Direct speciation analysis of arsenic in sub-cellular compartments using micro-X-ray absorption spectroscopy.

Identification of arsenic chemical species at a sub-cellular level is a key to understanding the mechanisms involved in arsenic toxicology and antitumor pharmacology. When performed with a microbeam, X-ray absorption near-edge structure (mu-XANES) enables the direct speciation analysis of arsenic in sub-cellular compartments avoiding cell fractionation and other preparation steps that might modify the chemical species. This methodology couples tracking of cellular organelles in a single cell by confocal or epifluorescence microscopy with local analysis of chemical species by mu-XANES. Here we report the results obtained with a mu-XANES experimental setup based on Kirkpatrick-Baez X-ray focusing optics that maintains high flux of incoming radiation (>10(11)ph/s) at micrometric spatial resolution (1.5 x 4.0 microm(2)). This original experimental setup enabled the direct speciation analysis of arsenic in sub-cellular organelles with a 10(-15) g detection limit. mu-XANES shows that inorganic arsenite, As(OH)3, is the main form of arsenic in the cytosol, nucleus, and mitochondrial network of cultured cancer cells exposed to As2O3. On the other hand, a predominance of As(III) species is observed in HepG2 cells exposed to As(OH)3 with, in some cases, oxidation to a pentavalent form in nuclear structures of HepG2 cells. The observation of intra-nuclear mixed redox states suggests an inter-individual variability in a cell population that can only be evidenced with direct sub-cellular speciation analysis.

Multiple inorganic toxic substances contaminating the groundwater of Myingyan Township, Myanmar: arsenic, manganese, fluoride, iron, and uranium.

In South Asia, the technological and societal shift from drinking surface water to groundwater has resulted in a great reduction of acute diseases due to water borne pathogens. However, arsenic and other naturally occurring inorganic toxic substances present in groundwater in the region have been linked to a variety of chronic diseases, including cancers, heart disease, and neurological problems. Due to the highly specific symptoms of chronic arsenic poisoning, arsenic was the first inorganic toxic substance to be noticed at unsafe levels in the groundwater of West Bengal, India and Bangladesh. Subsequently, other inorganic toxic substances, including manganese, uranium, and fluoride have been found at unsafe levels in groundwater in South Asia. While numerous drinking water wells throughout Myanmar have been tested for arsenic, relatively little is known about the concentrations of other inorganic toxic substances in Myanmar groundwater. In this study, we analyzed samples from 18 drinking water wells (12 in Myingyan City and 6 in nearby Tha Pyay Thar Village) and 2 locations in the Ayeyarwaddy River for arsenic, boron, barium, beryllium, cadmium, cobalt, chromium, copper, fluoride, iron, mercury, manganese, molybdenum, nickel, lead, antimony, selenium, thallium, uranium, vanadium, and zinc. Concentrations of arsenic, manganese, fluoride, iron, or uranium exceeded health-based reference values in most wells. In addition, any given well usually contained more than one toxic substance at unsafe concentrations. While water testing and well sharing could reduce health risks, none of the wells sampled provide water that is entirely safe with respect to inorganic toxic substances. It is imperative that users of these wells, and users of other wells that have not been tested for multiple inorganic toxic substances throughout the region, be informed of the need for drinking water testing and the health consequences of drinking water contaminated with inorganic toxic substances.

A survey of arsenic, manganese, boron, thorium, and other toxic metals in the groundwater of a West Bengal, India neighbourhood.

Around 150 million people are at risk from arsenic-contaminated groundwater in India and Bangladesh. Multiple metal analysis in Bangladesh has found other toxic elements above the World Health Organization (WHO) health-based drinking water guidelines which significantly increases the number of people at risk due to drinking groundwater. In this study, drinking water samples from the Bongaon area (North 24 Parganas district, West Bengal, India) were analyzed for multiple metal contamination in order to evaluate groundwater quality on the neighbourhood scale. Each sample was analyzed for arsenic (As), boron (B), barium (Ba), chromium (Cr), manganese (Mn), molybdenum (Mo), nickel (Ni), lead (Pb), and uranium (U). Arsenic was found above the WHO health-based drinking water guideline in 50% of these tubewells. Mn and B were found at significant concentrations in 19% and 6% of these tubewells, respectively. The maps of As, Mn, and B concentrations suggest that approximately 75% of this area has no safe tubewells. The concentrations of As, Mn, B, and many other toxic elements are independent of each other. The concentrations of Pb and U were not found above WHO health-based drinking water guidelines but they were statistically related to each other (p-value = 0.001). An analysis of selected isotopes in the Uranium, Actinium, and Thorium Radioactive Decay Series revealed the presence of thorium (Th) in 31% of these tubewells. This discovery of Th, which does not have a WHO health-based drinking water guideline, is a potential public health challenge. In sum, the widespread presence and independent distribution of other metals besides As must be taken into consideration for drinking water remediation strategies involving well switching or home-scale water treatment.

Public health strategies for western Bangladesh that address arsenic, manganese, uranium, and other toxic elements in drinking water.

BACKGROUND: More than 60,000,000 Bangladeshis are drinking water with unsafe concentrations of one or more elements. OBJECTIVES: Our aims in this study were to evaluate and improve the drinking water testing and treatment plans for western Bangladesh. METHODS: We sampled groundwater from four neighborhoods in western Bangladesh to determine the distributions of arsenic, boron, barium, chromium, iron, manganese, molybdenum, nickel, lead, antimony, selenium, uranium, and zinc, and to determine pH. RESULTS: The percentages of tube wells that had concentrations exceeding World Health Organization (WHO) health-based drinking water guidelines were 78% for Mn, 48% for U, 33% for As, 1% for Pb, 1% for Ni, and 1% for Cr. Individual tube wells often had unsafe concentrations of both Mn and As or both Mn and U. They seldom had unsafe concentrations of both As and U. CONCLUSIONS: These results suggest that the ongoing program of identifying safe drinking water supplies by testing every tube well for As only will not ensure safe concentrations of Mn, U, Pb, Ni, Cr, and possibly other elements. To maximize efficiency, drinking water testing in Bangladesh should be completed in three steps: 1) all tube wells must be sampled and tested for As; 2) if a sample meets the WHO guideline for As, then it should be retested for Mn and U; 3) if a sample meets the WHO guidelines for As, Mn, and U, then it should be retested for B, Ba, Cr, Mo, Ni, and Pb. All safe tube wells should be considered for use as public drinking water supplies.

Subcellular speciation analysis of trace element oxidation states using synchrotron radiation micro-X-ray absorption near-edge structure.

Identification of chemical species at a subcellular level is a key to understand the mechanisms involved in the biology of chemical elements. When performed with a microbeam, X-ray absorption near-edge structure (micro-XANES) enables the direct speciation analysis of oxidation states in subcellular compartments avoiding cell fractionation and other preparation steps that might modify the chemical species. Here we report the principal characteristics in terms of spatial resolution, detection limit, reproducibility, and repeatability of a micro-XANES experimental setup based on Kirkpatrick-Baez X-ray focusing optics that maintains high flux of incoming radiation (>10(11) photons/s) at micrometric spatial resolution (1.5 x 4.0 microm2). Applications and limitations of this setup are illustrated by examples of iron and arsenic absorption spectra obtained from the cytosol, nucleus, and mitochondrial network of cultured cells. A better repeatability and sensitivity with no oxidation state modification and minimal beam damage is achieved when cells are analyzed in a frozen hydrated state, as compared to freeze-dried cells. This original experimental setup can now be applied for the direct speciation analysis of most trace elements at the subcellular level.