Marianne E. Stuart

Review of risk from potential emerging contaminants in UK groundwater

This paper provides a review of the types of emerging organic groundwater contaminants (EGCs) which are beginning to be found in the UK. EGCs are compounds being found in groundwater that were previously not detectable or known to be significant and can come from agricultural, urban and rural point sources. EGCs include nanomaterials, pesticides, pharmaceuticals, industrial compounds, personal care products, fragrances, water treatment by-products, flame retardants and surfactants, as well as caffeine and nicotine. Many are relatively small polar molecules which may not be effectively removed by drinking water treatment. Data from the UK Environment Agencys groundwater screening programme for organic pollutants found within the 30 most frequently detected compounds a number of EGCs such as pesticide metabolites, caffeine and DEET. Specific determinands frequently detected include pesticides metabolites, pharmaceuticals including carbamazepine and triclosan, nicotine, food additives and alkyl phosphates. This paper discusses the routes by which these compounds enter groundwater, their toxicity and potential risks to drinking water and the environment. It identifies challenges that need to be met to minimise risk to drinking water and ecosystems.

Climate change and water in the UK - past changes and future prospects

Climate change is expected to modify rainfall, temperature and catchment hydrological responses across the world, and adapting to these water-related changes is a pressing challenge. This paper reviews the impact of anthropogenic climate change on water in the UK and looks at projections of future change. The natural variability of the UK climate makes change hard to detect; only historical increases in air temperature can be attributed to anthropogenic climate forcing, but over the last 50 years more winter rainfall has been falling in intense events. Future changes in rainfall and evapotranspiration could lead to changed flow regimes and impacts on water quality, aquatic ecosystems and water availability. Summer flows may decrease on average, but floods may become larger and more frequent. River and lake water quality may decline as a result of higher water temperatures, lower river flows and increased algal blooms in summer, and because of higher flows in the winter. In communicating this important work, researchers should pay particular attention to explaining confidence and uncertainty clearly. Much of the relevant research is either global or highly localized: decision-makers would benefit from more studies that address water and climate change at a spatial and temporal scale appropriate for the decisions they make.

The influence of polyatomic ion interferences in analysis by inductively coupled plasma source mass spectrometry (ICP-MS)

Abstract The application of inductively coupled plasma source mass spectrometry (ICP-MS) to the determination of some major, minor and trace elements in limestones and manganese nodules is described. The effect of polyatomic ion interferences characteristic of the sample matrix is evaluated, and the effectiveness of correction procedures is demonstrated. Data are presented for a wide range of elements in three NBS standard reference calcium-rich samples (NBS SRM 1b, 88a and 120b) and the two USGS manganese nodule standard reference materials (Nod-A-1 and Nod-P-1).

A review of the impact of climate change on future nitrate concentrations in groundwater of the UK

This paper reviews the potential impacts of climate change on nitrate concentrations in groundwater of the UK using a Source-Pathway-Receptor framework. Changes in temperature, precipitation quantity and distribution, and atmospheric carbon dioxide concentrations will affect the agricultural nitrate source term through changes in both soil processes and agricultural productivity. Non-agricultural source terms, such as urban areas and atmospheric deposition, are also expected to be affected. The implications for the rate of nitrate leaching to groundwater as a result of these changes are not yet fully understood but predictions suggest that leaching rate may increase under future climate scenarios. Climate change will affect the hydrological cycle with changes to recharge, groundwater levels and resources and flow processes. These changes will impact on concentrations of nitrate in abstracted water and other receptors, such as surface water and groundwater-fed wetlands. The implications for nitrate leaching to groundwater as a result of climate changes are not yet well enough understood to be able to make useful predictions without more site-specific data. The few studies which address the whole cycle show likely changes in nitrate leaching ranging from limited increases to a possible doubling of aquifer concentrations by 2100. These changes may be masked by nitrate reductions from improved agricultural practices, but a range of adaption measures need to be identified. Future impact may also be driven by economic responses to climate change.

Screening for long-term trends in groundwater nitrate monitoring data

Alarge body of UK groundwater nitrate data has been analysed by linear regression to define past trends and estimate future concentrations. Robust regression was used. The datasets showed too many irregularities to justify more traditional time-series approaches such as ARIMA-type methods. Tests were included for lack of linearity, outliers, seasonality and a break in the trend (by piecewise linear regression). Of the series analysed, 21% showed a significant improvement in the overall fit when a break was included. Half of these indicated an increase in trend with time. Significant seasonality was found in about one-third of the series, with the largest nitrate concentrations usually found during winter months. Inclusion of nearby water-level data as an additional explanatory variable successfully accounted for much of this seasonality. Based on 309 datasets from 191 distinct sites, nitrate concentrations were found to be rising at an average of 0.34 mg NO3 l−1 a−1. In 2000, 34% of the sites analysed exceeded the 50 mg l−1 EU drinking water standard. If present trends continue, 41% could exceed the standard by 2015. We explored an alternative to the previously proposed Water Framework Directive aggregation approach for estimating trends in whole groundwater bodies (the ‘Grath’ approach: spatially average then find the trend). We first determined the trends for single boreholes and then spatially averaged these. This approach preserves information about the spatial distribution of trends within the water body and is less sensitive to ‘missing data’.

Fingerprinting groundwater pollution in catchments with contrasting contaminant sources using microorganic compounds.

Evaluating the occurrence of microorganics helps to understand sources and processes which may be controlling the transport and fate of emerging contaminants (ECs). A study was carried out at the contrasting instrumented environmental observatory sites at Oxford, on the peri-urban floodplain gravel aquifer of the River Thames and Boxford, in the rural valley of the River Lambourn on the chalk aquifer, in Southern England to explore the use of ECs to fingerprint contaminant sources and flow pathways in groundwater. At Oxford compounds were typical of a local waste tip plume (not only plasticisers and solvents but also barbiturates and N,N-diethyl-m-toluamide (DEET)) and of the urban area (plasticisers and mood-enhancing drugs such as carbamazepine). At Boxford the results were different with widespread occurrence of agricultural pesticides, their metabolites and the solvent trichloroethene, as well as plasticisers, caffeine, butylated food additives, DEET, parabens and trace polyaromatic hydrocarbons (PAHs). Groups of compounds used in pharmaceuticals and personal care products of different provenance in the environment could be distinguished, i) historical household and medical waste, ii) long-term household usage persistent in groundwater and iii) current usage and contamination from surface water. Co-contaminant and degradation products can also indicate the likely source of contaminants. A cocktail of contaminants can be used as tracers to provide information on catchment pathways and groundwater/surface water interactions. A prominent feature in this study is the attenuation of many EC compounds in the hyporheic zone.

The changing trend in nitrate concentrations in major aquifers due to historical nitrate loading from agricultural land across England and Wales from 1925 to 2150

Nitrate is necessary for agricultural productivity, but can cause considerable problems if released into aquatic systems. Agricultural land is the major source of nitrates in UK groundwater. Due to the long time-lag in the groundwater system, it could take decades for leached nitrate from the soil to discharge into freshwaters. However, this nitrate time-lag has rarely been considered in environmental water management. Against this background, this paper presents an approach to modelling groundwater nitrate at the national scale, to simulate the impacts of historical nitrate loading from agricultural land on the evolution of groundwater nitrate concentrations. An additional process-based component was constructed for the saturated zone of significant aquifers in England and Wales. This uses a simple flow model which requires modelled recharge values, together with published aquifer properties and thickness data. A spatially distributed and temporally variable nitrate input function was also introduced. The sensitivity of parameters was analysed using Monte Carlo simulations. The model was calibrated using national nitrate monitoring data. Time series of annual average nitrate concentrations along with annual spatially distributed nitrate concentration maps from 1925 to 2150 were generated for 28 selected aquifer zones. The results show that 16 aquifer zones have an increasing trend in nitrate concentration, while average nitrate concentrations in the remaining 12 are declining. The results are also indicative of the trend in the flux of groundwater nitrate entering rivers through baseflow. The model thus enables the magnitude and timescale of groundwater nitrate response to be factored into source apportionment tools and to be taken into account alongside current planning of land-management options for reducing nitrate losses.

In-situ tryptophan-like fluorescence: A real-time indicator of faecal contamination in drinking water supplies.

Enteric pathogens are typically inferred from the presence of surrogate indicator organisms such as thermotolerant (faecal) coliforms (TTCs). The analysis of TTCs requires time-consuming incubation in suitable laboratories, which can limit sampling resolution, particularly during critical pollution events. Here, we demonstrate the use of in-situ fluorimeters targeting tryptophan-like compounds as a rapid, reagentless indicator of TTCs in groundwater-derived potable water supplies in Africa. A range of other common indicators of TTCs were also determined including nitrate, turbidity, and sanitary risk survey scores. Sampling was conducted during both the dry and wet seasons to investigate seasonality. Tryptophan-like fluorescence was the most effective predictor of both presence/absence and number of TTCs during both seasons. Seasonal changes in tryptophan-like fluorescence in deeper supplies suggest it is transported more efficiently through the aquifer than TTCs. Moreover, the perennial elevated concentrations in some wells suggest it is more resilient than TTCs in groundwater. Therefore tryptophan-like fluorescence could also be a better indicator of some smaller, more easily transported, and long-lived, pathogenic enteric viruses. These sensors have the potential to be included in real-time pollution alert systems for drinking water supplies throughout the world, as well as for mapping enteric pathogen risks in developing regions.

Persistent and emerging micro-organic contaminants in Chalk groundwater of England and France.

The Chalk aquifer of Northern Europe is an internationally important source of drinking water and sustains baseflow for surface water ecosystems. The areal distribution of microorganic (MO) contaminants, particularly non-regulated emerging MOs, in this aquifer is poorly understood. This study presents results from a reconnaissance survey of MOs in Chalk groundwater, including pharmaceuticals, personal care products and pesticides and their transformation products, conducted across the major Chalk aquifers of England and France. Data from a total of 345 sites collected during 2011 were included in this study to provide a representative baseline assessment of MO occurrence in groundwater. A suite of 42 MOs were analysed for at each site including industrial compounds (n=16), pesticides (n=14) and pharmaceuticals, personal care and lifestyle products (n=12). Occurrence data is evaluated in relation to land use, aquifer exposure, well depth and depth to groundwater to provide an understanding of vulnerable groundwater settings.

Application of inductively coupled plasma mass spectrometry to the simultaneous determination of chlorine, bromine and iodine in the National Bureau of Standards Standard Reference Material 1648 Urban Particulate

The application of inductively coupled plasma mass spectrometry (ICP-MS) to the simultaneous determination of chlorine, bromine and iodine in the National Bureau of Standards (NBS) Standard Reference Material (SRM) 1648 Urban Particulate is described. The potential of ICP-MS for simultaneous multi-element trace determinations after a conventional dissolution procedure is illustrated. Various possible methods for including the halides are considered, and various sample dissolution procedures are investigated. Data presented for the NBS SRM 1648 Urban Particulate are considered in terms of the previously published results and polyatomic ion interferences from sample fusion procedures. It has been shown that the method has great potential for the determination of total chlorine, bromine and iodine in environmental dust and other samples.