Dan Lapworth

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.

Quantification of natural DOM from UV absorption at two wavelengths.

Environmental context. Dissolved organic matter (DOM) is part of the global carbon cycle, ecologically and geochemically active, and costly to remove in water treatment. Spectroscopic monitoring at a single wavelength provides some indication of DOM concentration, but variations in optical properties mean that accurate determinations currently rely on slow and costly laboratory methods. We show that for water samples containing non-anthropogenic DOM, ultraviolet absorbance at two wavelengths can quantify DOM rapidly, cheaply and accurately, and also indicate its quality. Abstract. The precise simulation of ultraviolet absorption by 23 contrasting surface-water DOM samples was achieved with a model based on two components, one absorbing light strongly (A) and the other weakly (B). The parameterised model can be used to predict (DOC) in water samples simply from absorbance values at two wavelengths, while information on DOM quality is provided by the calculated fractionation into A and B. The model was tested by predicting (DOC) for a separate dataset obtained by combining results for 12 samples each from surface waters in the UK, Canada and the USA, and from UK groundwaters. A close correlation (R 2 = 0.997) was obtained, with only slight underestimation of the true (DOC). The proportions of components A and B varied considerably among the sites, which explains why precise prediction of (DOC) from absorbance data at a single wavelength was not possible. When the model was applied to samples collected from river locations in a heterogeneous UK catchment with areas of industry and high human population, (DOC) was underestimated in many cases, which may indicate the presence of non-absorbing pollutant DOM. Additional keywords: dissolved organic carbon, dissolved organic matter, two-component model, UV spectra.

Understanding groundwater, surface water and hyporheic zone biogeochemical processes in a Chalk catchment using fluorescence properties of dissolved and colloidal organic matter

Understanding groundwater–surface water (GW–SW) interaction in Chalk catchments is complicated by the degree of geological heterogeneity. At this study site, in southern England (United Kingdom), alluvial deposits in the riparian zone can be considered as a patchwork of varying grades and types with an equally varied lateral connectivity. Some display good connection with the river system and others good connection with the groundwater system and by definition poorer connectivity with the surface water. By coupling tangential flow fractionation (TFF) with fluorescence analysis we were able to characterise the organic matter in the river and hyporheic zone. There is a significant proportion of particulate and colloidal fluorescent organic matter (FOM) within the river system, and at depth within the gravels beneath the river channel. At depth in the hyporheic zone the surface water inputs are dampened by mixing with deeper groundwater FOM. The shallow (0-0.5 m below river bed) hyporheic zone is highly dynamic as a result of changing surface water inputs from upstream processes. Labile C in the form of protein-like FOM appears to be attenuated preferentially compared to fulvic-like fluorescence in the hyporheic zone compared to the adjacent gravel and sand deposits. These preliminary findings have important implications for understanding nutrient and trace element mobility and attenuation within the groundwater, surface water and hyporheic zone of permeable Chalk catchments. Fluorescence analysis of dissolved organic matter has been shown to be a useful environmental tracer that can be used in conjunction with other methods to understand GW-SW processes within a permeable Chalk catchment.

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.

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.

Nitrogen sources, transport and processing in peri-urban floodplains

Peri-urban floodplains are an important interface between developed land and the aquatic environment and may act as a source or sink for contaminants moving from urban areas towards surface water courses. With increasing pressure from urban development the functioning of floodplains is coming under greater scrutiny. A number of peri-urban sites have been found to be populated with legacy landfills which could potentially cause pollution of adjacent river bodies. Here, a peri-urban floodplain adjoining the city of Oxford, UK, with the River Thames has been investigated over a period of three years through repeated sampling of groundwaters from existing and specially constructed piezometers. A nearby landfill has been found to have imprinted a strong signal on the groundwater with particularly high concentrations of ammonium and generally low concentrations of nitrate and dissolved oxygen. An intensive study of nitrogen dynamics through the use of N-species chemistry, nitrogen isotopes and dissolved nitrous oxide reveals that there is little or no denitrification in the majority of the main landfill plume, and neither is the ammonium significantly retarded by sorption to the aquifer sediments. A simple model has determined the flux of total nitrogen and ammonium from the landfill, through the floodplain and into the river. Over an 8 km reach of the river, which has a number of other legacy landfills, it is estimated that 27.5 tonnes of ammonium may be delivered to the river annually. Although this is a relatively small contribution to the total river nitrogen, it may represent up to 15% of the ammonium loading at the study site and over the length of the reach could increase in-stream concentrations by nearly 40%. Catchment management plans that encompass floodplains in the peri-urban environment need to take into account the likely risk to groundwater and surface water quality that these environments pose.

Using boreholes as windows into groundwater ecosystems.

Groundwater ecosystems remain poorly understood yet may provide ecosystem services, make a unique contribution to biodiversity and contain useful bio-indicators of water quality. Little is known about ecosystem variability, the distribution of invertebrates within aquifers, or how representative boreholes are of aquifers. We addressed these issues using borehole imaging and single borehole dilution tests to identify three potential aquifer habitats (fractures, fissures or conduits) intercepted by two Chalk boreholes at different depths beneath the surface (34 to 98 m). These habitats were characterised by sampling the invertebrates, microbiology and hydrochemistry using a packer system to isolate them. Samples were taken with progressively increasing pumped volume to assess differences between borehole and aquifer communities. The study provides a new conceptual framework to infer the origin of water, invertebrates and microbes sampled from boreholes. It demonstrates that pumping 5 m3 at 0.4–1.8 l/sec was sufficient to entrain invertebrates from five to tens of metres into the aquifer during these packer tests. Invertebrates and bacteria were more abundant in the boreholes than in the aquifer, with associated water chemistry variations indicating that boreholes act as sites of enhanced biogeochemical cycling. There was some variability in invertebrate abundance and bacterial community structure between habitats, indicating ecological heterogeneity within the aquifer. However, invertebrates were captured in all aquifer samples, and bacterial abundance, major ion chemistry and dissolved oxygen remained similar. Therefore the study demonstrates that in the Chalk, ecosystems comprising bacteria and invertebrates extend from around the water table to 70 m below it. Hydrogeological techniques provide excellent scope for tackling outstanding questions in groundwater ecology, provided an appropriate conceptual hydrogeological understanding is applied.

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.

Short note: An R script for visualising and analysing fluorescence excitation-emission matrices (EEMs)

Fluorescence excitation–emission matrix (EEM) spectroscopy is an important technique for investigating organic material and produces a complex output that often requires further processing for useful analysis. This computer note outlines a tool for producing a range of plots of fluorescence EEM data in the open–source statistical package R. A script has been written that allows the user to input data from Excel worksheets (CSV files) and process multiple input data files. The R script will then produce the plots and summary statistics, in the form of a CSV table, and write the output files to a user specified folder. Plot types include filled contour plots and 3D wireframe perspective plots for whole EEMs, filled contour plots for selected regions within an EEM and plots for specified slices across the EEM. This script provides a free tool to enable the user to rapidly visualise EEMs and produce tailored EEM plots and slices through EEMs of publication quality.

Characterization of suboxic groundwater colloids using a multi-method approach

Anoxic groundwater colloid properties were measured using a minimally perturbing procedure for sampling, processing, and analysis. Analytical methods included atomic force microscopy (AFM), flow field flow fractionation (FlFFF), and transmission and scanning electron microscopy (TEM and SEM). Shallow groundwater samples showed abundant iron rich nanoparticles (NP) with diameters of 10-30 nm as well as a smaller heterogeneous polydisperse dissolved organic matter (DOM) fraction. AFM results showed NP with average heights of 10 ± 2 nm, which was corroborated by high-resolution TEM and SEM. FlFFF with UV254 nm detection found particles with number average diffusion coefficients of 2-3 × 10(-10) m(2) s(-1) and hydrodynamic diameters between 1.5 and 2 nm probably representing smaller organic macromolecules. Aeration of the samples resulted in extensive agglomeration of NP to form larger (>50 nm) colloids, and a reduction of UV-absorbing material in the 0.5-4 nm range. The complementary methods described have potential applications for investigating the fate and transport of NP in suboxic hotspots such as leachate plumes, wastewater treatment plants, and within the hyporheic mixing zone.