A field and reactive transport model study of arsenic in a basaltic rock aquifer

The use of geothermal energy as a source for electricity and district heating has increased over recent decades. Dissolved As can be an important constituent of the geothermal fluids brought to the Earth's surface. Here the field application of laboratory measured adsorption coefficients of aqueous As species on basaltic glass surfaces is discussed. The mobility of As species in the basaltic aquifer in the Nesjavellir geothermal system, Iceland was modelled by the one-dimensional (1D) reactive transport model PHREEQC ver. 2, constrained by a long time series of field measurements with the chemical composition of geothermal effluent fluids, pH, Eh and, occasionally, Fe- and As-dissolved species measurements. Di-, tri- and tetrathioarsenic species (As(OH)S22-, AsS₃H^2-, AsS33- and As(SH)4-) were the dominant form of dissolved As in geothermal waters exiting the power plant (2.556μM total As) but converted to some extent to arsenite (H₃AsO₃) and arsenate HAsO42- oxyanions coinciding with rapid oxidation of S2- to S2O32- and finally to SO42- during surface runoff before feeding into a basaltic lava field with a total As concentration of 0.882μM following dilution with other surface waters. A continuous 25-a data set monitoring groundwater chemistry along a cross section of warm springs on the Lake Thingvallavatn shoreline allowed calibration of the 1D model. Furthermore, a series of ground water wells located in the basaltic lava field, provided access along the line of flow of the geothermal effluent waters towards the lake. The conservative ion Cl^- moved through the basaltic lava field (4100m) in less than10a but As was retarded considerably due to surface reactions and has entered a groundwater well 850m down the flow path as arsenate in accordance to the prediction of the 1D model. The 1D model predicted a complete breakthrough of arsenate in the year 2100. In a reduced system arsenite should be retained for about 1ka. © 2011 Elsevier Ltd.

Fate and transport of volatile organic compounds in glacial till and groundwater at an industrial site in Northern Ireland

Volatile organic compound (VOC) contamination of subsurface geological material and groundwater was discovered on the Nortel Monkstown industrial site, Belfast, Northern Ireland. The objectives of this study were to (1) investigate the characteristics of the geological material and its influences on contaminated groundwater flow across the site using borehole logs and hydrological evaluations, and (2) identify the contaminants and examine their distribution in the subsurface geological material and groundwater using chemical analysis. This report focuses on the eastern car park (ECP) which was a former storage area associated with trichloroethene (TCE) degreasing operations. This is where the greatest amount of volatile organic compounds (VOCs), particularly TCE, were detected. The study site is on a complex deposit of clayey glacial till with discontinuous coarser grained lenses, mainly silts, sands and gravel, which occur at 0.45–7.82 m below ground level (bgl). The lenses overall form an elongated formation that acts as a small unconfined shallow aquifer. There is a continuous low permeable stiff clayey till layer beneath the lenses that performs as an aquitard to the groundwater. Highest concentrations of VOCs, mainly TCE, in the geological material and groundwater are in these coarser lenses at ~4.5–7 m bgl. Highest TCE measurements at 390,000 µg L-1 for groundwater and at 39,000 µg kg-1 at 5.7 m for geological material were in borehole GA19 in the coarse lens zone. It is assumed that TCE gained entrance to the subsurface near this borehole where the clayey till was thin to absent above coarse lenses which provided little retardation to the vertical migration of this dense non-aqueous phase liquid (DNAPL) into the groundwater. However, TCE is present in low concentrations in the geological material overlying the coarse lens zone. Additionally, VOCs appear to be associated with poorly drained layers and in peat

Performance of a Sequential Reactive Barrier for Bioremediation of Coal Tar Contaminated Groundwater

Following a thorough site investigation, a biological Sequential Reactive Barrier (SEREBAR), designed to remove Polycyclic Aromatic Hydrocarbons (PAHs) and BTEX compounds, was installed at a Former Manufactured Gas Plant (FMGP) site. The novel design of the barrier comprises, in series, an interceptor and six reactive chambers. The first four chambers (2 nonaerated-2 aerated) were filled with sand to encourage microbial colonization. Sorbant Granular Activated Carbon (GAC) was present in the final two chambers in order to remove any recalcitrant compounds. The SEREBAR has been in continuous operation for 2 years at different operational flow rates (ranging from 320 L/d to 4000 L/d, with corresponding residence times in each chamber of 19 days and 1.5 days, respectively). Under low flow rate conditions (320-520 L/d) the majority of contaminant removal (>93%) occurred biotically within the interceptor and the aerated chambers. Under high flow rates (1000-4000 L/d) and following the installation of a new interceptor to prevent passive aeration, the majority of contaminant removal (>80%) again occurred biotically within the aerated chambers. The sorption zone (GAC) proved to be an effective polishing step, removing any remaining contaminants to acceptable concentrations before discharge down-gradient of the SEREBAR (overall removals >95%).

Isotopic assessment of sources and processes affecting sulfate and nitrate in surface water and groundwater of Luxembourg

Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40 mg/L, d34Ssulfate values between -3.0 and -20.0‰, and d18Osulfate values between +1.5 and +5.0‰; nitrate was characterized by concentrations varying between

Ten Year Performance Evaluation of a Field-Scale Zero-Valent Iron Permeable Reactive Barrier Installed to Remediate Trichloroethene Contaminated Groundwater

The Monkstown Fe0 PRB, Europe’s oldest commercially installed PRB, had been treating trichloroethene (TCE) contaminated groundwater for about 10 years on the Nortel Network site in Northern Ireland when cores were collected in December, 2006. Groundwater data from 2001-2006 indicated that TCE is being remediated to below detection limits as the contaminated groundwater flows through the PRB, Ca and Fe carbonates, crystalline and amorphous FeS, and Fe (oxy)hydroxides precipitates are present in the Fe0 filing material within the PRB. A greater variety of minerals are associated with a 1 cm thick slightly cemented crust at the entrance of the Fe0 section of the reactive vessel and the discontinuous cemented Fe0 material directly below it. Also, a greater presence of microbial communities occurred in the upper portion of the PRB compared to the lower section which might be due to less favourable conditions (i.e. high pH, low oxygen) for microbial growth in the lower section of the PRB. Visual estimation suggests that the Fe0 filings in the effluent section of the PRB have life-span of 10+ years compared to the Fe0 filings in the thin influent section of the PRB which may have a life span of only ~2-5 more years. Multi-tracer tests indicated that preferential pathways have formed in this PRB over the 10 years of operation.

Development and validation of an optical SPR biosensor assay for tiamulin in grass and groundwater

Tiamulin (TIA) is an antimicrobial veterinary drug administered subtherapeutically to prevent swine dysentery and pneumonia. Due to its stability, crystalline structure, and water-soluble properties, TIA is a prime candidate for environmental monitoring. However, there are currently no screening methods available for TIA in environmental matrices, such as grass or ground water. In this paper, the development and validation of a screening method using optical SPR biosensor technology is presented. A solvent extraction was carried out on samples prior to analysis using the Biacore Q instrument. The limit of detection for the assay in grass and ground water was 10.8 ng/g and 2.4 ng/ml, respectively. In addition, the assay was shown to be of an acceptable standard with regard to both accuracy and reproducibility.

Haematite in Lateritic Soils Aids Groundwater Disinfection

Microbiologically contaminated water severely impacts public health in low-income countries, where treated water supplies are often inaccessible to much of the population. Groundwater represents a water source that commonly has better microbiological quality than surface water. A 2-month intensive flow and quality monitoring programme of a spring in a densely settled, unsewered parish of Kampala, Uganda, revealed the persistent presence of high chloride and nitrate concentrations that reflect intense loading of sewage in the spring’s catchment. Conversely, thermotolerant coliform bacteria counts in spring water samples remained very low outside of periods of intense rainfall. Laboratory investigations of mechanisms responsible for this behavior, achieved by injecting a pulse of H40/1 bacteriophage tracer into a column packed with locally derived granular laterite, resulted in near-total tracer adsorption. X-ray diffraction (XRD) analysis showed the laterite to consist predominantly of quartz and kaolinite, with minor amounts (<5%) of haematite. Batch studies comparing laterite adsorption capacity with a soil having comparable mineralogy, but with amorphous iron oxide rather than haematite, showed the laterite to have a significantly greater capacity to adsorb bacteriophage. Batch study results using pure haematite confirmed that its occurrence in laterite contributes substantially to micro-organism attenuation observed and serves to protect underlying groundwater.

Degradation of carbon disulphide (CS2) in soils and groundwater from a CS2 -contaminated site

This study is the first investigation of biodegradation of carbon disulphide (CS₂) in soil that provides estimates of degradation rates and identifies intermediate degradation products and carbon isotope signatures of degradation. Microcosm studies were undertaken under anaerobic conditions using soil and groundwater recovered from CS₂-contaminated sites. Proposed degradation mechanisms were validated using equilibrium speciation modelling of concentrations and carbon isotope ratios. A first-order degradation rate constant of 1.25 × 10-2 h-1 was obtained for biological degradation with soil. Carbonyl sulphide (COS) and hydrogen sulphide (H₂S) were found to be intermediates of degradation, but did not accumulate in vials. A 13C/12C enrichment factor of -7.5 ± 0.8 ‰ was obtained for degradation within microcosms with both soil and groundwater whereas a 13C/12C enrichment factor of -23.0 ± 2.1 ‰ was obtained for degradation with site groundwater alone. It can be concluded that biological degradation of both CS2-contaminated soil and groundwater is likely to occur in the field suggesting that natural attenuation may be an appropriate remedial tool at some sites. The presence of biodegradation by-products including COS and H₂S indicates that biodegradation of CS₂ is occurring and stable carbon isotopes are a promising tool to quantify CS₂ degradation.

Arsenic in groundwater and its influence on exposure risks through traditionally cooked rice in Prey Vêng Province, Cambodia

Arsenic (As) contamination of communal tubewells in Prey Vêng, Cambodia, has been observed since 2000. Many of these wells exceed the WHO As in drinking water standard of 10 µg/L by a factor of 100. The aim of this study was to assess how cooking water source impacts dietary As intake in a rural community in Prey Vêng. This aim was fulfilled by (1) using geostatistical analysis techniques to examine the extent of As contaminated groundwater in Prey Vêng and identify a suitable study site, (2) conducting an on-site study in two villages to measure As content in cooked rice prepared with water collected from tubewells and locally harvested rainwater, and (3) determining the dietary intake of As from consuming this rice. Geostatistical analysis indicated that high risk tubewells (>50 µg As/L) are concentrated along the Mekong River's east bank. Participants using high risk tubewells are consuming up to 24 times more inorganic As daily than recommended by the previous FAO/WHO provisional tolerable daily intake value (2.1 µg/kgBW/day). However, As content in rice cooked in rainwater was significantly reduced, therefore, it is considered to be a safer and more sustainable option for this region.

Production of porous aluminium and iron sulphated oxyhydroxides using industrial grade coagulants for optimised arsenic removal from groundwater

The optimisation of Fe and Al oxyhydroxide materials produced using industrial grade coagulants is presented in this work. The effects of synthesis pH and post-synthesis washing procedure onto the arsenic adsorption capacity of the materials were investigated. It was shown that the materials produced at higher pH were more efficient in removing As(V), especially after cleaning procedure. The materials produced at lower pH were less efficient in removing As(V) but the higher presence of sulphate groups in the materials produced at lower pH enhanced As(III) adsorption. Most performing materials can remove up to 84.7 mg As(V) g^-1 or 77.9 mg As(III) g^-1.

Integrating petrography, mineralogy and hydrochemistry to constrain the influence and distribution of groundwater contributions to baseflow in poorly productive aquifers: Insights from Gortinlieve catchment, Co. Donegal, NW Ireland

Identifying groundwater contributions to baseflowforms an essential part of surfacewater body characterisation. The Gortinlieve catchment (5 km2) comprises a headwater stream network of the Carrigans River, itself a tributary of the River Foyle, NW Ireland. The bedrock comprises poorly productive metasediments that are characterised by fracture porosity. We present the findings of a multi-disciplinary study that integrates new hydrochemical and mineralogical investigations with existing hydraulic, geophysical and structural data to identify the scales of groundwater flow and the nature of groundwater/bedrock interaction (chemical denudation). At the catchment scale, the development of deep weathering profiles is controlled by NE-SW regional scale fracture zones associated with mountain building during the Grampian orogeny. In-situ chemical denudation of mineral phases is controlled by micro- to meso-scale fractures related to Alpine compression during Palaeocene to Oligocene times. The alteration of primary muscovite, chlorite (clinochlore) and albite along the surfaces of these small-scale fractures has resulted in the precipitation of illite, montmorillonite and illite/montmorillonite clay admixtures. The interconnected but discontinuous nature of these small-scale structures highlights the role of larger scale faults and fissures in the supply and transportation of weathering solutions to/from the sites of mineral weathering. The dissolution of primarily mineral phases releases the major ions Mg, Ca and HCO3 that are shown to subsequently formthe chemical makeup of groundwaters. Borehole groundwater and stream baseflow hydrochemical data are used to constrain the depths of groundwater flow pathways influencing the chemistry of surface waters throughout the stream profile. The results show that it is predominantly the lower part of the catchment, which receives inputs from catchment/regional scale groundwater flow, that is found to contribute to the maintenance of annual baseflow levels. This study identifies the importance
of deep groundwater in maintaining annual baseflow levels in poorly productive bedrock systems.

Microbial Ecology and Geo-electrical Responses across a Groundwater Plume

We have used geophysics, microbiology, and geochemistry to link large-scale (30+ m) geophysical self-potential (SP) responses at a groundwater contaminant plume with its chemistry and microbial ecology of groundwater and soil from in and around it. We have found that microbially mediated transformation of ammonia to nitrite, nitrate, and nitrogen gas was likely to have promoted a well-defined electrochemical gradient at the edge of the plume, which dominated the SP response. Phylogenetic analysis demonstrated that the plume fringe or anode of the geobattery was dominated by electrogens and biodegradative microorganisms including Proteobacteria alongside Geobacteraceae, Desulfobulbaceae, and Nitrosomonadaceae. The uncultivated candidate phylum OD1 dominated uncontaminated areas of the site. We defined the redox boundary at the plume edge using the calculated and observed electric SP geophysical measurements. Conductive soils and waste acted as an electronic conductor, which was dominated by abiotic iron cycling processes that sequester electrons generated at the plume fringe. We have suggested that such geoelectric phenomena can act as indicators of natural attenuation processes that control groundwater plumes. Further work is required to monitor electron transfer across the geoelectric dipole to fully define this phenomenon as a geobattery. This approach can be used as a novel way of monitoring microbial activity around the degradation of contaminated groundwater plumes or to monitor in situ bioelectric systems designed to manage groundwater plumes.