The nitrate time bomb: a numerical way to investigate nitrate storage and lag time in the unsaturated zone.

Nitrate pollution in groundwater, which is mainly from agricultural activities, remains an international problem. It threatens the environment, economics and human health. There is a rising trend in nitrate concentrations in many UK groundwater bodies. Research has shown it can take decades for leached nitrate from the soil to discharge into groundwater and surface water due to the 'store' of nitrate and its potentially long travel time in the unsaturated and saturated zones. However, this time lag is rarely considered in current water nitrate management and policy development. The aim of this study was to develop a catchment-scale integrated numerical method to investigate the nitrate lag time in the groundwater system, and the Eden Valley, UK, was selected as a case study area. The method involves three models, namely the nitrate time bomb-a process-based model to simulate the nitrate transport in the unsaturated zone (USZ), GISGroundwater--a GISGroundwater flow model, and N-FM--a model to simulate the nitrate transport in the saturated zone. This study answers the scientific questions of when the nitrate currently in the groundwater was loaded into the unsaturated zones and eventually reached the water table; is the rising groundwater nitrate concentration in the study area caused by historic nitrate load; what caused the uneven distribution of groundwater nitrate concentration in the study area; and whether the historic peak nitrate loading has reached the water table in the area. The groundwater nitrate in the area was mainly from the 1980s to 2000s, whilst the groundwater nitrate in most of the source protection zones leached into the system during 1940s-1970s; the large and spatially variable thickness of the USZ is one of the major reasons for unevenly distributed groundwater nitrate concentrations in the study area; the peak nitrate loading around 1983 has affected most of the study area. For areas around the Bowscar, Beacon Edge, Low Plains, Nord Vue, Dale Springs, Gamblesby, Bankwood Springs, and Cliburn, the peak nitrate loading will arrive at the water table in the next 34 years; statistical analysis shows that 8.7 % of the Penrith Sandstone and 7.3 % of the St Bees Sandstone have not been affected by peak nitrate. This research can improve the scientific understanding of nitrate processes in the groundwater system and support the effective management of groundwater nitrate pollution for the study area. With a limited number of parameters, the method and models developed in this study are readily transferable to other areas.

Deep urban groundwater vulnerability in India revealed through the use of emerging organic contaminants and residence time tracers.

Demand for groundwater in urban centres across Asia continues to rise with ever deeper wells being drilled to avoid shallow contamination. The vulnerability of deep alluvial aquifers to contaminant migration is assessed in the ancient city of Varanasi, India, using a novel combination of emerging organic contaminants (EOCs) and groundwater residence time tracers (CFC and SF6). Both shallow and intermediate depth private sources (<100 m) and deep (>100 m) municipal groundwater supplies were found to be contaminated with a range of EOCs including pharmaceuticals (e.g. sulfamethoxazole, 77% detection frequency, range <0.0001-0.034 µg L-1), perfluoroalkyl substances (e.g. PFOS, range <0.0001-0.033 µg L-1) as well as a number of pesticides (e.g. phenoxyacetic acid, range <0.02-0.21 µg L-1). The profile of EOCs found in groundwater mirror those found in surface waters, albeit at lower concentrations, and reflect common waste water sources with attenuation in the subsurface. Mean groundwater residence times were found to be comparable between some deep groundwater and shallow groundwater sources with residence times ranging from >70 to 30 years. Local variations in aquifer geology influence the extent of modern recharge at depth. Both tracers provide compelling evidence of significant inputs of younger groundwater to depth >100 m within the aquifer system.

Phosphorus fluxes to the environment from mains water leakage: Seasonality and future scenarios.

Accurate quantification of sources of phosphorus (P) entering the environment is essential for the management of aquatic ecosystems. P fluxes from mains water leakage (MWL-P) have recently been identified as a potentially significant source of P in urbanised catchments. However, both the temporal dynamics of this flux and the potential future significance relative to P fluxes from wastewater treatment works (WWT-P) remain poorly constrained. Using the River Thames catchment in England as an exemplar, we present the first quantification of both the seasonal dynamics of current MWL-P fluxes and future flux scenarios to 2040, relative to WWT-P loads and to P loads exported from the catchment. The magnitude of the MWL-P flux shows a strong seasonal signal, with pipe burst and leakage events resulting in peak P fluxes in winter (December, January, February) that are >150% of fluxes in either spring (March, April, May) or autumn (September, October, November). We estimate that MWL-P is equivalent to up to 20% of WWT-P during peak leakage events. Winter rainfall events control temporal variation in both WWT-P and riverine P fluxes which consequently masks any signal in riverine P fluxes associated with MWL-P. The annual average ratio of MWL-P flux to WWT-P flux is predicted to increase from 15 to 38% between 2015 and 2040, associated with large increases in P removal at wastewater treatment works by 2040 relative to modest reductions in mains water leakage. However, further research is required to understand the fate of MWL-P in the environment. Future P research and management programmes should more fully consider MWL-P and its seasonal dynamics, alongside the likely impacts of this source of P on water quality.

Online fluorescence spectroscopy for the real-time evaluation of the microbial quality of drinking water.

We assessed the utility of online fluorescence spectroscopy for the real-time evaluation of the microbial quality of untreated drinking water. Online fluorimeters were installed on the raw water intake at four groundwater-derived UK public water supplies alongside existing turbidity sensors that are used to forewarn of the presence of microbial contamination in the water industry. The fluorimeters targeted fluorescent dissolved organic matter (DOM) peaks at excitation/emission wavelengths of 280/365 nm (tryptophan-like fluorescence, TLF) and 280/450 nm (humic-like fluorescence, HLF). Discrete samples were collected for Escherichia coli, total bacterial cell counts by flow cytometry, and laboratory-based fluorescence and absorbance. Both TLF and HLF were strongly correlated with E. coli (ρ = 0.71-0.77) and total bacterial cell concentrations (ρ = 0.73-0.76), whereas the correlations between turbidity and E. coli (ρ = 0.48) and total bacterial cell counts (ρ = 0.40) were much weaker. No clear TLF peak was observed at the sites and all apparent TLF was considered to be optical bleed-through from the neighbouring HLF peak. Therefore, a HLF fluorimeter alone would be sufficient to evaluate the microbial water quality at these sources. Fluorescent DOM was also influenced by site operations such as pump start-up and the precipitation of cations on the sensor windows. Online fluorescent DOM sensors are a better indicator of the microbial quality of untreated drinking water than turbidity and they have wide-ranging potential applications within the water industry.

Assessing the applicability of global CFC and SF(6) input functions to groundwater dating in the UK.

Chlorofluorocarbons (CFCs) and sulphur hexafluoride (SF(6)) are increasingly being used to date recent groundwater components. While these trace gases are generally well-mixed in the atmosphere, there is evidence that local atmospheric excesses (LAEs) exist in some areas of the world, primarily associated with urbanisation and thereby affecting the interpretation of data derived from groundwater studies. Since the soil acts as a low-pass filter for atmospheric trace gas fluctuations, the possible existence of LAEs in the UK has been investigated by measuring the mixing ratios of CFC-11, CFC-12 and SF(6) in soil gases from sites within the UK's two largest cities (London and Birmingham) and a smaller urban area, Bristol. While there was some evidence of excesses, most of the measured mixing ratios for CFC-12 and SF(6) were less than 10% above the current northern hemisphere atmospheric mixing ratio (NH-AMR) values. CFC-11 was more variable, but usually less than 20% above the NH-AMR value. Surface waters were also investigated as possible short-term archives of trace-gas information but were much less consistent in performance. While the lack of significant current LAEs for SF(6) can justifiably be extrapolated to past decades, different global emission patterns mean that this is much harder to justify for the CFCs. Nevertheless, in the absence of further evidence it is concluded that the use of CFC and SF(6) input functions based on the NH-AMR curves is generally justified for the UK, with the proviso that urban groundwater investigations should not rely on the CFCs as age tracers.

The significance of colloids in the transport of pesticides through Chalk.

Agrochemical contamination in groundwater poses a significant long term threat to water quality and is of concern for legislators, water utilities and consumers alike. In the dual porosity, dual permeability aquifers such as the Chalk aquifer, movement of pesticides and their metabolites through the unsaturated zone to groundwater is generally considered to be through one of two pathways; a rapid by-pass flow and a slower 'piston-flow' route via the rock matrix. However, the dissolved form or 'colloidal species' in which pesticides move within the water body is poorly understood. Following heavy rainfall, very high peaks in pesticide concentration have been observed in shallow Chalk aquifers. These concentrations might be well explained by colloidal transport of pesticides. We have sampled a Chalk groundwater beneath a deep (30 m) unsaturated zone known to be contaminated with the pesticide diuron. Using a tangential flow filtration technique we have produced colloidal fractions from 0.45 microm to 1 kDa. In addition, we have applied agricultural grade diuron to a typical Chalk soil and created a soil water suspension which was also subsequently fractionated using the same filtration system. The deep groundwater sample showed no evidence of association between colloidal material and pesticide concentration. In comparison, despite some evidence of particle trapping or sorption to the filters, the soil water clearly showed an association between the <0.45 microm and <0.1 microm colloidal fractions which displayed significantly higher pesticide concentrations than the unfiltered sample. Degradation products were also observed and found to behave in a similar manner to the parent compound. Although relatively large colloids can be generated in the Chalk soil zone, it appears transport to depth in a colloidal-bound form does not occur. Comparison with other field and monitoring studies suggests that rapid by-pass flow is unlikely to occur beneath 4-5 m. Therefore, shallow groundwaters are most at risk from rapid transport of high concentrations of pesticide-colloidal complexes. The presence of a deep unsaturated zone will mean that most of the colloidal-complexes will be filtered by the narrow Chalk pores and the majority of pesticide transport will occur in a 'dissolved' form through the more gradual 'piston-flow' route.

Global patterns of nitrate storage in the vadose zone.

Global-scale nitrogen budgets developed to quantify anthropogenic impacts on the nitrogen cycle do not explicitly consider nitrate stored in the vadose zone. Here we show that the vadose zone is an important store of nitrate that should be considered in future budgets for effective policymaking. Using estimates of groundwater depth and nitrate leaching for 1900-2000, we quantify the peak global storage of nitrate in the vadose zone as 605-1814 Teragrams (Tg). Estimates of nitrate storage are validated using basin-scale and national-scale estimates and observed groundwater nitrate data. Nitrate storage per unit area is greatest in North America, China and Europe where there are thick vadose zones and extensive historical agriculture. In these areas, long travel times in the vadose zone may delay the impact of changes in agricultural practices on groundwater quality. We argue that in these areas use of conventional nitrogen budget approaches is inappropriate.

Source and persistence of pesticides in a semi-confined chalk aquifer of southeast England.

Pesticide contamination in groundwater is an increasing problem that poses a significant long-term threat to water quality. Following the detection of elevated concentrations of diuron in boreholes in a semi-confined chalk aquifer from southeast England, a sampling programme was undertaken. Between 2003 and 2004 diuron was observed in 90% of groundwaters analysed. In 60% of groundwater samples metabolites of diuron were more prevalent than the parent compound. Longer-term (1989-2005) monitoring shows that pollution of the aquifer by atrazine, simazine, and more recently diuron, shows a positive correlation with periods of high groundwater levels. Results from groundwater residence time indicators suggest that the highest diuron concentrations are associated with waters containing the greatest proportion of recent recharge. There is some evidence to indicate that diuron occurrence can be spatially related to areas of urban and industrial development and is probably correlated with amenity usage.

Impacts of climate change on the fate and behaviour of pesticides in surface and groundwater--A UK perspective.

Over the last two decades significant effort has been dedicated to understanding the fate and transport of pesticides in surface water and groundwater and to use this understanding in the development of environmental policy and regulation. However, there have been few studies that have investigated the relationships between pesticides and climate change, and where this work has been undertaken it has principally been in relation to the impacts of climate change on agricultural production rather than in the context of environmental protection. This study addresses that gap by reviewing how climate change may impact the fate and transport of pesticides in surface and groundwaters as a pre-cursor to quantitative studies. In order to structure the review, we have adopted a source-pathway-receptor approach where climate sensitivities of pesticide source terms, environmental pathways and receptors are reviewed. The main climate drivers for changing pesticide fate and behaviour are thought to be changes in rainfall seasonality and intensity and increased temperatures, but the effect of climate change on pesticide fate and transport is likely to be very variable and difficult to predict. In the long-term, indirect impacts, such as land-use change driven by changes in climate, may have a more significant effect on pesticides in surface and groundwaters than the direct impacts of climate change on pesticide fate and transport. The review focuses on climate change scenarios and case studies from the UK; however, the general conclusions can be applied more widely.

Estimating the leakage contribution of phosphate dosed drinking water to environmental phosphorus pollution at the national-scale.

Understanding sources of phosphorus (P) to the environment is critical for the management of freshwater and marine ecosystems. Phosphate is added at water treatment works for a variety of reasons: to reduce pipe corrosion, to lower dissolved lead and copper concentrations at customer's taps and to reduce the formation of iron and manganese precipitates which can lead to deterioration in the aesthetic quality of water. However, the spatial distribution of leakage into the environment of phosphate added to mains water for plumbosolvency control has not been quantified to date. Using water company leakage rates, leak susceptibility and road network mapping, we quantify the total flux of P from leaking water mains in England and Wales at a 1km grid scale. This is validated against reported leaks for the UKs largest water utility. For 2014, we estimate the total flux of P from leaking mains to the environment to be c. 1.2ktP/year. Spatially, P flux is concentrated in urban areas where pipe density is highest, with major cities acting as a significant source of P (e.g. London into the Thames, with potentially 30% of total flux). The model suggests the majority (69%) of the P flux is likely to be to surface water. This is due to leakage susceptibility being a function of soil corrosivity and shrink-swell behaviour which are both controlled by presence of low-permeability clays. The location of major cities such as London close to the coast results in a potentially significant flux of P from mains leakage to estuarine environments. The contribution of leakage of phosphate dosed mains water should be considered in future source apportionment and ecosystem management. The methodology presented is generic and can be applied in other countries where phosphate dosing is undertaken or used prior to dosing during investment planning.

Impacts of extreme flooding on riverbank filtration water quality.

Riverbank filtration schemes form a significant component of public water treatment processes on a global level. Understanding the resilience and water quality recovery of these systems following severe flooding is critical for effective water resources management under potential future climate change. This paper assesses the impact of floodplain inundation on the water quality of a shallow aquifer riverbank filtration system and how water quality recovers following an extreme (1 in 17 year, duration >70 days, 7 day inundation) flood event. During the inundation event, riverbank filtrate water quality is dominated by rapid direct recharge and floodwater infiltration (high fraction of surface water, dissolved organic carbon (DOC) >140% baseline values, >1 log increase in micro-organic contaminants, microbial detects and turbidity, low specific electrical conductivity (SEC) <90% baseline, high dissolved oxygen (DO) >400% baseline). A rapid recovery is observed in water quality with most floodwater impacts only observed for 2-3 weeks after the flooding event and a return to normal groundwater conditions within 6 weeks (lower fraction of surface water, higher SEC, lower DOC, organic and microbial detects, DO). Recovery rates are constrained by the hydrogeological site setting, the abstraction regime and the water quality trends at site boundary conditions. In this case, increased abstraction rates and a high transmissivity aquifer facilitate rapid water quality recoveries, with longer term trends controlled by background river and groundwater qualities. Temporary reductions in abstraction rates appear to slow water quality recoveries. Flexible operating regimes such as the one implemented at this study site are likely to be required if shallow aquifer riverbank filtration systems are to be resilient to future inundation events. Development of a conceptual understanding of hydrochemical boundaries and site hydrogeology through monitoring is required to assess the suitability of a prospective riverbank filtration site.

The potential for methane emissions from groundwaters of the UK.

Methane (CH4) is only a trace constituent of the atmosphere but an important greenhouse gas. Although groundwater is unlikely to be a major source of atmospheric CH4, its contribution to the CH4 budget of the UK has up to now been poorly characterised. Groundwater CH4 concentrations have been measured on 85 samples from water-supply boreholes and a further eight from other miscellaneous water sources. Concentrations in abstracted groundwaters ranged from <0.05-42.9 microg/l for Chalk, <0.05-22 microg/l for the Lower Greensand, 0.05-21.2 microg/l for the Lincolnshire Limestone and from <0.05-465 microg/l for the Triassic sandstone. Having the largest abstraction volume, the Chalk is likely to be the main UK groundwater contributor to global CH4 emissions. A calculation to estimate the total emissions of CH4 from water-supply groundwater sources based on the median and the maximum CH4 concentrations gave values of 2.2x10(-6) and 3.3x10(-4) Tg/year. Estimates show groundwater contributes a maximum of 0.05% of all UK CH4 emissions and a further two orders of magnitude less in terms of the global CH4 budget. Other groundwater sources such as inflows to tunnels may have significantly higher CH4 concentrations, but the volume of water discharged is much lower and the overall amount of CH4 outgassed is likely to be of the same order as the aquifer release. The generally low concentrations of CH4 in groundwater supplies suggest no threat of explosion, although groundwater released by excavations remains a hazard.

Emerging contaminants in urban groundwater sources in Africa.

The occurrence of emerging organic contaminants within the aquatic environment in Africa is currently unknown. This study provides early insights by characterising a broad range of emerging organic contaminants (n > 1000) in groundwater sources in Kabwe, Zambia. Groundwater samples were obtained during both the dry and wet seasons from a selection of deep boreholes and shallow wells completed within the bedrock and overlying superficial aquifers, respectively. Groundwater sources were distributed across the city to encompass peri-urban, lower cost housing, higher cost housing, and industrial land uses. The insect repellent DEET was ubiquitous within groundwater at concentrations up to 1.8 µg/L. Other compounds (n = 26) were detected in less than 15% of the sources and included the bactericide triclosan (up to 0.03 µg/L), chlorination by-products - trihalomethanes (up to 50 µg/L), and the surfactant 2,4,7,9-tetramethyl-5-decyne-4,7-diol (up to 0.6 µg/L). Emerging contaminants were most prevalent in shallow wells sited in low cost housing areas. This is attributed to localised vulnerability associated with inadequate well protection, sanitation, and household waste disposal. The five-fold increase in median DEET concentration following the onset of the seasonal rains highlights that more mobile compounds can rapidly migrate from the surface to the aquifer suggesting the aquifer is more vulnerable than previously considered. Furthermore it suggests DEET is potentially useful as a wastewater tracer in Africa. There was a general absence of personal care products, life-style compounds, and pharmaceuticals which are commonly detected in the aquatic environment in the developed world. This perhaps reflects some degree of attenuation within the subsurface, but could also be a result of the current limited use of products containing emerging contaminants by locals due to unaffordability and unavailability. As development and population increases in Africa, it is likely a wider-range of emerging contaminants will be released into the environment.

Penetration of herbicides to groundwater in an unconfined chalk aquifer following normal soil applications.

The persistence and penetration of the herbicides isoproturon and chlorotoluron in an unconfined chalk aquifer has been monitored over a 4-year period through soil sampling, shallow coring and groundwater monitoring. Chlorotoluron was applied on plots as a marker compound, having never been used previously on that, or surrounding fields. The fieldsite had a 5 degree slope with soil depths of 0.5 to 1.5 m and a water table between 20 and 5 m from the soil surface. Where the water table was deepest (9-20 m below surface (mbs)) little or no positive herbicide detections were made. However, where the water table was at only 4-5 mbs, a regular pesticide signal of around 0.1 microg/l for isoproturon and chlorotoluron could be distinguished. Over the winter recharge period automatic borehole samplers revealed a series of short-lived peaks of isoproturon and chlorotoluron reaching up to 0.8 microg/l. This is consistent with a preferential flow mechanism operating at this particular part of the field. Such peaks were occurring over 2 years after the last application of these compounds. Shallow coring failed to uncover any significant pesticide pulse moving through the deep unsaturated zone matrix at the fieldsite.

Assessing herbicide concentrations in the saturated and unsaturated zone of a Chalk aquifer in southern England.

The behavior of the herbicides isoproturon (IPU) and chlortoluron (CTU) in ground water and shallow unsaturated zone sediments were evaluated at a site situated on the Chalk in southern England. Concentrations of IPU in ground water samples varied from < 0.05 to 0.23 microgram/L over a five-year period of monitoring, and were found to correlate with application of the pesticide. Concentrations of pesticides in ground water samples collected during periods of rising water table were significantly higher than pumped samples and suggest that rapidly infiltrating recharge water contains higher herbicide concentrations than the native ground water. Significant variations in herbicide concentrations were observed over a three-month period in ground water samples collected by an automated system, with concentrations of IPU ranging from 0.1 to 0.5 microgram/L, and concentrations of a recent application of CTU ranging from 0.2 to 0.8 microgram/L. Different extraction methods were used to assess pore water concentrations of herbicides in the unsaturated zone, and samples were analyzed by standard HPLC analysis and immunoassay (ELISA) methods. These data indicated highly variable concentrations of herbicide ranging from 4 to 200 g/ha for HPLC and 0.01 to 0.04 g/ha for ELISA, but indicate a general pattern of decreasing concentrations with depth. The results of this study indicate that transport of IPU and CTU through the unsaturated zone to shallow ground water occurs and that this transport increases immediately following herbicide application. Measured concentrations of herbicides are generally lower than specified by the European Union Drinking Water Directive, but are observed to spike above this limit. These results imply that, while delivery of pesticides to ground water can occur as a result of normal agricultural practices, the impact on potable supplies is likely to be negligible due to the potential for degradation during the relatively long travel time through the unsaturated zone and high degree of dilution that occurs within the aquifer. As a result of the wide variation in concentrations detected by different techniques, it is suggested that for future site investigations more than one sampling strategy be employed to characterize the occurrence of pesticide residues and elucidate the transport mechanisms.

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.

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.

Wettability changes in trichloroethylene-contaminated sandstone.

It is usually assumed that chlorinated solvent nonaqueous-phase liquids (NAPLs) are nonwetting with respect to water-saturated porous media. The focus of this work was to examine whether this supposition is appropriate for used trichloroethylene (TCE) samples. In this work, the term "used" indicates that the sample has been employed industrially and therefore contains solutes and breakdown products related to its previous use. The data obtained in this study indicate that exposure of initially water wet quartz slides to industrially used solvents can cause a contact angle change, measured through the aqueous phase, of 100 degrees with a maximum stable contact angle of 170 degrees (indicative of strong NAPL wetting characteristics) being recorded. The work on quartz slides was complemented by the use of sandstone cores. Wettability was measured using the Amott test. Used TCE again proved able to alter the wetting properties of sandstone to neutral wetting. The complexity of the industrially used samples precluded any realistic attempt to examine the agents causing these wetting changes. The data captured in these experiments were compared with laboratory grade TCE, and some attempts were made to synthesize known mixtures in order to replicate wetting changes. These experiments resulted in contact angle changes but did not alter the overall wettability of the quartz slides or sandstone cores. Finally the work reported here also demonstrates that increasing the duration of exposure to solvent has an important impact upon measured contact angle.