ALBERT

Description: The dispersion and sediment-water partitioning of Pb and Zn have been studied in the Conwy River, North Wales. Analysis included major and trace element water chemistry and concentrations of sediment-hosted Pb and Zn. In situ solution pH, Eh, temperature and conductivity were also measured. Sediments were characterized via SEM, XRD, nitric acid leaching and sequential chemical extraction to quantify metal distribution and sediment phase associations. Dissolved and sediment-bound Pb and Zn within river and estuary waters and sediments have been used to calculate whole sediment- and phase-specific apparent partition coefficients.Weathering of galena and sphalerite, associated with the Llanrwst Mining Field, provide point sources of elevated dissolved and sedimentary Pb and Zn in the upper catchment. Dissolved Pb is actively adsorbed onto sedimentary surface coatings of Fe-Mn (hydr)oxides and organics whilst Fe-Mn (hydr)oxides, organics and carbonates were the main hosts for Zn. Systematic changes in metal sorption are evident between the estuary and the upper catchment, with organic matter becoming progressively more important upstream. This change is ascribed to the sorptive properties of sedimentary organic material. Solution pH, [Cl] and aqueous metal speciation are the dominant solution controls on metal partitioning. Laboratory sorption experiments parallel Pb sorption behaviour in the natural system.

Description: In many areas of south and south-eastern Asia, concentrations of As in ground water have been found to exceed the WHO maximum concentration limit of 10 μg/l. This is adversely affecting the health of millions of people and has grave current and future health implications. It has recently been suggested that extensive abstraction of ground water in these areas may accelerate the release of As to ground water. This study uses geochemical and isotopic data to assess this hypothesis. The area investigated in this study is in the Chakdaha block of the Nadia District, West Bengal. The ground water is predominantly of the Ca-Mg-HCO3 type, although some samples were found to contain elevated concentrations of Na, Cl and SO4. This is thought to reflect a greater degree of water-rock interaction at the locations of these particular samples. Arsenic concentrations exceeded the national limit of 50 μg/l in 13 of the 22 samples collected. Four of the 13 samples with high As were recovered from tubewells with depths of 60 m or more. Shallow ground water samples were found to have a stable isotopic composition which falls subparallel to the Global Meteoric Water Line. This probably represents a contribution of evaporated surface water to the ground water, possibly from surface ponds or re-infiltrating irrigation water. Deep ground water, conversely, was shown to have a composition that closely reflects that of meteoric water. The data presented in this study suggest that, whilst the drawdown of surface waters may drive As release in shallow ground waters, it is not responsible for driving As release in deep ground water. However, local abstraction may have resulted in changes in the ground water flow regime of the area, with contaminated shallow ground waters being drawn into previously uncontaminated deep aquifers.

Description: 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 mm 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.

Description: The major and trace element composition of over 40 wolframites from the Barroca Grande mine of the Panasqueira W-Sn-Cu quartz-vein hosted orebody have been determined by electron probe microanalysis.The hübnerite content of wolframite is largely uniform (12 to 20 mol. %) throughout most of the mine, suggesting relative uniformity in composition of the main stage ore-forming fluids. However, wolframites show a striking pattern of enrichment in niobium adjacent to major sub-vertical fault zones. Typical wolframite Nb2O5 contents are below 1000 ppm, whilst values greater than 1000, 2000 and 4000 ppm are generally only found in wolframites less than 50, 30, and 10 metres respectively from major sub-vertical faults. This strongly suggests that some of these fault zones acted as major pathways for hydrothermal fluid migration during ore formation. The idea that the greisened cupola at Panasqueira was the sole major pathway for fluid movement is discounted.

Description: Determination of the solid-phase arsenic speciation in sediments hosting high-arsenic groundwaters, utilized for drinking and irrigation in Bengal, SE Asia and elsewhere is important in order to understand the biogeochemistry of arsenic. Despite this, there is a relative paucity of speciation data for solid-phase arsenic in such systems, due to preservation difficulties, low arsenic concentrations in the sediments, multiple coordination environments and sample heterogeneity. In this study, X-ray absorption near edge structure spectroscopy was used in conjunction with linear least-squares fitting of model compounds to determine the oxidation state of arsenic in sediments from West Bengal and Cambodia. Whatever the collection and storage method used, substantial oxidation of arsenic was commonly observed over periods of weeks to several months. Sands were particularly susceptible to changes in arsenic oxidation state during storage. Analysis within two or three weeks of collection is therefore recommended, whilst on-site storage under a nitrogen atmosphere immediately after collection is particularly recommended for the preservation of sandy samples. Both muds and sands from West Bengal and Cambodia were dominated by arsenite (As(III)) with

Description: Previous studies from our laboratory have suggested a role for indigenous metal-reducing bacteria in the reduction of sediment-bound As(V), and have also shown that a stable enrichment culture of Fe(III)-reducing bacteria was able to mobilize arsenic (as As(III)) from sediments collected from West Bengal (Islam et al., 2004). To identify the Fe(III)-reducing bacteria that may play a role in the reduction of As(V) and mobilization of As(III), we made a detailed molecular analysis of this enrichment culture. It was dominated by a close relative of Geothrix fermentans, but the type strain of this organism was unable to conserve energy for growth via the dissimilatory reduction of As(V), or reduce As(V) present in a defined medium containing fumarate as the electron acceptor. Furthermore, when the cells were grown using soluble Fe(III)-citrate as an electron acceptor in the presence of As(V), bacterial Fe(III) reduction resulted in the precipitation of the Fe(II)-bearing mineral vivianite in 2 weeks. This was accompanied by the efficient removal of As from solution. These results demonstrate that Geothrix fermentans, in common with other key Fe(III)-reducing bacteria such as Geobacter sulfurreducens, does not reduce As(V) enzymatically, but can capture arsenic in Fe(II) minerals formed during respiration using Fe(III) as an electron acceptor. Thus, the reduction of arsenic-bearing Fe(III) oxide minerals is not sufficient to mobilize arsenic, but may result in the formation of Fe(II) biominerals that could potentially act as sinks for arsenic in sediments. Additional mechanisms, including dissimilatory As(V) reduction by other specialist anaerobic bacteria, are implicated in the mobilization of arsenic from sediments.

Description: 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 modern 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.

Description: Arsenic-rich scales are widely associated with geothermal fields and constitute a potential hazard to human health. Such arsenic has hitherto been reported to be almost exclusively hosted by sulphide or oxide phases or occurring as surface species. We report here, however, the occurrence of an arsenic-rich (1500 to 4000 mg kg—1 As) smectite from geothermal precipitates from a geothermal field in northwestern Japan and present evidence that the arsenic is predominantly hosted within this silicate mineral.Consistently ∼80% of the total arsenic determined in these geothermal precipitates was found by selective chemical extractions to be associated with an operationally defined clay mineral fraction, with lesser proportions being associated with operationally defined amorphous silica, Fe oxide and sulphide fractions. Analysis by XRD, ATR IR and XRF showed the clay fraction to be dominated by Mg-rich trioctahedral smectite.Arsenic K-edge XAS spectra of the smectite suggested the dominance of As(III)-O coordinated species with significant contributions from As(V)-O coordinated species. Both XPS and a magnesium chloride chemical extraction indicated minimal adsorption of arsenic on smectite surfaces suggesting that the arsenic was predominantly either dissolved within the smectite or occurred within mineral occlusions. No such occlusions greater than 1 μm in size were observed in the As-rich smectites.The potential occurrence of arsenic-bearing clays should be considered when determining remediation strategies for geothermal environments or evaluating risks associated with the industrial usage of geothermal precipitates.

Description: Soluble inorganic As is toxic with both cancer and non-cancer endpoints. Of the 80 million people in West Bengal, 50 million are living in the nine As-affected districts with millions at risk from using water for drinking, cooking or irrigation (Chakrabortiet al., 2004). An environmental tragedy is developing in West Bengal with an alarming number of cases of skin lesions (Guha Mazumderet al., 1998; Mukherjeeet al., 2005), respiratory symptoms (von Ehrensteinet al., 2005), adverse pregnancy outcomes and infant mortality (von Ehrensteinet al., 2006) and neurological complications (Mukherjeeet al., 2005) associated with ingestion of As-contaminated water.