Redox Dependence of Thioarsenate Occurrence in Paddy Soils and the Rice Rhizosphere.

In flooded paddy soils, inorganic and methylated thioarsenates contribute substantially to arsenic speciation besides the much-better-investigated oxyarsenic species, and thioarsenate uptake into rice plants has recently been shown. To better understand their fate when soil redox conditions change, that is, from flooding to drainage to reflooding, batch incubations and unplanted microcosm experiments were conducted with two paddy soils covering redox potentials from EH -260 to +200 mV. Further, occurrence of thioarsenates in the oxygenated rice rhizosphere was investigated using planted rhizobox experiments. Soil flooding resulted in rapid formation of inorganic thioarsenates with a dominance of trithioarsenate. Maximum thiolation of inorganic oxyarsenic species was 57% at EH -130 mV and oxidation caused nearly complete dethiolation. Only monothioarsenate formed again upon reflooding and was the major inorganic thioarsenate detected in the rhizosphere. Maximum thiolation of mono- and dimethylated oxyarsenates was about 70% and 100%, respectively, below EH 0 mV. Dithiolated species dominated over monothiolated species below EH -100 mV. Among all thioarsenates, dimethylated monothioarsenate showed the least transformation upon prolonged oxidation. It also was the major thiolated arsenic species in the rhizosphere with concentrations comparable to its precursor dimethylated oxyarsenate, which is especially critical since dimethylated monothioarsenate is highly carcinogenic.

Thioarsenate Toxicity and Tolerance in the Model System Arabidopsis thaliana.

Thioarsenates form from arsenite under sulfate-reducing conditions, e.g., in rice paddy soils, and are structural analogues of arsenate. Even though rice is one of the most important sources of human arsenic intake, nothing is published about uptake, toxicity, or tolerance of thioarsenates in plants. Experiments using the model system Arabidopsis thaliana showed that monothioarsenate is less toxic than arsenite, but more toxic than arsenate at concentrations ≥25 µM As, reflected in stronger seedling growth inhibition on agar plates. Despite higher toxicity, total As accumulation in roots was lower upon exposure to monothioarsenate compared to arsenate, and a higher root efflux was confirmed. Root-shoot translocation was higher for monothioarsenate than for arsenate. Compared to the wild type (Col-0), both arsenate and monothioarsenate induced higher toxicity in phytochelatin (PC)-deficient mutants (cad1-3) as well as in glutathione biosynthesis (cad2) and PC transport (abcc12) mutants, demonstrating the important role of the PC pathway, not only for arsenate, but also for monothioarsenate detoxification. In Col-0, monothioarsenate induced relatively higher accumulation of PCs than arsenate. The observed differences in plant uptake, toxicity, and tolerance of thioarsenate vs oxyarsenate show that studying the effects of As on plants should include experiments with thiolated As species.

Speciation of arsenic in saliva samples from a population of West Bengal, India.

Saliva, an easily accessible biofluid, is validated as biomarker of arsenic (As) exposure in several villages of West Bengal, India. Pentavalent arsenic [As(V)] was found to be the predominant species in saliva, with the amount of inorganic As [As(V) and trivalent form, As(III)] being more than half of the total As in the samples. Significant association was found between total daily ingestion of As and As(V) (r = 0.59; p = 0.000), As(III) (r = 0.60; p = 0.000), dimethylarsinous acid (DMA(V)) (r = 0.40; p = 0.000), and monomethylarsonous acid (MMA(V)) (r = 0.44; p = 0.000), implying that these species have mainly been derived from the methylation of the inorganic As in the water that study participants drank and the food they ate. Analysis of confounding effects of age, sex, smoking, body mass index and the prevalence of skin lesion suggests that women and controls with no skin lesion had a higher capacity to methylate the ingested As compared to the rest of the population. Thus, our study demonstrates that As species in saliva can be an useful tool to predict the individual susceptibility where higher As exposure and a lower methylation capacity are implicated in the development of As-induced health effects.

Is saliva a potential biomarker of arsenic exposure? A case-control study in West Bengal, India.

Saliva is a biological fluid that has not been used extensively as a biomonitoring tool in epidemiological studies. This study presents the arsenic (As) concentrations in saliva and urine samples collected from populations of West Bengal, India who had been previously exposed to high As levels in their drinking water. We found a significant (p < 0.05) association between the Log transformed Daily Ingestion of As (µg day(-1)) and the As concentration in saliva (r = 0.68). Additionally, As concentration of saliva and urine also had a significant positive correlation (r = 0.60, p < 0.05). Male participants, smokers, and cases of skin lesion were independently and significantly associated with an increase in salivary As. Thus our findings show that saliva is a useful biomarker of As exposure in the study population. The study also advocates that measurement of the forms of As in saliva may additionally provide insight into the internal dose and any individual differences in susceptibility to As exposure.

Risk of arsenic exposure from drinking water and dietary components: implications for risk management in rural Bengal.

This study investigates the risk of arsenic (As) exposure to the communities in rural Bengal, even when they have been supplied with As safe drinking water. The estimates of exposure via dietary and drinking water routes show that, when people are consuming water with an As concentration of less than 10 µg L(-1), the total daily intake of inorganic As (TDI-iAs) exceeds the previous provisional tolerable daily intake (PTDI) value of 2.1 µg day(-1) kg(-1) BW, recommended by the World Health Organization (WHO) in 35% of the cases due to consumption of rice. When the level of As concentration in drinking water is above 10 µg L(-1), the TDI-iAs exceeds the previous PTDI for all the participants. These results imply that, when rice consumption is a significant contributor to the TDI-iAs, supplying water with an As concentration at the current national drinking water standard for India and Bangladesh would place many people above the safety threshold of PTDI. We also found that the consumption of vegetables in rural Bengal does not pose a significant health threat to the population independently. This study suggests that any effort to mitigate the As exposure of the villagers in Bengal must consider the risk of As exposure from rice consumption together with drinking water.

Consumption of brown rice: a potential pathway for arsenic exposure in rural Bengal.

This study assesses the arsenic (As) accumulation in different varieties of rice grain, that people in rural Bengal mostly prefer for daily consumption, to estimate the potential risk of dietary As exposure through rice intake. The rice samples have been classified according to their average length (L) and L to breadth (B) ratio into four categories, such as short-bold (SB), medium-slender (MS), long-slender (LS), and extra-long slender (ELS). The brown colored rice samples fall into the SB, MS, or LS categories; while all Indian Basmati (white colored) are classified as ELS. The study indicates that the average accumulation of As in rice grain increases with a decrease of grain size (ELS: 0.04; LS: 0.10; MS: 0.16; and SB: 0.33 mg kg(-1)), however people living in the rural villages mostly prefer brown colored SB type of rice because of its lower cost. For the participants consuming SB type of brown rice, the total daily intake of inorganic As (TDI-iAs) in 29% of the cases exceeds the previous WHO recommended provisional tolerable daily intake value (2.1 µg day(-1) kg(-1) BW), and in more than 90% of cases, the As content in the drinking water equivalent to the inorganic As intake from rice consumption (C(W,eqv)) exceeds the WHO drinking water guideline of 10 µg L(-1). This study further demonstrates that participants in age groups 18-30 and 51-65 yrs are the most vulnerable to the potential health threat of dietary As exposure compared to participants of age group 31-50 yrs, because of higher amounts of brown rice consumption patterns and lower BMI.

Testing tubewell platform color as a rapid screening tool for arsenic and manganese in drinking water wells.

A low-cost rapid screening tool for arsenic (As) and manganese (Mn) in groundwater is urgently needed to formulate mitigation policies for sustainable drinking water supply. This study attempts to make statistical comparison between tubewell (TW) platform color and the level of As and Mn concentration in groundwater extracted from the respective TW (n = 423), to validate platform color as a screening tool for As and Mn in groundwater. The result shows that a black colored platform with 73% certainty indicates that well water is safe from As, while with 84% certainty a red colored platform indicates that well water is enriched with As, compared to WHO drinking water guideline of 10 µg/L. With this guideline the efficiency, sensitivity, and specificity of the tool are 79%, 77%, and 81%, respectively. However, the certainty values become 93% and 38%, respectively, for black and red colored platforms at 50 µg/L, the drinking water standards for India and Bangladesh. The respective efficiency, sensitivity, and specificity are 65%, 85%, and 59%. Similarly for Mn, black and red colored platform with 78% and 64% certainty, respectively, indicates that well water is either enriched or free from Mn at the Indian national drinking water standard of 300 µg/L. With this guideline the efficiency, sensitivity, and specificity of the tool are 71%, 67%, and 76%, respectively. Thus, this study demonstrates that TW platform color can be potentially used as an initial screening tool for identifying TWs with elevated dissolved As and Mn, to make further rigorous groundwater testing more intensive and implement mitigation options for safe drinking water supplies.

Accumulation of essential and non-essential trace elements in rice grain: Possible health impacts on rice consumers in West Bengal, India.

Rice is the major staple food to the population in rural West Bengal, India and Bangladesh. Depletion and excess accumulation of different trace elements, which are essential and non-essential to the human body, in rice can have a detrimental impact on the rice consumer. Therefore, this study has investigated the accumulation of different trace elements in rice consumed in rural households in West Bengal. The mean concentration (mg kg-1) of essential elements in rice follows the order of Fe (39.4) > Zn (9.79) > Mn (4.40) > Cu (3.26) > Se (0.28) > Co (0.03), while this order for non-essential elements is Pb (1.70) > As (0.34) > Ni (0.22) > Cd (0.04). In general, accumulation in rice is higher for elements that show higher mobility under reducing conditions (e.g. Fe, Mn, As, etc.) compared to elements with lower mobility under such conditions (e.g. Se, Cd, etc.). These orders of accumulation can be attributed to the irrigation practice of continuous flooding of the soil during rice cultivation and the abundance of these elements in the paddy soil itself. By combining these analytical results to the data obtained from questionnaire survey it is estimated that rice consumption can be either enough or a major source to fulfill the daily requirement of Fe, Cu, Se, Mn, and Zn necessary for different physiological functions in the human body for the population in rural Bengal. At the same time, it can be a potential route of As, Cd, Ni, and Pb exposure to develop their non-carcinogenic and carcinogenic health effects among the population. This study highlights that attempts should be made to reduce the accumulation of other non-essential elements together with As in rice grain to ensure the health safety of the people who rarely get a balanced diet and relay on rice consumption to meet the daily calorific intake in rural Bengal.

Arsenic species in raw and cooked rice: implications for human health in rural Bengal.

This study compares the concentrations of total and different species of arsenic (As) in 29 pairs of raw and cooked rice samples collected from households in an area of West Bengal affected by endemic arsenicism. The aim is to investigate the effects of indigenous cooking practice of the rural villagers on As accumulation and speciation in cooked rice. It is found that inorganic As is the predominant species in both raw (93.8%) and cooked rice (88.1%). Cooking of rice with water low in As (<10 µg L(-1)) significantly decreases the total and inorganic As content in cooked rice compared to raw rice. Arsenic concentration is mainly decreased during boiling of rice grains with excess water. Washing of rice grains with low As water has negligible effect on grain As concentration. The study suggests that rice cooking with low As water by the villagers is a beneficial risk reduction strategy. Despite reductions in As content in cooked rice because of cooking with low As water, the consumption of cooked rice represents a significant health threat (in terms of chronic As toxicity) to the study population.

Role of competing ions in the mobilization of arsenic in groundwater of Bengal Basin: insight from surface complexation modeling.

This study assesses the role of competing ions in the mobilization of arsenic (As) by surface complexation modeling of the temporal variability of As in groundwater. The potential use of two different surface complexation models (SCMs), developed for ferrihydrite and goethite, has been explored to account for the temporal variation of As(III) and As(V) concentration, monitored in shallow groundwater of Bengal Basin over a period of 20 months. The SCM for ferrihydrite appears as the better predictor of the observed variation in both As(III) and As(V) concentrations in the study sites. It is estimated that among the competing ions, PO4(3-) is the major competitor of As(III) and As(V) adsorption onto Fe oxyhydroxide, and the competition ability decreases in the order PO4(3-) â‰« Fe(II) > H4SiO4 = HCO3(-). It is further revealed that a small change in pH can also have a significant effect on the mobility of As(III) and As(V) in the aquifers. A decrease in pH increases the concentration of As(III), whereas it decreases the As(V) concentration and vice versa. The present study suggests that the reductive dissolution of Fe oxyhydroxide alone cannot explain the observed high As concentration in groundwater of the Bengal Basin. This study supports the view that the reductive dissolution of Fe oxyhydroxide followed by competitive sorption reactions with the aquifer sediment is the processes responsible for As enrichment in groundwater.

Arsenic mobilization in the aquifers of three physiographic settings of West Bengal, India: understanding geogenic and anthropogenic influences.

A comparative hydrogeochemical study was carried out in West Bengal, India covering three physiographic regions, Debagram and Chakdaha located in the Bhagirathi-Hooghly alluvial plain and Baruipur in the delta front, to demonstrate the control of geogenic and anthropogenic influences on groundwater arsenic (As) mobilization. Groundwater samples (n = 90) from tube wells were analyzed for different physico-chemical parameters. The low redox potential (Eh = -185 to -86 mV) and dominant As(III) and Fe(II) concentrations are indicative of anoxic nature of the aquifer. The shallow (<100 m) and deeper (>100 m) aquifers of Bhagirathi-Hooghly alluvial plains as well as shallow aquifers of delta front are characterized by Ca(2+)HCO3(-) type water, whereas Na(+) and Cl(-) enrichment is found in the deeper aquifer of delta front. The equilibrium of groundwater with respect to carbonate minerals and their precipitation/dissolution seems to be controlling the overall groundwater chemistry. The low SO4(2-) and high DOC, PO4(3-) and HCO3(-) concentrations in groundwater signify ongoing microbial mediated redox processes favoring As mobilization in the aquifer. The As release is influenced by both geogenic (i.e. geomorphology) and anthropogenic (i.e. unsewered sanitation) processes. Multiple geochemical processes, e.g., Fe-oxyhydroxides reduction and carbonate dissolution, are responsible for high As occurrence in groundwaters.

Hydrogeochemical contrast between brown and grey sand aquifers in shallow depth of Bengal Basin: consequences for sustainable drinking water supply.

Delineation of safe aquifer(s) that can be targeted by cheap drilling technology for tubewell (TW) installation becomes highly imperative to ensure access to safe and sustainable drinking water sources for the arsenic (As) affected population in Bengal Basin. This study investigates the potentiality of brown sand aquifers (BSA) as a safe drinking water source by characterizing its hydrogeochemical contrast to grey sand aquifers (GSA) within shallow depth (<70 m) over an area of 100 km(2) in Chakdaha Block of Nadia district, West Bengal, India. The results indicate that despite close similarity in major ion composition, the redox condition is markedly different in groundwater of the two studied aquifers. The redox condition in the BSA is delineated to be Mn oxy-hydroxide reducing, not sufficiently lowered for As mobilization into groundwater. In contrast, the enrichments of NH(4)(+), PO(4)(3-), Fe and As along with lower Eh in groundwater of GSA reflect reductive dissolution of Fe oxy-hydroxide coupled to microbially mediated oxidation of organic matter as the prevailing redox process causing As mobilization into groundwater of this aquifer type. In some portions of GSA the redox status even has reached to the stage of SO(4)(2-) reduction, which to some extent might sequester dissolved As from groundwater by co-precipitation with authigenic pyrite. Despite having low concentration of As in groundwater of the BSA the concentration of Mn often exceeds the drinking water guidelines, which warrants rigorous assessment of attendant health risk for Mn prior to considering mass scale exploitation of the BSA for possible sustainable drinking water supply.

Assessment of arsenic exposure from groundwater and rice in Bengal Delta Region, West Bengal, India.

Arsenic (As) induced identifiable health outcomes are now spreading across Indian subcontinent with continuous discovery of high As concentrations in groundwater. This study deals with groundwater hydrochemistry vis-à-vis As exposure assessment among rural population in Chakdaha block, West Bengal, India. The water quality survey reveals that 96% of the tubewells exceed WHO guideline value (10 µg/L of As). The groundwaters are generally anoxic (-283 to -22 mV) with circum-neutral pH (6.3 to 7.8). The hydrochemistry is dominated by HCO(3)(-) (208 to 440 mg/L), Ca(2+) (79 to 178 mg/L) and Mg(2+) (17 to 45 mg/L) ions along with high concentrations of As(T) (As total, below detection limit to 0.29 mg/L), Fe(T) (Fe total, 1.2 to 16 mg/L), and Fe(II) (0.74 to 16 mg/L). The result demonstrates that Fe(II)-Fe(III) cycling is the dominant process for the release of As from aquifer sediments to groundwater (and vice versa), which is mainly controlled by the local biogeochemical conditions. The exposure scenario reveals that the consumption of groundwater and rice are the major pathways of As accumulation in human body, which is explained by the dietary habit of the surveyed population. Finally, regular awareness campaign is essential as part of the management and prevention of health outcomes.