Paul R. Lythgoe

Arsenic hazard in shallow Cambodian groundwaters

Abstract Our recent discovery of hazardous concentrations of arsenic in shallow sedimentary aquifers in Cambodia raises the spectre of future deleterious health impacts on a population that, particularly in non-urban areas, extensively use untreated groundwater as a source of drinking water and, in some instances, as irrigation water. We present here small-scale hazard maps for arsenic in shallow Cambodian groundwaters based on >1000 groundwater samples analysed in the Manchester Analytical Geochemistry Unit and elsewhere. Key indicators for hazardous concentrations of arsenic in Cambodian groundwaters include: (1) well depths greater than 16 m; (2) Holocene host sediments; and (3) proximity to major modem channels of the Mekong (and its distributary the Bassac). However, high-arsenic well waters are also commonly found in wells not exhibiting these key characteristics, notably in some shallower Holocene wells, and in wells drilled into older Quaternary and Neogene sediments. It is emphasized that the maps and tables presented are most useful for identifying current regional trends in groundwater arsenic hazard and that their use for predicting arsenic concentrations in individual wells, for example for the purposes of well switching, is not recommended, particularly because of the lack of sufficient data (especially at depths >80 m) and because, as in Bangladesh and West Bengal, there is considerable heterogeneity of groundwater arsenic concentrations on a scale of metres to hundreds of metres. We have insufficient data at this time to determine unequivocally whether or not arsenic concentrations are increasing in shallow Cambodian groundwaters as a result of groundwater-abstraction activities.

High arsenic in rice is associated with elevated genotoxic effects in humans

Arsenic in drinking water may cause major deleterious health impacts including death. Although arsenic in rice has recently been demonstrated to be a potential exposure route for humans, there has been to date no direct evidence for the impact of such exposure on human health. Here we show for the first time, through a cohort study in West Bengal, India, involving over 400 human subjects not otherwise significantly exposed to arsenic through drinking water, elevated genotoxic effects, as measured by micronuclei (MN) in urothelial cells, associated with the staple consumption of cooked rice with >200 μg/kg arsenic. Further work is required to determine the applicability to populations with different dietary and genetic characteristics, but with over 3 billion people in the world consuming rice as a staple food and several percent of this rice containing such elevated arsenic concentrations, this study raises considerable concerns over the threat to human health.

IC-ICP-MS and IC-ICP-HEX-MS determination of arsenic speciation in surface and groundwaters: preservation and analytical issues

Abstract Understanding the biogeochemical behaviour of arsenic in the weathering and shallow subsurface environment depends critically upon determining the nature and distribution of the chemical species present in natural waters. To this end, coupled ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS) is widely used, though species fractionation during ultrasonic nebulization, and matrix-dependent ionization in the plasma are analytical issues that need to be addressed. Hexapole collision cell technology is shown to be effective in suppressing chloride-based polyatomic interferences. Irrespective of the analytical technique used, As(III)/As(V) ratios of natural waters may change substantially during storage due to (1) differential adsorption of arsenic species on hydrated ferric oxides (HFOs); and (2) microbial activity. A wide range of apparently contradictory speciation changes observed by various workers can be rationalized in terms of the differences of microbial consortia present in different water samples. Arsenic speciation in certain water types can be stabilized for days or even weeks by combined filtration, acidification and refrigeration whilst the addition of EDTA and the use of 0.1 μm filters is indicated for iron-rich waters and waters with high activities of redox-active bacteria, respectively. Although the use of hydrochloric acid has been reported elsewhere as resulting in the apparent oxidation of As(III), we show that for certain water types it acts as an extremely effective preservative of arsenic speciation.

Arsenic speciation in surface waters and sediments in a contaminated waterway: an IC–ICP-MS and XAS based study

Abstract An integrated approach involving the use of ion chromatography–inductively coupled plasma-mass spectrometry (IC–ICP-MS), X-ray absorption spectroscopy (XAS) and sequential extraction procedures has been employed to elucidate the solution and solid phase speciation and partitioning of As in a polluted urban watercourse. Dissolved As concentrations exceeding 130 μg l −1 and comprising entirely inorganic species were determined in the waters of Tinker Brook, a contaminated stream. Upon mixing with a relatively As-free stream, White Ash Brook, both the total concentration of dissolved As and the proportion of As(V) were observed to decrease dramatically below values expected for conservative mixing. This was ascribed to adsorption onto the Fe (oxyhydr)oxides that characterise White Ash Brook on the basis of sequential extraction and direct analysis of the solids via XAS . The shift in oxidation state is speculated to be due to the faster rate of adsorption of As(V) on Fe (oxyhydr)oxides than As(III) in this fast flowing stream system. During periods of reduced supply of anthropogenic As, a small, secondary input of As(III) to White Ash Brook is detectable, delivered by a small ochreous seepage. The Fe (oxyhydr)oxide As-rich deposits surrounding this discharge may also act as a significant source of As upon dissolution during stormflow conditions.

Seasonal Variation of Total Dissolved Arsenic and Arsenic Speciation in A Polluted Surface Waterway

Seasonal differences in the dissolved arsenic concentration and speciation in a contaminated urban waterway in northwest England have been determined using a coupled ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) technique. Waters sampled in the vicinity of an industrial works during relatively dry conditions in April 2000 were found to contain total arsenic concentrations (ΣAs) of up to 132 μg L−1, more than an order magnitude greater than the 4 μg L−1 maximum found in December 2000. The difference in ΣAs between the April and December sampling periods is speculated to be largely due to the irregular anthropogenic supply of arsenic to the watercourse. For both sampling periods, the dissolved arsenic was exclusively inorganic in nature and had an As(V)/ΣAs ratio of between 0.6 and 0.8. Analysis of samples taken downstream of the industrial site, after the confluence with a relatively As-poor stream, revealed that As(III), As(V) and ΣAs concentrations were lower than would be expected from conservative mixing. The As(V)/ΣAs ratio was also observed to decrease markedly. The loss of arsenic from solution is thought to be due to adsorption on the iron oxyhydroxide-rich sediment observed to coat the riverbed downstream of the confluence. The reduction in the As(V)/ΣAs ratio is believed to be due to the more rapid adsorption of As(V) compared to that of As(III). Deviations from conservative behaviour were more marked during the relatively dry April 2000 sampling period and suggest the increased importance of adsorption processes controlling arsenic availability during this time.

Age and Smoking Related Changes in Metal Ion Levels in Human Lens: Implications for Cataract Formation

Age-related cataract formation is the primary cause of blindness worldwide and although treatable by surgical removal of the lens the majority of sufferers have neither the finances nor access to the medical facilities required. Therefore, a better understanding of the pathogenesis of cataract may identify new therapeutic targets to prevent or slow its progression. Cataract incidence is strongly correlated with age and cigarette smoking, factors that are often associated with accumulation of metal ions in other tissues. Therefore this study evaluated the age-related changes in 14 metal ions in 32 post mortem human lenses without known cataract from donors of 11 to 82 years of age by inductively coupled plasma mass spectrometry; smoking-related changes in 10 smokers verses 14 non-smokers were also analysed. A significant age-related increase in selenium and decrease in copper ions was observed for the first time in the lens tissue, where cadmium ion levels were also increased as has been seen previously. Aluminium and vanadium ions were found to be increased in smokers compared to non-smokers (an analysis that has only been carried out before in lenses with cataract). These changes in metal ions, i.e. that occur as a consequence of normal ageing and of smoking, could contribute to cataract formation via induction of oxidative stress pathways, modulation of extracellular matrix structure/function and cellular toxicity. Thus, this study has identified novel changes in metal ions in human lens that could potentially drive the pathology of cataract formation.

Analysis of fountain solutions for anionic components, including alkylbenzenesulfonates, carboxylates and polyphosphates, by a combination of ion-exchange and ion-exclusion chromatography and inductively coupled plasma atomic emission spectrometry

A method for the quantitative determination of the major anionic constituents of fountain solutions, typically mono-, di- and hydroxycarboxylates, alkylbenzenesulfonates, and inorganic anions, including orthophosphate and polyphosphates, is presented here for the first time. The analytical problems arising from extensive co-elution of many of these analytes on an ion-exchange column have been resolved through a combination of (i) careful selection of the concentration gradient of the sodium hydroxide eluent; (ii) parallel analysis by ion-exclusion chromatography; and (iii) determination of total phosphorus by inductively coupled plasma atomic emission spectrometry.

Bioreduction of iodate in sediment microcosms

Abstract Iodine-129 is a high-yield fission product formed in nuclear reactors and is a risk-driving radionuclide in both contaminated land and radioactive waste disposal due to its high mobility and long half-life. Here, the bioreduction behaviour of iodate was investigated by tracking iodine speciation and concentration in solution during the development of progressive anoxia in sediment microcosm experiments incubated at neutral pH. Experiments with acetate added as an electron donor showed the expected cascade of terminal electron-accepting processes. Analysis of solution chemistry showed reduction of iodate to iodide during the early stages of metal (Mn(IV) and Fe(III)) reduction, but with no significant retention of iodine species on solids. There was, however, a net release of natural iodine associated with the sediments to solution when robust iron reduction / sulfate reduction had developed. In addition, over 210 days, the controls with no electron donor and the sterile controls showed no Mn(IV) or Fe(III) reduction but displayed modest sorption of iodate to the sediments in the absence of bioreduction. Overall these results show that under oxic conditions iodate may be partially sorbed to sediments over extended periods but that development of mildly reducing conditions leads to the reductive release of iodine to solution as iodide.

The masquerade of alkaline–carbonatitic tuffs by zeolites: a new global pathfinder hypothesis

Rapid and progressive reaction of alkaline–carbonatitic tuffs with magmatic and crustal fluids disguises their initial character and origin. This is collectively indicated from (a) the extensive literature on zeolite formation from volcanic glass precursors and alkaline fluids, (b) mineralogical characteristics of specific zeolite species, (c) a comparative review of global distributions of alkaline–carbonatite suites and of zeolite minerals, and (d) new trace element data from zeolite samples. A unifying conceptual model based on tectonic and geological settings, hydrological regime and mineralogy is presented that helps to explain the global distributions and current understanding of occurrences. The model will assist in resource exploration by contributing deeper understanding of the economically important bedded zeolite deposits and further, serve as a guide to the discovery of new alkaline–carbonatitic suites, potentially of economic significance (metallic ores and rare earth elements). It follows that future testing of the hypothesis will impact on models of natural carbon cycling as volcanic contributions of CO2 are reviewed.

Multiple environmental factors influence 238U, 232Th and 226Ra bioaccumulation in arbuscular mycorrhizal-associated plants

Ecological consequences of low-dose radioactivity from natural sources or radioactive waste are important to understand but knowledge gaps still remain. In particular, the soil transfer and bioaccumulation of radionuclides into plant roots is poorly studied. Furthermore, better knowledge of arbuscular mycorrhizal (AM) fungi association may help understand the complexities of radionuclide bioaccumulation within the rhizosphere. Plant bioaccumulation of uranium, thorium and radium was demonstrated at two field sites, where plant tissue concentrations reached up to 46.93 μg g-1 238U, 0.67 μg g-1 232Th and 18.27 kBq kg-1 226Ra. High root retention of uranium was consistent in all plant species studied. In contrast, most plants showed greater bioaccumulation of thorium and radium into above-ground tissues. The influence of specific soil parameters on root radionuclide bioaccumulation was examined. Total organic carbon significantly explained the variation in root uranium concentration, while other soil factors including copper concentration, magnesium concentration and pH significantly correlated with root concentrations of uranium, radium and thorium, respectively. All four orders of Glomeromycota were associated with root samples from both sites and all plant species studied showed varying association with AM fungi, ranging from zero to >60% root colonisation by fungal arbuscules. Previous laboratory studies using single plant-fungal species association had found a positive role of AM fungi in root uranium transfer, but no significant correlation between the amount of fungal infection and root uranium content in the field samples was found here. However, there was a significant negative correlation between AM fungal infection and radium accumulation. This study is the first to examine the role of AM fungi in radionuclide soil-plant transfer at a community level within the natural environment. We conclude that biotic factors alongside various abiotic factors influence the soil-plant transfer of radionuclides and future mechanistic studies are needed to explain these interactions in more detail.