Voltammetric determination of inorganic arsenic in mildly acidified (pH 4.7) groundwaters from Mexico and India.

Routine monitoring of inorganic arsenic in groundwater using sensitive, reliable, easy-to-use and affordable analytical methods is integral to identifying sources, and delivering appropriate remediation solutions, to the widespread global issue of arsenic pollution. Voltammetry has many advantages over other analytical techniques, but the low electroactivity of arsenic(V) requires the use of either reducing agents or relatively strong acidic conditions, which both complicate the analytical procedures, and require more complex material handling by skilled operators. Here, we present the voltammetric determination of total inorganic arsenic in conditions of near-neutral pH using a new commercially available 25 µm diameter gold microwire (called the Gold Wirebond), which is described here for the first time. The method is based on the addition of low concentrations of permanganate (10 µM MnO4-) which fulfils two roles: (1) to ensure that all inorganic arsenic is present as arsenate by chemically oxidising arsenite to arsenate and, (2) to provide a source of manganese allowing the sensitive detection of arsenate by anodic stripping voltammetry at a gold electrode. Tests were carried out in synthetic solutions of various pH (ranging from 4.7 to 9) in presence/absence of chloride. The best response was obtained in 0.25 M chloride-containing acetate buffer resulting in analytical parameters (limit of detection of 0.28 µg L-1 for 10 s deposition time, linear range up to 20 µg L-1 and a sensitivity of 63.5 nA ppb-1. s-1) better than those obtained in acidic conditions. We used this new method to measure arsenic concentrations in contrasting groundwaters: the reducing, arsenite-rich groundwaters of India (West Bengal and Bihar regions) and the oxidising, arsenate-rich groundwaters of Mexico (Guanajuato region). Very good agreement was obtained in all groundwaters with arsenic concentrations measured by inductively coupled plasma-mass spectrometry (slope = +1.029, R2 = 0.99). The voltammetric method is sensitive, faster than other voltammetric techniques for detection of arsenic (typically 10 min per sample including triplicate measurements and 2 standard additions), easier to implement than previous methods (no acidic conditions, no chemical reduction required, reproducible sensor, can be used by non-voltammetric experts) and could enable cheaper groundwater surveying campaigns with in-the-field analysis for quick data reporting, even in remote communities.

Epigenetic modifications from arsenic exposure: A comprehensive review.

Arsenic is a notorious element with the potential to harm exposed individuals in ways that include cancerous and non-cancerous health complications. Millions of people across the globe (especially in South and Southeast Asian countries including China, Vietnam, India and Bangladesh) are currently being unknowingly exposed to precarious levels of arsenic. Among the diverse effects associated with such arsenic levels of exposure is the propensity to alter the epigenome. Although a large volume of literature exists on arsenic-induced genotoxicity, cytotoxicity, and inter-individual susceptibility due to active research on these subject areas from the last millennial, it is only recently that attention has turned on the ramifications and mechanisms of arsenic-induced epigenetic changes. The present review summarizes the possible mechanisms involved in arsenic induced epigenetic alterations. It focuses on the mechanisms underlying epigenome reprogramming from arsenic exposure that result in improper cell signaling and dysfunction of various epigenetic components. The mechanistic information articulated from the review is used to propose a number of novel therapeutic strategies with a potential for ameliorating the burden of worldwide arsenic poisoning.

Arsenic exposure from drinking water and staple food (rice): A field scale study in rural Bengal for assessment of human health risk.

Arsenic is a well-known carcinogen with emerging reports showing a range of health outcomes even for low to moderate levels of exposure. This study deals with arsenic exposure and associated increased lifetime cancer risk for populations in arsenic-endemic regions of rural Bengal, where arsenic-safe drinking water is being supplied at present. We found a median total exposure of inorganic arsenic to be 2. 9 µg/Kg BW/day (5th and 95th percentiles were 1.1 µg/Kg BW/day and 7.9 µg/Kg BW/day); with major contribution from cooked rice intake (2.4 µg/Kg BW/day). A significant number of households drank arsenic safe water but used arsenic-rich water for rice cooking. As a result, 67% participants had inorganic arsenic intake above the JEFCA threshold value of 3 µg/Kg BW/day for cancer risk from only rice consumption when arsenic contaminated water was used for cooking (median: 3.5 µg/Kg BW/day) compared to 29% participants that relied on arsenic-free cooking water (median: 1.0 µg/kg BW/day). Arsenic in urine samples of study participants ranged from 31.7 to 520 µg/L and was significantly associated with the arsenic intake (r = 0.76); confirming the preponderance of arsenic exposure from cooked rice. The median arsenic attributable cancer risks from drinking water and cooked rice were estimated to be 2.4 × 10-5 and 2.7 × 10-4 respectively, which further emphasized the importance of arsenic exposure from staple diet. Our results show that any mitigation strategy should include both drinking water and local staple foods in order to minimize the potential health risks of arsenic exposure.

Arsenic contamination, impact and mitigation strategies in rice agro-environment: An inclusive insight.

Arsenic (As) contamination and its adverse consequences on rice agroecosystem are well known. Rice has the credit to feed more than 50% of the world population but concurrently, rice accumulates a substantial amount of As, thereby compromising food security. The gravity of the situation lays in the fact that the population in theAs uncontaminated areas may be accidentally exposed to toxic levels of As from rice consumption. In this review, we are trying to summarize the documents on the impact of As contamination and phytotoxicity in past two decades. The unique feature of this attempt is wide spectrum coverages of topics, and that makes it truly an interdisciplinary review. Aprat from the behaviour of As in rice field soil, we have documented the cellular and molecular response of rice plant upon exposure to As. The potential of various mitigation strategies with particular emphasis on using biochar, seed priming technology, irrigation management, transgenic variety development and other agronomic methods have been critically explored. The review attempts to give a comprehensive and multidiciplinary insight into the behaviour of As in Paddy -Water - Soil - Plate prospective from molecular to post-harvest phase. From the comprehensive literature review, we may conclude that considerable emphasis on rice grain, nutritional and anti-nutritional components, and grain quality traits under arsenic stress condition is yet to be given. Besides these, some emerging mitigation options like seed priming technology, adoption of nanotechnological strategies, applications of biochar should be fortified in large scale without interfering with the proper use of biodiversity.

Synthesis of Ni2P/CdS and Pt/TiO2 nanocomposite for photoreduction of CO2 into methanol.

It is a great challenge to convert thermochemically stable CO2 into value-added products such as CH4, CH3OH, CO via utilizing solar energy. It is also a difficult task to develop an efficient catalyst for the reduction of CO2. We have designed and synthesized noble metal-free photocatalytic nanostructure Ni2P/CdS and Pt/TiO2 for conversion of CO2 to methanol in the presence of sacrificial donor triethylamine (TEA) and hydrogen peroxide. The synthesised catalysts physicochemical properties were studied by using several spectroscopic techniques like; XRD, UV-DRS, XPS, TEM, SEM and PL. Quantification of methanol by GC-MS showed encouraging results of 1424.8 and 2843 µmol g-1 of catalyst for Pt/TiO2 and 5 wt% Ni2P/CdS composites, respectively. Thus, Ni2P/CdS is a promising catalyst with higher productivity and significant selectivity than in-vogue catalysts.

Removal of As(V), Cr(VI) and Cu(II) using novel amine functionalized composite nanofiltration membranes fabricated on ceramic tubular substrate.

Novel amine functionalized composite membranes were prepared over tubular ceramic substrate using facile dip-coating and cross-flow filtration approach. The two fabricated membranes, P-60S and P-60S-EDTA with polyethyleneimine (PEI) and EDTA-modified PEI as functional layers respectively, were characterized in terms of EDX, FTIR, XPS, FESEM, AFM and contact angle analyses which confirmed their stable physical and chemical structure for use in high pressure application. Clean water permeability and MWCO study revealed the superior permeability and rejection efficiency of the P-60S-EDTA compared to the P-60S membrane. Incorporation of bulky EDTA molecules in the membrane functional layer simultaneously decreased pore size and increased membrane hydrophilicity. The removal of As(V), Cr(VI) and Cu(II) heavy metals by both membranes were found to be highly pH dependent and overall rejection improved in case of P-60S-EDTA membrane [99.82% for Cu(II), 96.75% for As(V) and 97.22% for Cr(VI)]. Interestingly, rejection of As(V) and Cr(VI) was significantly improved in presence of Cu(II) due to volume resistance provided by EDTA-Cu(II) complex towards the passage of other heavy metal ions. Excellent stability of P-60S-EDTA membrane in continuous operation of 36 h in both ideal and practical water environment suggests its promising application in real field heavy metal contaminated waste water treatment.

Arsenic retention in cooked rice: Effects of rice type, cooking water, and indigenous cooking methods in West Bengal, India.

This study evaluated the concentration of arsenic in paired raw and cooked rice prepared by individual households in arsenic-endemic rural area of West Bengal. The aim was to investigate how the cooking habits of rural villagers of West Bengal might influence the arsenic content of rice meals. It was found that the use of arsenic-rich groundwater for cooking could elevate the arsenic concentration in cooked rice (up to 129% above the raw sample), thereby enhancing the vulnerability of the rural population of West Bengal to arsenic exposure through rice consumption. The risk is heightened by the habit of drinking the stewed rice water (gruel) in the local communities. The cooking method employed, rice variety, background arsenic concentration in raw rice and cooking water arsenic concentration were found to be important predisposing factors that could affect the accumulation of arsenic in cooked form. The fundamental indigenous cooking practice followed by the villagers requires use of low-arsenic water for cooking as a necessary strategy to alleviate arsenic exposure in their staple food.

Arsenic in groundwater of West Bengal, India: A review of human health risks and assessment of possible intervention options.

This paper reviews how active research in West Bengal has unmasked the endemic arsenism that has detrimental effects on the health of millions of people and their offspring. It documents how the pathways of exposure to this toxin/poison have been greatly expanded through intensive application of groundwater in agriculture in the region within the Green Revolution framework. A goal of this paper is to compare and contrast the similarities and differences in arsenic occurrence in West Bengal with those of other parts of the world and assess the unique socio-cultural factors that determine the risks of exposure to arsenic in local groundwater. Successful intervention options are also critically reviewed with emphasis on integrative strategies that ensure safe water to the population, proper nutrition, and effective ways to reduce the transfer of arsenic from soil to crops. While no universal model may be suited for the vast areas of the world affected with by natural contamination of groundwater with arsenic, we have emphasized community-specific sustainable options that can be adapted. Disseminating scientifically correct information among the population coupled with increased community level participation and education are recognized as necessary adjuncts for an engineering intervention to be successful and sustainable.

Assessment of toxic metals in groundwater and saliva in an arsenic affected area of West Bengal, India: A pilot scale study.

Communities in many parts of the world are unintentionally exposed to arsenic (As) and other toxic metals through ingestion of local drinking water and foods. The concentrations of individual toxic metals often exceed their guidelines in drinking water but the health risks associated with such multiple-metal exposures have yet to receive much attention. This study examines the co-occurrence of toxic metals in groundwater samples collected from As-rich areas of Nadia district, West Bengal, India. Arsenic in groundwater (range: 12-1064 µg L(-1); mean ± S.D: 329±294 µg L(-1)) was the most important contaminant with concentrations well above the WHO guideline of 10 µg L(-1). Another important toxic metal in the study area was manganese (Mn) with average concentration of 202±153 µg L(-1), range of 18-604 µg L(-1). The average concentrations (µg L(-1)) of other elements in groundwater were: Cr (5.6±5.9), Mo (3.5±2.1), Ni (8.3±8.7), Pb (2.9±1.3), Ba (119±43), Zn (56±40), Se (0.60±0.33), U (0.50±0.74). Saliva collected from the male participants of the area had mean concentrations of 6.3±7.0 µg As L(-1) (0.70-29 µg L(-1)), 5.4±5.5 µg Mn L(-1) (0.69-22 µg L(-1)), 2.6±3.1 µg Ni L(-1) (0.15-13 µg L(-1)), 0.78±1.0µg Cr L(-1) (

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.

Remediation of inorganic arsenic in groundwater for safe water supply: a critical assessment of technological solutions.

Arsenic contaminations of groundwater in several parts of the world are the results of natural and/or anthropogenic sources, and have a large impact on human health. Millions of people from different countries rely on groundwater containing As for drinking purposes. This paper reviews removal technologies (oxidation, coagulation flocculation, adsorption, ion exchange and membrane processes) with attention for the drawbacks and limitations of these applied technologies. The technologies suggested and applied for treatment of As rich water have various problems, including the need for further treatment of As containing secondary waste generated from these water treatment processes. More efficient technologies, with a lower tendency to generate waste include the removal of As by membrane distillation or forward osmosis, instead of using pressure driven membrane processes and subsequently reducing soluble As to commercially valuable metallic As are surveyed. An integrated approach of two or more techniques is suggested to be more beneficial than a single process. Advanced technologies such as membrane distillation, forward osmosis as well as some hybrid integrated techniques and their potentials are also discussed in this review. Membrane processes combined with other process (especially iron based technologies) are thought to be most sustainable for the removal of arsenic and further research allowing scale up of these technologies is suggested.

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.

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.

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.

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.