been collected. Arsenic concentrations range from 11.4 to 1660 μg L⁻¹ leaving 100% of the investigated waters above the provisional WHO guideline value of 10 μg L⁻¹. A strong positive correlation among As, F, and V in shallow groundwaters was found. The correlations among those trace elements and U, B and Mo have less significance. High pH (up to 9.2) and high bicarbonate (HCO₃) concentrations favour leaching from pyroclastic materials, including volcanic glass which is present to 20-25% in the loess-type aquifer sediments and yield higher trace element concentrations in groundwater from shallow aquifers compared to deep and artesian aquifers. The significant increase in minor and trace element concentrations and salinity in shallow aquifers is related to strong evaporation under semi-arid climatic conditions. Sorption of As and associated minor and trace elements (F, U, B, Mo and V) onto the surface of Fe-, Al- and Mn-oxides and oxi-hydroxides, restricts the mobilization of these elements into groundwater. Nevertheless, this does not hold in the case of the shallow unconfined groundwaters with high pH and high concentrations of potential competitors for adsorption sites (HCO₃, V, P, etc.). Under these geochemical conditions, desorption of the above mentioned anions and oxyanions occurs as a key process for As mobilization, resulting in an increase of minor and trace element concentrations. These geochemical processes that control the concentrations of dissolved As and other trace elements and which determine the groundwater quality especially in the shallow aquifers, are comparable to other areas with high As concentrations in groundwater of oxidizing aquifers and semi-arid or arid climate, which are found in many parts of the world, such as the western sectors of the USA, Mexico, northern Chile, Turkey, Mongolia, central and northern China, and central and northwestern Argentina.     

Effects of water chemistry on arsenic removal from drinking water by electrocoagulation

Exposure to arsenic through drinking water poses a threat to human health. Electrocoagulation is a water treatment technology that involves electrolytic oxidation of anode materials and in-situ generation of coagulant. The electrochemical generation of coagulant is an alternative to using chemical coagulants, and the process can also oxidize As(III) to As(V). Batch electrocoagulation experiments were performed in the laboratory using iron electrodes. The experiments quantified the effects of pH, initial arsenic concentration and oxidation state, and concentrations of dissolved phosphate, silica and sulfate on the rate and extent of arsenic removal. The iron generated during electrocoagulation precipitated as lepidocrocite (γ-FeOOH), except when dissolved silica was present, and arsenic was removed by adsorption to the lepidocrocite. Arsenic removal was slower at higher pH. When solutions initially contained As(III), a portion of the As(III) was oxidized to As(V) during electrocoagulation. As(V) removal was faster than As(III) removal. The presence of 1 and 4 mg/L phosphate inhibited arsenic removal, while the presence of 5 and 20 mg/L silica or 10 and 50 mg/L sulfate had no significant effect on arsenic removal. For most conditions examined in this study, over 99.9% arsenic removal efficiency was achieved. Electrocoagulation was also highly effective at removing arsenic from drinking water in field trials conducted in a village in Eastern India. By using operation times long enough to produce sufficient iron oxide for removal of both phosphate and arsenate, the performance of the systems in field trials was not inhibited by high phosphate concentrations.     

Health risk assessment of inorganic arsenic intake of Cambodia residents through groundwater drinking pathway

In order to compare the magnitudes and health impacts of arsenic and other toxic trace elements in well water, groundwater and hair samples were collected from three areas with different arsenic exposure scenarios in the Mekong River basin of Cambodia. Ampil commune in Kampong Cham province was selected as an uncontaminated area, Khsarch Andaet commune in Kratie province was selected as a moderately contaminated area, and Kampong Kong commune in Kandal Province was selected as an extremely contaminated area. Results of ICP-MS analyses of the groundwater samples revealed that As, Mn, Fe and Ba concentrations were significantly different among the three study areas (Kruskal-Wallis test, p < 0.0001). Out of 46 observed wells in the Kandal province study area, 100% detected As > 50 μg L⁻¹ and Fe > 300 μg L⁻¹; 52.17% had Mn > 400 μg L⁻¹ and 73.91% found Ba > 700 μg L⁻¹. In the Kratie province study area (n = 12), 25% of wells showed elevated arsenic levels above 10 μg L⁻¹ and 25% had Mn > 400 μg L⁻¹, whereas samples from Kampong Cham province study area (n = 18) were relatively clean, with As < 10 μg L⁻¹. A health risk assessment model derived from the USEPA was applied to calculate individual risks resulting from drinking groundwater. Computational results indicated that residents from Kandal Province study area (n = 297) confronted significantly higher non-carcinogenic and carcinogenic risks than those in Kratie (n = 89) and Kampong Cham (n = 184) province study areas (Kruskal-Wallis test, p < 0.0001). 98.65% of respondents from the Kandal province study area were at risk for the potential non-cancer effect and an average cancer risk index was found to be 5 in 1000 exposure. The calculations also indicated that, in the Kratie province study area, 13.48% of respondents were affected by non-cancer health risks and 33.71% were threatened by cancer, whereas none of respondents in the Kampong Cham province study area appeared to have non-carcinogenic effect. Positively significant correlations of the arsenic content in scalp hair (As_h) with both arsenic levels in groundwater (As_w) (r_s (304) = 0.757, p < 0.0001) and individual average daily doses (ADD) of arsenic (r_s (304) = 0.763, p < 0.0001) undoubtedly indicated that arsenic accumulation in the bodies of Cambodia residents in the Mekong River basin was mainly through a groundwater drinking pathway. To the best of our knowledge, this is the first comprehensive report comparing individual health risk assessments of arsenic exposure through a groundwater drinking pathway to enriched arsenic levels from groundwater in the Mekong River basin, Cambodia. This study indicates that elevated arsenic concentrations in groundwater may lead to thousands of cases of arsenicosis in the near future if mitigating actions are not taken.     

Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using δ³⁴S_[SO4] and δ¹⁸O_[SO4] sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of ³⁴S_[SO4] and ¹⁸O_[SO4] present in Type A, caused by microbial-mediated reduction of sulfate, and high ¹⁸O enrichment factor (ε_[SO4-H2O]), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high δ¹⁸O_[SO4] and low δ³⁴S_[SO4] values under mildly reducing conditions. Base on ¹⁸O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O₂, caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater.     

Arsenic biotransformation by arsenic-resistant fungi Trichoderma asperellum SM-12F1, Penicillium janthinellum SM-12F4, and Fusarium oxysporum CZ-8F1

Bioremediation of arsenic (As)-contaminated soil using microorganisms has been a focus of research because it is environment friendly and cost-effective. The As-resistant fungi Trichoderma asperellum SM-12F1, Penicillium janthinellum SM-12F4, and Fusarium oxysporum CZ-8F1 were exposed to 50 mg l^− 1 of As(V), and the biotransformation of As and the concomitant variance of Eh and pH in the media were studied. Fresh weights of all three isolates increased and then decreased depended on cultivation period. After cultivation for 2 or 3 days, the As(V) added to the media had been completely changed into As(III), whilst As(V) was predominate in fungal cells with concomitantly little As(III) during cultivation. After 15 days, little monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) besides of As(V) and As(III) were found in the cells of T. asperellum SM-12F1, and the total As content was the highest in cells of P. janthinellum SM-12F4 (about 41.5 μg) according to the quantitative analysis of As speciation in cultures. Moreover, when cultivation period reached 3 days, the Eh and pH in the media of T. asperellum SM-12F1 (312.5 mV and 4.8), P. janthinellum SM-12F4 (411.1 mV and 4.2), and F. oxysporum CZ-8F1 (269.4 mV and 4.8) might not responsible for the reduction of As(V) based on the previous study. Therefore, it is speculated that import/export, reduction, and methylation of As are conducted in fungal cells. Future studies investigating the biochemical behaviour of fungi responding to As are needed to gain a better understanding of bioremediation of As-contaminated soils.     

Pathways for arsenic from sediments to groundwater to streams: Biogeochemical processes in the Inner Coastal Plain, New Jersey, USA

The Cretaceous and Tertiary sediments that underlie the Inner Coastal Plain of New Jersey contain the arsenic-rich mineral glauconite. Streambed sediments in two Inner Coastal Plain streams (Crosswicks and Raccoon Creeks) that traverse these glauconitic deposits are enriched in arsenic (15-25 mg/kg), and groundwater discharging to the streams contains elevated levels of arsenic (>80 μg/L at a site on Crosswicks Creek) with arsenite generally the dominant species. Low dissolved oxygen, low or undetectable levels of nitrate and sulfate, detectable sulfide concentrations, and high concentrations of iron and dissolved organic carbon (DOC) in the groundwater indicate that reducing environments are present beneath the streambeds and that microbial activity, fueled by the DOC, is involved in releasing arsenic and iron from the geologic materials. In groundwater with the highest arsenic concentrations at Crosswicks Creek, arsenic respiratory reductase gene (arrA) indicated the presence of arsenic-reducing microbes. From extracted DNA, 16s rRNA gene sequences indicate the microbial community may include arsenic-reducing bacteria that have not yet been described. Once in the stream, iron is oxidized and precipitates as hydroxide coatings on the sediments. Arsenite also is oxidized and co-precipitates with or is sorbed to the iron hydroxides. Consequently, dissolved arsenic concentrations are lower in streamwater than in the groundwater, but the arsenic contributed by groundwater becomes part of the arsenic load in the stream when sediments are suspended during high flow. A strong positive relation between concentrations of arsenic and DOC in the groundwater samples indicates that any process—natural or anthropogenic—that increases the organic carbon concentration in the groundwater could stimulate microbial activity and thus increase the amount of arsenic that is released from the geologic materials.     

Arsenic speciation and uranium concentrations in drinking water supply wells in Northern Greece: correlations with redox indicative parameters and implications for groundwater treatment

The cities in the Aksios and Kalikratia areas in Northern Greece rely on arsenic contaminated groundwater for their municipal water supply. As remedial action strongly depends on arsenic speciation, the presence of other possible contaminants, and on the general water composition, a detailed study with samples from 21 representative locations was undertaken. Arsenic concentrations were typically 10-70 microg/L. In the groundwaters of the Aksios area with lower Eh values (87-172 mV), pH 7.5-8.2 and 4-6 mM HCO(3) alkalinity, As(III) predominated. Manganese concentrations were mostly above the EC standard of 0.05 mg/L (0.1-0.7 mg/L). In groundwaters of the Kalikratia area with higher Eh values (272-352 mV), pH 6.7-7.5 and 6-12 mM HCO(3) alkalinity, As(V) was the main species. Uranium in the groundwaters was also investigated and correlations with total arsenic concentrations and speciation were examined to understand more of the redox chemistry of the examined groundwaters. Uranium concentrations were in the range 0.01-10 microg/L, with the higher concentrations to occur in the oxidizing groundwaters of the Kalikratia area. Uranium and total arsenic concentrations showed no correlation, whereas uranium concentrations correlated strongly with As(III)/As(tot) ratios, depicting their use as a possible indicator of groundwater redox conditions. Finally, boron was found to exceed the EC drinking water standard of 1 mg/L in some wells in the Kalikratia area and its removal should also be considered in the design of a remedial action.     

Arsenic speciation study in some spring waters of Guam, Western Pacific Ocean

A survey of the different forms of arsenic species: inorganic arsenic (As), As(III), As(V) and organic As(III) and (V) was carried out on spring waters located along Tumon Bay in Guam. The results show that total arsenic concentrations in the spring water samples ranged from <0.3-1.2 microg/L. Inorganic arsenate, As(V), appears to be the dominant species in the spring water samples tested. The concentrations are much lower than previously reported, probably due to a much more rigorous methodological approach and requires further investigations on the status of As contamination in groundwater on the island.     

Seasonal changes of arsenic speciation in lake waters in relation to eutrophication

In this study, the influence of eutrophication on arsenic speciation in lake waters was investigated. Surface water samples (n = 1-10) were collected from 18 lakes in Japan during July 2007 and February 2008. The lakes were classified into mesotrophic (7 lakes) and eutrophic (11 lakes) based on the total phosphate (T-P) and chlorophyll-a (Chl-a) concentrations in water column. Inorganic, methylated and ultraviolet-labile fractions of arsenic species were determined by combining hydride generation atomic absorption spectrometry with ultraviolet irradiation. Organoarsenicals (mainly methylated and ultraviolet-labile fractions) comprised 30-60% of the total arsenic in most lakes during summer. On the other hand, inorganic arsenic species (As(III + V)) dominates (about 60-85%) during winter. The occurrence of ultraviolet-labile fractions of arsenic was higher in eutrophic lakes than those in mesotrophic lakes in both seasons. The concentration of dimethyl arsenic (DMAA) was high in eutrophic lakes during winter; and in mesotrophic lakes during summer. The results suggest that the conversion of As(III + V) to more complicated organoarsenicals occurred frequently in eutrophic lakes compared to that in mesotrophic lakes, which is thought to be the influence of biological activity in the water column. The distribution of arsenic species were well correlated with phosphate concentrations than those of Chl-a. This might be due to the competitive uptake of As(V) and phosphate by phytoplankton. The organoarsenicals (OrgAs)/As(V) ratio was higher at low phosphate concentration indicating that conversion of As(V) to OrgAs species was more active in phosphate-exhausted lakes with high phytoplankton density.     

Removal of arsenic from contaminated drinking water by a chitosan/chitin mixture

A Chitosan/chitin mixture was studied as a potential agent for the removal of arsenic (V) from ground waters. The arsenic concentration of contaminated waters was lowered to levels accepted by the Canadian Department of Health and Welfare and the World Health Organization upon treatment with the mixture and, furthermore, the copper and sulfate levels were also reduced. The capacity of the mixture at pH 7 was found to be 0.13 μ-equiv As g⁻¹ mixture with a distribution coefficient of 65. The interaction between arsenic and these polymers is also discussed.     

Bioremoval of arsenic species from contaminated waters by sulphate-reducing bacteria

A mixed culture of sulphate-reducing bacteria was used to study the bioremoval of arsenic species (As(III) or As(V)) from groundwater. During growth of a mixed SRB culture adapted to 0.1 mg/L arsenic species through repeated sub-culturing, 1 mg/L of either As(III) or As(V) was reduced to 0.3 and 0.13 mg/L respectively. Sorption experiments on the precipitate produced by batch cultured sulphate-reducing bacteria (SRB-PP) indicated a removal of about 77 and 55% of As(V) and As(III) respectively under the following conditions: pH 6.9; biomass (2 g/L); 24 h contact time; initial arsenic concentration, 1 mg/L of either species. These results were compared with synthetic iron sulphide as adsorbent. The adsorption data were fitted to Langmuir and Freundlich isotherms. Energy dispersive X-ray analysis showed the SRB-PP contained elements such as sulphur, iron, calcium and phosphorus. Biosorption studies indicated that SRB cell pellets removed about 6.6% of the As(III) and 10.5% of the As(V) from water containing an initial concentration of 1 mg/L of either arsenic species after 24 h contact.     

Depth-resolved abundance and diversity of arsenite-oxidizing bacteria in the groundwater of Beimen,a blackfoot disease endemic area of southwestern Taiwan

The role of arsenite oxidizers in natural attenuation of arsenic pollution necessitates studies on their abundance and diversity in arsenic-contaminated aquifers. In this study, most probable number-polymerase chain reaction (MPN-PCR) and denaturing gradient gel electrophoresis (DGGE) was applied to monitor depth-wise abundance and diversity of aerobic arsenite oxidizers in arsenic-enriched groundwater of Beimen, southwestern Taiwan. The results revealed that the abundance of arsenite oxidizers ranged from 0.04 to 0.22, and the lowest ratio was observed in the most arsenic-enriched and comparatively more reduced groundwater (depth 200 m) of Beimen 1. The highest ratio was observed in the less arsenic-enriched and less reduced groundwater (depth 60 m) of Beimen 2B. DGGE profiles showed a shift in diversity of arsenite oxidizers, consisting of members of the Betaproteobacteria (61%), Alphaproteobacteria (28%) and Gammaproteobacteria (11%), depending on mainly arsenic concentration and redox level in groundwater. Groundwater with the lowest arsenic and highest dissolved oxygen at Beimen 2B harbored 78% of the arsenite oxidizers communities, while groundwater with the highest arsenic and lowest dissolved oxygen at Beimen 1 and Beimen–Jinhu harbored 17 and 22% of arsenite oxidizers communities, respectively. Pseudomonas sp. was found only in groundwater containing high arsenic at Beimen 1 and Beimen–Jinhu, while arsenite oxidizers belonging to Alpha- and Betaproteobacteria were dominated in groundwater containing low arsenic.     

Effects of hardness and alkalinity on the removal of arsenic(V) from humic acid-deficient and humic acid-rich groundwater by zero-valent iron

The effects of hardness (Ca²⁺) and alkalinity (HCO₃⁻) on arsenic(V) removal from humic acid (HA)-deficient and HA-rich groundwater by zero-valent iron (Fe⁰) were investigated using batch experiments. Arsenic, in general, is removed from groundwater possibly by adsorption and co-precipitation with the iron corrosion products. However, in the co-presence of HCO₃⁻ and Ca²⁺, the removal rate of arsenic increased with increasing concentrations of either Ca²⁺ or HCO₃⁻. It was observed that the removal of arsenic was significantly enhanced by the formation of CaCO₃ as a nucleation seed for the growth of large iron (hydr)oxide particles. In the co-existence of Ca²⁺, HCO₃⁻ and HA, the presence of HA diminished the positive role of Ca²⁺ due to the formation of Fe-humate complexes in solution and delaying of the formation of CaCO₃. As a result, the formation of the large iron (hydr)oxide particles was inhibited in the earlier stage which, in turn, affected the removal of arsenic. However, after the formation of CaCO₃ and the subsequent growth of such particles, the presence of large iron (hydr)oxide particles resulted in the rapid removing of arsenic and Fe-humate by adsorption and/or co-precipitation.