Method development for rapid quantification of Rn-222 in surface water and groundwater.

Understanding the risks of a developing unconventional hydrocarbons industry, including shale gas, to the chemical quality of surface water and groundwater involves firstly establishing baseline compositions against which any future changes can be assessed. Contaminants of geogenic origin are of particular interest and radon has been identified as one potential contaminant from shale sources. Robust measurement and monitoring of radon in water at environmental concentrations is essential for ensuring protection of water sources and maintaining public confidence. Traditional techniques for Rn-222 determination in water, such as inference by gamma spectrometry and direct alpha counting, are impractical for direct field measurement, and the relatively short half-life of Rn-222 (~ 3.82 days) means that longer analytical protocols from field to the laboratory may result in greater uncertainty for Rn-222 activity. Therefore, a rapid and low-cost method would be beneficial. We have developed and refined a laboratory procedure for Rn-222 monitoring using liquid scintillation counting (LSC). The accuracy of Rn-222 activities obtained via this procedure was evaluated by the analysis of almost 200 water samples collected from streams and boreholes as part of a detailed baseline investigation in the Vale of Pickering, Yorkshire, one potential location for future shale gas exploration. LSC was preferred for measurement of Rn-222 and had comparable accuracy to gamma spectrometry and direct alpha counting. The methodology provided a rapid, portable and low-maintenance option relative to the two established techniques and is shown to be a favourable choice for the measurement of radon in surface water and groundwater at environmental concentrations.

Geological factors controlling occurrence and distribution of arsenic in groundwaters from the southern margin of the Duero Basin, Spain.

Groundwater from springs and boreholes on the southern edge of the Cenozoic Duero Basin (DB) of Spain has concentrations of arsenic (As) which are commonly above the EC drinking-water limit of 10 µg/L and reach observed values up to 241 µg/L. Groundwater compositions within the sedimentary aquifer vary from Ca-HCO3 type, variably affected by evaporation and agricultural pollution at shallow levels, to Na-HCO3 compositions in deeper boreholes of the basin. Groundwater conditions are mainly oxidising, but reducing groundwaters exist in sub-basins within the aquifer, localised flow paths likely being influenced by basement structure. Arsenic concentrations are spatially variable, reaching up to 38 µg/L in springs of the Spanish Central System (SCS) basement aquifer and up to 62 µg/L in springs from the DB. Highest As concentrations are associated with the Na-HCO3 compositions in deep boreholes (200-450 m depth) within the DB. These have high pH values (up to 9.6) which can give rise to associated elevated concentrations of V and U (up to 64 and 30 µg/L, respectively). In the deep borehole waters of the DB, oxidising flows derived from the mineralised igneous-metamorphic basement and discharging via major faults, and are considered the origin of the higher concentrations. Compositions are consistent with desorption of As and other anionic species from metal oxyhydroxides in an oxic environment. Under locally reducing conditions prevalent in some low-flow parts of the DB, an absence of detectable dissolved As is coincident with low or undetectable SO4 concentrations, and consistent with loss via formation of authigenic sulphide minerals. Mitigation measures are needed urgently in this semi-arid region where provision of alternative sources of safe drinking water is logistically difficult and expensive.

Mobilization of arsenic and other trace elements of health concern in groundwater from the Salí River Basin, Tucumán Province, Argentina.

The Salí River Basin in north-west Argentina (7,000 km(2)) is composed of a sequence of Tertiary and Quaternary loess deposits, which have been substantially reworked by fluvial and aeolian processes. As with other areas of the Chaco-Pampean Plain, groundwater in the basin suffers a range of chemical quality problems, including arsenic (concentrations in the range of 12.2-1,660 µg L(-1)), fluoride (50-8,740 µg L(-1)), boron (34.0-9,550 µg L(-1)), vanadium (30.7-300 µg L(-1)) and uranium (0.03-125 µg L(-1)). Shallow groundwater (depths up to 15 m) has particularly high concentrations of these elements. Exceedances above WHO (2011) guideline values are 100% for As, 35% for B, 21% for U and 17% for F. Concentrations in deep (>200 m) and artesian groundwater in the basin are also often high, though less extreme than at shallow depths. The waters are oxidizing, with often high bicarbonate concentrations (50.0-1,260 mg L(-1)) and pH (6.28-9.24). The ultimate sources of these trace elements are the volcanic components of the loess deposits, although sorption reactions involving secondary Al and Fe oxides also regulate the distribution and mobility of trace elements in the aquifers. In addition, concentrations of chromium lie in range of 79.4-232 µg L(-1) in shallow groundwater, 129-250 µg L(-1) in deep groundwater and 110-218 µg L(-1) in artesian groundwater. All exceed the WHO guideline value of 50 µg L(-1). Their origin is likely to be predominantly geogenic, present as chromate in the ambient oxic and alkaline aquifer conditions.

Global Groundwater Solute Composition and Concentrations.

Informed analysis of policies related to food security, global climate change, wetland ecology, environmental nutrient flux, element cycling, groundwater weathering, continental denudation, human health, and others depends to a large extent on quantitative estimates of solute mass fluxes into and out of all global element pools including the enigmatic global aquifer systems. Herein for the first time, we proffer the mean global solute concentration of all major and selected minor and trace solutes in the active groundwater that represents 99% of liquid fresh water on Earth. Concentrations in this significant element pool have yielded to a geospatial machine learning kNN-nearest neighbors' algorithm with numerous geospatial predictors utilizing a large new lithology/climate/aquifer age/elevation based solute database. The predicted concentrations are consistent with traditional solute ratios, concentrations, and thermodynamic saturation indices.

Hazard Ranking Method for Populations Exposed to Arsenic in Private Water Supplies: Relation to Bedrock Geology.

Approximately one million people in the UK are served by private water supplies (PWS) where main municipal water supply system connection is not practical or where PWS is the preferred option. Chronic exposure to contaminants in PWS may have adverse effects on health. South West England is an area with elevated arsenic concentrations in groundwater and over 9000 domestic dwellings here are supplied by PWS. There remains uncertainty as to the extent of the population exposed to arsenic (As), and the factors predicting such exposure. We describe a hazard assessment model based on simplified geology with the potential to predict exposure to As in PWS. Households with a recorded PWS in Cornwall were recruited to take part in a water sampling programme from 2011 to 2013. Bedrock geologies were aggregated and classified into nine Simplified Bedrock Geological Categories (SBGC), plus a cross-cutting "mineralized" area. PWS were sampled by random selection within SBGCs and some 508 households volunteered for the study. Transformations of the data were explored to estimate the distribution of As concentrations for PWS by SBGC. Using the distribution per SBGC, we predict the proportion of dwellings that would be affected by high concentrations and rank the geologies according to hazard. Within most SBGCs, As concentrations were found to have log-normal distributions. Across these areas, the proportion of dwellings predicted to have drinking water over the prescribed concentration value (PCV) for As ranged from 0% to 20%. From these results, a pilot predictive model was developed calculating the proportion of PWS above the PCV for As and hazard ranking supports local decision making and prioritization. With further development and testing, this can help local authorities predict the number of dwellings that might fail the PCV for As, based on bedrock geology. The model presented here for Cornwall could be applied in areas with similar geologies. Application of the method requires independent validation and further groundwater-derived PWS sampling on other geological formations.

Redox patterns and trace-element behavior in the East Midlands Triassic Sandstone Aquifer, U.K.

Redox conditions exercise important controls on water chemistry in the red-bed Sherwood Sandstone Aquifer of the English East Midlands. A distinct redox boundary exists some 3 to 5 km downgradient of the onset of confined conditions, defined by a 300 mV drop in Eh and complete reaction of dissolved oxygen. The aerobic aquifer contains polluted water with high nitrate concentrations and organic carbon significantly above background concentrations (> 0.2 mg/L). Concentrations of Fe, Mn, and Mo are highest in reducing ground water. As, Sb, Se, and U show a residence-time-dependent increase in aerobic ground water, but are much lower under reducing conditions. Iron oxides are believed to play a key role in determining the spatial patterns in many of these trace elements as a result of Eh- and pH-controlled sorption/desorption reactions, as well as some reductive dissolution in the confined aquifer. Fresh ground water persists in the confined aquifer to approximately 30 km downgradient of the redox boundary. However, SO4 concentrations increase progressively along the flowline as a result of the dissolution of gypsum or anhydrite. Concentrations of available organic carbon are low in ground water (1 mg/L or less) and are also likely to be limited in the sediments; conditions are insufficiently reducing for significant sulphate reduction to have taken place. Only in the extreme down-gradient (eastern) part of the aquifer do conditions become sufficiently reducing with some evidence of sulphate reduction. In this part of the aquifer, ground water is more saline (TDS values up to 10 g/L) and is believed to be composed substantially of older formation water. This has distinctive concentrations of several redox-influenced trace elements, with relatively high Fe, Mn, As, and Sb, occasional high Cr, and low Mo relative to the confined fresh ground water upgradient.