Dissimilatory Arsenate Reduction and In Situ Microbial Activities and Diversity in Arsenic-rich Groundwater of Chianan Plain, Southwestern Taiwan.

Although dissimilatory arsenic reduction (DAsR) has been recognized as an important process for groundwater arsenic (As) enrichment, its characterization and association with in situ microbial activities and diversity in As-rich groundwater is barely studied. In this work, we collected As-rich groundwater at depths of 23, 300, and 313 m, respectively, from Yenshui-3, Budai-Shinwen, and Budai-4 of Chianan plain, southwestern Taiwan, and conducted incubation experiments using different electron donors, acceptors, and sulfate-reducing bacterial inhibitor (tungstate) to characterize DAsR. Moreover, bacterial diversity was evaluated using 454-pyrosequencing targeting bacterial 16S rRNAs. MPN technique was used to enumerate microorganisms with different in situ metabolic functions. The results revealed that DAsR in groundwater of Chianan plain was a biotic phenomenon (as DAsR was totally inhibited by filter sterilization), enhanced by the type of electron donor (in this case, lactate enhanced DAsR but acetate and succinate did not), and limited by the availability of arsenate. In addition to oxidative recycling of As(III), dissolution of As(V)-saturated manganese and iron minerals by indigenous dissimilatory Mn(IV)- and Fe(III)-reducing bacteria, and abiotic oxidation of As(III) with Mn(IV) regenerated As(V) in the groundwater. Sulfate-respiring bacteria contributed 7.4 and 28.2 % to the observed DAsR in groundwater of Yinshui-3 and Budai-Shinwen, respectively, whereas their contribution was negligible in groundwater of Budai-4. A noticeable variation in dominant genera Acinetobacter and Bacillus was observed within the groundwater. Firmicutes dominated in highly As-rich groundwater of Yenshui-3, whereas Proteobacteria dominated in comparatively less As-rich groundwater of Budai-Shinwen and Budai 4.

Bioaccessibility and health risk assessment of arsenic in arsenic-enriched soils, Central India.

Incidental soil ingestion is expected to be a significant exposure route to arsenic for children because of the potentially high arsenic contents found in certain soils. Therefore, it is prudent to get information on oral bioaccessibility of arsenic following incidental soil ingestion and its relevance in health risk assessment for future remediation strategies. Soil samples were collected from eight villages of Ambagarh Chauki block, Chhattisgarh, Central India. The soils from seven villages had total arsenic content more than the background level of 10mgkg(-1) (ranged from 16 to 417mgkg(-1)), whereas the total arsenic content of soil from Hauditola was 7mgkg(-1). Bioaccessible arsenic assessed by the simplified bioaccessibility extraction test (SBET) ranged from 5.7 to 46.3%. Arsenic bioaccessibility was significantly influenced by clay content (R(2)=0.53, p<0.05, n=8), TOC (R(2)=0.50, p<0.05, n=8), Fe content (R(2)=0.47, p<0.05, n=8) and soil pH (R(2)=0.75, p<0.01, n=8). Risk assessment of the study sites showed that hazard index of arsenic under incidental soil ingestion was below 1 in all the study sites, except Kaudikasa. However, carcinogenic risk probability for arsenic to children from the villages Meregaon, Thailitola, Joratarai and Kaudikasa was below acceptable level (<1×10(-4)), suggesting potential health risk for children from these sites could not be overlooked. With high carcinogenic risk value (3.8E-05) and HI index (>1) for arsenic in soils of Kaudikasa, attention should be paid for development of remediation measure.

Evaluation of remediation process with soapberry derived saponin for removal of heavy metals from contaminated soils in Hai-Pu, Taiwan.

The use of a biodegradable natural plant-based surfactant extracted from soapberry is proposed for the remediation of Ni, Cr and Mn from industrial soil site in Hai-Pu, Taiwan. Batch experiments were performed under variation of fundamental factors (saponin concentration, pH, and incubation time) for metal remediation. Removal of Ni and Mn were increased with increasing saponin concentration (0.015-0.150 g/L), whereas the removal of Cr was increased upto 0.075 g/L saponin. The Ni, Cr and Mn were removed significantly (p < or = 0.05) at near to the neutral and slightly acidic (pH 5 to 8) conditions. Removal efficiency of Ni (99%) from the soil was found to be greater than that of Cr (73%) or Mn (25%) in the presence of saponin at a concentration of 0.150 g/L at pH 5. The removal percentage increased with incubation time where the removal of Ni was faster than that of Cr and Mn. The result indicates the feasibility of eco-friendly removal of heavy metal (Ni, Cr and Mn) from industrial soil by soil washing process in presence of plant derived saponin.

Arsenic-induced health crisis in peri-urban Moyna and Ardebok villages, West Bengal, India: an exposure assessment study.

Drinking of arsenic (As)-contaminated groundwater has adverse effects on health of millions of people worldwide. This study aimed to determine the degree of severity of As exposure from drinking water in peri-urban Moyna and Ardebok villages, West Bengal, India. Arsenic concentrations in hair, nail and urine samp les of the individuals were determined. Arsenical dermatosis, keratosis and melanosis were investigated through medical evaluation. We have evaluated the association between As exposure from drinking water, and keratosis and melanosis outcomes. The results showed that 82.7 % of the sampled tube wells contain As concentrations above 10 µg/L, while 57.7 % contain As concentrations above 50 µg/L. The hair, nail and urine As concentrations were positively correlated with As concentrations in drinking water. In our study population, we observed a strong association between As concentrations ranging 51-99 µg/L and keratosis and melanosis outcomes, although the probability decreases at higher concentration ranges perhaps due to switching away from the use of As-contaminated tube wells for drinking and cooking purposes. High As concentrations in hair, nail and urine were observed to be associated with the age of the study population. The level of As concentrations in hair, nail and urine samples of the study population indicated the degree of severity of As exposure in the study region.

The potential for reductive mobilization of arsenic [As(V) to As(III)] by OSBH(2) (Pseudomonas stutzeri) and OSBH(5) (Bacillus cereus) in an oil-contaminated site.

Microbial reduction of arsenate [As(V)] plays an important role in arsenic (As) mobilization in aqueous environments. In this study, we investigated reduction of arsenate by different bacterial isolates such as OSBH(1) (GU329913), OSBH(2) (GU329914), OSBH(3) (GU329915), OSBH(4) (GU329916) and OSBH(5) (GU329917), isolated from the oil sludge of a sewage treatment plant operated by the China Petroleum Refinery Company in Kaohsiung, southern Taiwan. Bacterial strains of pure culture were identified by 16S rRNA analysis (≥99 % nucleotide similarity). Morphological and 16S rRNA analysis show that the isolate OSBH(1) is similar to E. coli, OSBH(2) is similar to P. stutzeri, OSBH(3) is similar to P. putida, OSBH(4) is similar to P. aeruginosa, and OSBH(5) is similar to B. Cereus. The As(V) was transformed to As(III) in the presence of isolates OSBH(2) and OSBH(5) by a detoxification process. The potential reduction rates of As(V) were higher in the presence of isolate OSBH(5) compared to the isolate OSBH(2). The microbial growth (cell/mL) of isolate OSBH(5) was significantly higher in culture medium compared to OSBH(2). The bacterial isolates such as OSBH(1), OSBH(3) and OSBH(4) were found to be incapable of transforming the As(V). It is concluded that the activity of the oil-degrading bacterial isolates described in this work contributes to the mobilization of As in the more toxic As(III) form that affects biotic life.

Health risks for human intake of aquacultural fish: Arsenic bioaccumulation and contamination.

Aquacultural tilapia (Oreochromis mossambicus L.) and shrimp (Penaeus monodon L.) from groundwater-cultured ponds in southwestern Taiwan were analyzed to estimate arsenic (As) bioaccumulation and the potential health risk to human intake. Most of aquacultural ponds exhibited higher arsenic than maximum allowed concentrations (50 µg L(-1)) in pond water of Taiwan. Arsenic levels in tilapia in Budai, Yichu and Beimen were 0.92 ± 0.52 µg g(-1), 0.93 ± 0.19 µg g(-1) and 0.76 ± 0.03 µg g(-1), respectively and in shrimp was 0.36 ± 0.01 µg g(-1) in Beimen. Total arsenic in tilapia is highly correlated (R(2) = 0.80) with total arsenic concentration of pond water. Total arsenic in fish showed high correlation with that in bone (R(2) = 0.98), head (R(2) = 0.97) and tissue (R(2) = 0.96). Organic arsenic species (DMA) was found higher relative to inorganic species of As(III) and As(V). The average percent contribution of inorganic arsenic to total arsenic in fish samples was 12.5% and ranged between 11.7 to 14.2%. Bioaccumulation factors (BAFs) for total arsenic in fish ranged from 10.3 to 22.1, whereas BAF for inorganic arsenic ranged from 1.33 to 2.82. The mean human health cancer risk associated with the ingestion of inorganic arsenic in the fish was estimated at 2.36 × 10(-4) ± 0.99 × 10(-4), which is over 200 times greater than a de Minimus cancer risk of 1 × 10(-6). The mean human health hazard quotient associated with ingesting inorganic arsenic in the fish was 1.22 ± 0.52, indicating that expected human exposure exceeds the reference dose for non-cancer health effects by 22%. These results suggest that the inhabitants in this region are being subjected to moderately elevated arsenic exposure through the consumption of tilapia and shrimp raised in aquaculture ponds.

A comparative study on arsenic and humic substances in alluvial aquifers of Bengal delta plain (NW Bangladesh), Chianan plain (SW Taiwan) and Lanyang plain (NE Taiwan): implication of arsenic mobilization mechanisms.

Humic substances in groundwater and aquifer sediments from the arsenicosis and Blackfoot disease (BFD) affected areas in Bangladesh (Bengal delta plain) and Taiwan (Lanyang plain and Chianan plain) were characterized using fluorescence spectrophotometry and Fourier transform infrared (FT-IR) spectroscopy. The results demonstrate that the mean concentration of As and relative intensity of fluorescent humic substances are higher in the Chianan plain groundwater than those in the Lanyang plain and Bengal delta plain groundwater. The mean As concentrations in Bengal delta plain, Chianan plain, and Lanyang plain are 50.65 µg/l (2.8-170.8 µg/l, n=20), 393 µg/l (9-704 µg/l, n=5), and 104.5 µg/l (2.51-543 µg/l, n = 6), respectively. Average concentrations and relative fluorescent intensity of humic substances in groundwater are 25.381 QSU (quinine standard unit) and 17.78 in the Bengal delta plain, 184.032 QSU and 128.41 in the Chianan plain, and 77.56 QSU and 53.43 in the Lanyang plain. Moreover, FT-IR analysis shows that the humic substances extracted from the Chianan plain groundwater contain phenolic, alkanes, aromatic ring and amine groups, which tend to form metal carbon bonds with As and other trace elements. By contrast, the spectra show that humic substances are largely absent from sediments and groundwater in the Bengal delta plain and Lanyang plain. The data suggest that the reductive dissolution of As-adsorbed Mn oxyhydroxides is the most probable mechanism for mobilization of As in the Bengal delta plain. However, in the Chianan plain and Lanyang plain, microbially mediated reductive dissolution of As-adsorbed amorphous/crystalline Fe oxyhydroxides in organic-rich sediments is the primary mechanism for releasing As to groundwater. High levels of As and humic substances possibly play a critical role in causing the unique BFD in the Chianan plain of SW Taiwan.

Arsenic-enriched groundwaters of India, Bangladesh and Taiwan--comparison of hydrochemical characteristics and mobility constraints.

Arsenic (As) enrichment in groundwater has become a major global environmental disaster. Groundwater samples were collected from 64 sites located in the districts of 24-Parganas (S), and Nadia in West Bengal, India (Bhagirathi sub-basin), and 51 sites located in the districts of Comilla, Noakhali, Magura, Brahman baria, Laxmipur, Munshiganj, Faridpur and Jhenaida in Bangladesh (Padma-Meghna sub-basin). Groundwater samples were also collected from two As-affected areas (Chianan and Lanyang plains) of Taiwan (n = 26). The concentrations of major solutes in groundwater of the Padma-Meghna sub-basin are more variable than the Bhagirathi sub-basin, suggesting variations in the depositional and hydrological settings. Arsenic concentrations in groundwaters of the studied areas showed large variations, with mean As concentrations of 125 µg/L (range: 0.20 to 1,301 µg/L) in Bhagirathi sub-basin, 145 µg/L (range: 0.20 to 891 µg/L) in Padma-Meghna sub-basin, 209 µg/L (range: 1.3 to 575 µg/L) in Chianan plain, and 102 µg/L (range: 2.5 to 348 µg/L) in Lanyang plain groundwater. The concentrations of Fe, and Mn are also highly variable, and are mostly above the WHO-recommended guideline values and local (Indian and Bangladeshi) drinking water standard. Piper plot shows that groundwaters of both Bhagirathi and Padma-Meghna sub-basins are of Ca-HCO(3) type. The Chianan plain groundwaters are of Na-Cl type, suggesting seawater intrusion, whereas Lanyang plain groundwaters are mostly of Na-HCO(3) type. The study shows that reductive dissolution of Fe(III)-oxyhydroxides is the dominant geochemical process releasing As from sediment to groundwater in all studied areas.

Role of organic matter and humic substances in the binding and mobility of arsenic in a Gangetic aquifer.

Arsenic (As) enrichment in groundwater has led to extensive research, particularly on the factors responsible for its release into groundwater. In the Gangetic plain, organic matter driven microbial reduction of Fe-oxyhydroxides is considered as the most plausible mechanism of As release into groundwater. However, the role of organic matter in the aqueous environment is not well known and particularly that of organometallic complex. In this study, we have characterized bulk sediment and groundwater samples, collected from Barasat, West Bengal, India, to understand the effect of organic matter in the binding and mobility of As in the subsurface environment. The results showed a moderate correlation (R(2) = 0.49, p < 0.05) between dissolved organic carbon (DOC) and As in groundwater, suggesting that DOC has a role in releasing As into groundwater. The relative fluorescent intensity (RFI) of the dissolved humic substances in groundwater showed a maximum value of 65 QSU (mean: 47 ± 8 QSU). FT-IR spectra of the extracted humic acid fractions of the sediment showed COO-, C = O, OH, and C = C (aromatic ring) functional groups, which may act as a chelating agents with the metal(loid)s. FT-IR spectra of the HA-As complex exhibited specific peaks at 1242 and 832 cm(-1) in the fingerprint region. This is similar to the extracted humic acid fractions of the Gangetic sediment, suggesting binding of As with humic substances.

Biogeochemical characteristics of Kuan-Tzu-Ling, Chung-Lun and Bao-Lai hot springs in southern Taiwan.

Hot springs are the important natural sources of geothermally heated groundwater from the Earth's crust. Kuan-Tzu-Ling (KTL), Chung-Lun (CL) and Bao-Lai (BL) are well-known hot springs in southern Taiwan. Fluid and mud (sediments) samples were collected from the eruption points of three hot springs for detailed biogeochemical characterization. The fluid sample displays relatively high concentrations of Na(+) and Cl(-) compared with K(+), Mg(2+), Ca(2+), NO(2) (-), and SO(4) (2-), suggesting a possible marine origin. The concentrations of Fe, Cr, Mn, Ni, V and Zn were significantly higher in the mud sediments compared with fluids, whereas high concentrations of As, Ba, Cu, Se, Sr and Rb were observed in the fluids. This suggests that electronegative elements were released during sediment-water interactions. High As concentration in the fluids was observed to be associated with low redox (Eh) conditions. The FTIR spectra of the humic acid fractions of the sediments showed the presence of possible functional groups of secondary amines, ureas, urethanesm (amide), and silicon. The sulfate-reducing deltaproteobacterium 99% similar to Desulfovibrio psychrotolerans (GU329907) were rich in the CL hot spring while mesophilic, proteolytic, thiosulfate- and sulfur-reducing bacterium that 99% similar to Clostridium sulfidigenes (GU329908) were rich in the BL hot spring.

Biogeochemical interactions among the arsenic, iron, humic substances, and microbes in mud volcanoes in southern Taiwan.

Fluid and mud samples collected from Hsiaokunshui (HKS), Wushanting (WST), Yenshuikeng (YSK), Kunshuiping (KSP), Liyushan (LYS), and Sinyangnyuhu (SYNH) mud volcanoes of southwestern Taiwan were characterized for major ions, humic substances (HS) and trace elements concentrations. The relationship between the release of arsenic (As) and activities of sulfate-reducing bacteria has been assessed to understand relevant geochemical processes in the mud volcanoes. Arsenic (0.02-0.06 mg/L) and humic substances (4.13 × 10(-4) to 1.64 × 10(-3) mM) in the fluids of mud volcanoes showed a positive correlation (r = 0.99, p < 0.05) except in Liyushan mud volcano. Arsenic and iron in mud sediments formed two separate groups i) high As, but low Fe in HKS, WST, and SYNH; and ii) low As, but high Fe in the YSK, KSP, and LYS mud volcanoes. The Eh(S.H.E.) values of the mud volcano liquids were characterized by mild to strongly reducing conditions. The HKS, SYNH, and WST mud volcanoes (near the Chishan Fault) belongs to strong reducing environment (-33 to -116 mV), whereas the LYS, YSK, and KSP mud volcanoes located near the coastal plain are under mild reducing environment (-11 to 172 mV). At low Eh values mud volcanoes, saturation index (SI) values of poorly crystalline phases such as amorphous ferric hydroxide indicate understaturation, whereas saturation is reached in relatively high Eh(S.H.E.) values mud volcanoes. Arsenic contents in sediments are low, presumably due to its release to fluids (As/Fe ratio in YSK, KSP, and LYS sediment: 4.86 × 10(-4)-6.20 × 10(-4)). At low Eh(S.H.E.) values (mild to strong reducing environment), arsenic may co-precipitate with sulfides as a consequence of sulfate reduction (As/Fe ratios in WST, HKS, and SYNH sediments: 0.42-0.69).

Arsenic removal from groundwater of the Chaco-Pampean plain (Argentina) using natural geological materials as adsorbents.

Use of natural geological materials for arsenic (As) removal is an emerging solution at a household level for poor people in remote rural settlements, especially when the materials are locally available and can be collected by the local population. Their low or zero cost makes these materials very attractive compared with synthetic or commercial materials. Sometimes, this may be the only option to provide safe water to very poor settlements. Their suitability for As removal from water is mainly due to adsorption, co-precipitation and ion exchange processes involving Fe- and Al-rich minerals and clay minerals present in the soils or sediments. In the present study, various clay-rich soils from the Santiago del Estero province (SDE, NW Argentina) and, for comparison, a laterite from the Misiones province have been tested as adsorbents for As in shallow naturally contaminated groundwaters of the Río Dulce alluvial aquifer in SDE. Batch adsorption experiments showed higher As(V) removal for the Misiones laterite sample (99 %) as compared with the soils from SDE (40-53 %), which can be related to lower contents of water-soluble and oxalate extractable Al and Fe in the last samples. These results suggest the application of the Misiones laterite soil as an alternative for As removal. However, high transportation costs from Misiones to SDE can be an economical restriction for the low-income population of SDE.

Biological synthesis of gold and silver nanoparticles mediated by the bacteria Bacillus subtilis.

Biological synthesis of gold and silver nanoparticles was carried out using the bacteria Bacillus subtilis. The reduction processes of chloroaurate and silver ions by B. subtilis were found to be different. Gold nanoparticles were synthesized both intra- and extracellularly, while silver nanoparticles were exclusively formed extracellularly. The gold nanoparticles were formed after 1 day of addition of chloroaurate ions, while the silver nanoparticles were formed after 7 days. The nanoparticles were characterized by X-ray diffraction, UV-vis spectra and transmission electron spectroscopy. X-ray diffraction revealed the formation of face-centered cubic (fcc) crystalline gold nanoparticles in the supernatant, broth solution and bacterial pellet. Silver nanoparticles also exhibited diffraction peaks corresponding to fcc metallic silver. UV-vis spectra showed surface plasmon vibrations for gold and silver nanoparticles centered at 530 and 456 nm, respectively. TEM micrographs depicted the formation of gold nanoparticles intra- and extracellularly, which had an average size of 7.6 +/- 1.8 and 7.3 +/- 2.3 nm, respectively, while silver nanoparticles were exclusively formed extracellularly, with an average size of 6.1 +/- 1.6 nm. The bacterial proteins were analyzed by sodium dodecyl sulfonate-polyacrylamide electrophoresis (SDS-PAGE) before and after the addition of metal ion solutions. We believe that proteins of a molecular weight between 25 and 66 kDa could be responsible for chloroaurate ions reduction, while the formation of silver nanoparticles can be attributed to proteins of a molecular weight between 66 and 116 kDa. We also believe that the nanoparticles were stabilized by the surface-active molecules i.e., surfactin or other biomolecules released into the solution by B. subtilis.

Adsorption and desorption properties of arsenate onto nano-sized iron-oxide-coated quartz.

This study was conducted to investigate the adsorption and desorption properties of arsenate [As(V)] on nano-sized iron-oxide-coated quartz (IOCQ) through batch experiments. The coating of nano-sized iron oxide on the quartz surface was performed using the heat treatment process which aimed to utilize the adsorption properties of the nano-sized iron oxide and the filtration properties of the quartz. Environmental SEM-EDAX and BET techniques were used to analyze the surface morphology, elemental composition, surface area and the porosity of the adsorbent. SEM-EDAX analyses confirmed that arsenate was adsorbed on the IOCQ surface. BET results showed that the IOCQ adsorbent had higher pore volumes and high specific surface areas compared with the pure quartz. The study revealed that the adsorption rate of As(V) ion was very rapid and reached the equilibrium within 5 min. This study also revealed that almost 100% of As(V) removal was achieved within 5 minutes of adsorption reaction from the initial solution containing 1,000 microg-As(V)/L. The Langmuir adsorption isotherm model suitably explained the sorption characteristics of As(V) onto IOCQ. This desorption study showed that the adsorbent could be reused after reacting with mild HCl solution but the concentration of acid eluant or pH has a great impact on the coated adsorbent surface. The results indicate that the nano-sized iron oxide-coated adsorbent is potentially suitable for removal of arsenate from drinking water.

Synthesis of gold nanoparticles via an environmentally benign route using a biosurfactant.

Anionic biosurfactant surfactin-mediated gold nanoparticles were synthesized for the first time in this study. Differing proton concentrations is believed to cause structural changes in the lipopeptide surfactin used to stabilize the gold nanoparticles in aqueous solution, the effects of which on the morphology of the nanoparticles were investigated. Synthesis of gold nanoparticles by borohydrate reduction was performed at three pH levels (pH 5, 7 and 9) and two different temperatures, and the nanoparticles were characterized by UV-visible spectroscopy, X-ray diffraction and transmission electron microscopy. The UV-vis spectra showed a blue shift with increasing pH from 5 to 9 (from 528 to 566 nm) at both 4 degrees C and room temperature. The nanoparticles synthesized at pH 7 and 9 remained stable for 2 months, while aggregates were observed at pH 5 within 24 h. TEM micrographs revealed that the mean particle size was about 13.11, 8.16 and 4.70 nm at pH 5, 9 and 7, respectively, at 4 degrees C. The nanoparticles formed at pH 7 were uniform in shape and size, and polydispersed and anisotropic at pH 5 and 9. The nanoparticles synthesized at room temperature were monodispersed and were more uniform as compared with those formed at 4 degrees C. This report describes the use of a renewable and environmentally green and biodegradable surfactant as a template and stabilizing agent in the synthesis of gold nanoparticles.

The whole genome insight on condition-specific redox activity and arsenopyrite interaction promoting As-mobilization by strain Lysinibacillus sp. B2A1.

A gram-positive spore former, Lysinibacillus sp. B2A1 was isolated from a high arsenic containing groundwater of Beimen2A well, Chianan Plain area, Southwestern Taiwan. Noteworthy, in the subsurface-mimicking anoxic incubation with a Na-lactate amendment system, this isolate could interact with arsenic-source mineral arsenopyrite and enhance arsenic mobilization. Further, the isolate showed elevated levels of arsenic resistance, 200 mM and 7.5 mM for arsenate and arsenite, respectively. Lysinibacillus sp. B2A1 demonstrated condition-specific redox activities including salient oxic oxidation of arsenite and anoxic reduction of arsenate. The elevated rate of As(III) oxidation (Vmax = 0.13 µM min-1 per 106 cells, Km = 15.3 µM) under oxic conditions was potent. Correlating with stout persistence in an arsenic-rich niche, remarkably, the lesser toxic effects of arsenic ions on bacterial sporulation frequency and germination highlight this strain's ability to thrive under catastrophic conditions. Moreover, the whole genome analysis elucidated diverse metal redox/resistance genes that included a potential arsenite S-adenosylmethyltransferase capable of mitigating arsenite toxicity. Owing to its arsenic resistance, conditional redox activities and ability to interact with arsenic minerals leading to arsenic mobilization, the presence of such spore-forming strains could be a decisive indication towards arsenic mobilization in subsurface aquifers having a high concentration of soluble arsenic or its source minerals.

Micro-colonization of arsenic-resistant Staphylococcus sp. As-3 on arsenopyrite (FeAsS) drives arsenic mobilization under anoxic sub-surface mimicking conditions.

We investigated the subsurface biomatrix of the most abundant As-mineral, arsenopyrite (FeAsS), and meticulously studied a potential biogenic arsenic mobilization phenomenon. An arsenic-resistant [up to 7.5 mM As(III) and 200 mM As(V)] and arsenate-reducing bacterial strain (Staphylococcus sp. As-3) was isolated from a sediment core sample taken from the Budai borehole, on the southwestern coast of Taiwan. Isolate As-3 could reduce 5 mM As(V) to 3.04 mM in 96 h, generating 1.6 mM As(III) under anoxic conditions. Isolate As-3, which adsorbed As(V) up to 19.02 mg g-1 (cdw) and As(III) up to 0.46 mg g-1 (cdw), demonstrated effective As-bioaccumulating ability, as corroborated by a TEM-EDS analysis. Under anaerobic batch conditions, isolate As-3 micro-colonies could grow on as well as interact with arsenopyrite (FeAsS), mobilizing arsenic into soluble phase as As(III) and As(V). Using synchrotron radiation-based FTIR micro-spectroscopy, various functional group signatures and critical chemical bonds enabling a direct interaction with arsenopyrite were underpinned, such as a potential P-OFe bond involved in facilitating bacteria-mineral interaction. Using atomic force microscopy, we analyzed the scattered bacterial cell arrangement and structure and measured various biomechanical properties of micro-colonized Staphylococcus sp. As-3 cells on arsenopyrite. We suggest that the release of organic acids from As-3 drives soluble arsenic release in the aqueous phase under anoxic conditions through oxidative dissolution. Furthermore, arsC-encoding putative cytoplasmic arsenic reductase sequencing and transcript characterization indicated that arsC plays a possible role in the reduction of moderately soluble As(V) to highly soluble toxic As(III) under anoxic conditions. Thus, we suggest that firmicutes such as Staphylococcus sp. As-3 may play an important role in microbially-mediated arsenic mobilization, leading to arsenic release in the sub-surface niche.

Effects of inorganic nutrient levels on the biodegradation of benzene, toluene, and xylene (BTX) by Pseudomonas spp. in a laboratory porous media sand aquifer model.

The effect of inorganic nutrients (sulfate, phosphate, and ammonium chloride) on the aerobic biodegradation of benzene, toluene, and xylene (BTX) by Pseudomonas spp. was studied in the laboratory using a glass sand tank. The increase of nutrient levels resulted in enhanced bacterial growth and BTX degradation. Sulfate and phosphate serve as key electron acceptors in the microbiological processes degrading BTX. The observed bacterial morphological changes during BTX degradation reveal that the filamentous bacteria were the dominant species at low temperatures about 20 degrees C. The spherical and rod-shaped cells became dominant at higher temperatures ranging from 25 degrees C to 28 degrees C. When the BTX mixture was allowed to be biodegraded for longer incubation periods of 21-42 h at high phosphate concentrations, large amounts of rod-shaped cells were clustered. The morphological adaptation appears to be controlled by the temperature and nutrient levels in the sandy medium where Pseudomonas spp. thrives.

Geochemistry of high arsenic groundwater in Chia-Nan plain, Southwestern Taiwan: possible sources and reactive transport of arsenic.

Major ion, trace element, and stable isotope analyses were performed on groundwater samples collected during November 2005 and 2006 in Chia-Nan plain of southwestern Taiwan to examine As mobilization in aquifers. The high concentrations of As, Fe and Mn in the groundwater is consistent with low Eh values (under moderately reduced state). Moreover, the observed Na/Cl and SO(4)/Cl molar ratios in groundwater demonstrate the influence of seawater intrusion. Seawater intrusion could provide required electron acceptors (i.e., SO(4)) for bacterial sulfate reduction and promote reducing conditions that are favorable for As mobilization. The concurrent increases in the concentrations of Fe and Mn from 2005 to 2006 may be caused by bacterial Fe(III) and Mn(IV) reduction. Geochemical modeling demonstrate that As(III) is the dominant As species and the presence of Fe-bearing carbonates, sulfides, and oxide phases may locally act as potential sinks for As. Mud volcano fluids were also collected and analyzed to assess the possible source of As in the Chia-Nan plain groundwater. The oxygen and hydrogen isotopic signatures indicate that the As-rich mud volcano fluids may have been modified by chemical exchange with (18)O-rich crustal rocks and possibly originated from mixing of deep brines with circulating meteoric water. Thus As in the Chia-Nan plain groundwater may have been evolved from deep crustal fluids or rock sources. The hydrogeochemistry and widespread As enrichment in groundwater of Chia-Nan plain result from multiple processes, e.g., de-watering of deep crustal fluids, seawater intrusion, and biogeochemical cycling of Fe, As, and S in alluvial sediments.

Hydrogeochemical behavior of arsenic-enriched groundwater in the deltaic environment: comparison between two study sites in West Bengal, India.

Groundwaters have been collected from deltaic areas of West Bengal (Chakdaha and Baruipur blocks) to record their hydrogeochemical characteristics, and to verify the mechanism of arsenic (As) release. The data reveals that shallow (<70 m) groundwaters in both areas are of Ca-Mg-HCO(3) type; however deeper (>70 m) groundwaters in Baruipur areas are slightly enriched with Na, Cl and SO(4), indicating possible saline water intrusion. The groundwater is anoxic (mean Eh: -124 and -131 mV) with high levels of As (mean: 116 and 293 microg/L), Fe (mean: 4.74 and 3.83 mg/L), PO(4) (mean: 3.73 and 3.21 mg/L) and Mn (mean: 0.37 and 0.49 mg/L), respectively for Chakdaha and Baruipur areas. The observed values of As and bicarbonate (mean: 409 and 499 mg/L) in the shallow aquifer are indicative of redox processes (e.g., oxidation of organic matter) favouring the release of As. Moreover, the presence of DOC in the shallow aquifer suggests that organic matter is young and reactive, and may actively engage in redox driven processes. Our study further confirms that both Fe- and Mn-reduction processes are the dominant mechanisms for As release in these groundwaters.