Groundwater quality: Global threats, opportunities and realising the potential of groundwater.

Groundwater is a critical resource enabling adaptation due to land use change, population growth, environmental degradation, and climate change. It can be a driver of change and adaptation, as well as effectively mitigate impacts brought about by a range of human activities. Groundwater quality is key to assessing groundwater resources and we need to improve our understanding and coverage of groundwater quality threats if we are to use groundwater sustainably to not further burden future generations by limiting resources and/or increasing treatment or abstraction costs. Good groundwater quality is key to progress on a range of Sustainable Development Goals, but achievement of those goals most affected by groundwater contamination is often hindered by of a lack of resources to enable adaptation. A range of threats to groundwater quality exist, both natural and anthropogenic, which may constrain groundwater use. However, groundwater often provides good quality water for a range of purposes and is the most important water resource in many settings. This special issue explores some of the key groundwater quality challenges we face today as well as the opportunities good groundwater quality and treatment solutions bring to enhance safe groundwater use. Legacy anthropogenic contaminants and geogenic contaminants may be well documented in certain places, such as N America, Europe and parts of Asia. However, there is a real issue of data accessibility in some regions, even for more common contaminants. This paucity of information can restrict our understanding and ability to manage and protect groundwater sources. Compared to surface water quality, large scale assessments for groundwater quality are still scarce and often rely on inadequate data sets. Better access to existing data sets and more research is needed on many groundwater quality threats. Identification and quantification of these threats will support the wise use and protection of this subsurface resource, allow society to adequately address future challenges, and help communities realise the full potential of groundwater.

Emerging organic compounds in European groundwater.

In Europe, emerging organic compounds (EOCs) in groundwater is a growing research area. Prioritisation for monitoring EOCs in Europe was formalised in 2019 through the development of the first voluntary groundwater watch list (GWWL). Despite this, groundwater occurrence data in the peer reviewed literature for Europe has not been reviewed to date. Questions surrounding the effect, toxicity, movement in the subsurface and unsaturated zone make the process of regulating EOC use difficult. The aim in Europe is to develop a unified strategy for the classification, and prioritisation of EOCs to be monitored in groundwater. This paper compiles evidence from the recent published studies from across Europe, since 2012, when the last major literature global review of EOCs in groundwater took place. A total of 39 studies were identified for review based on specific selection criteria (geography, publication date, sample size>10, inclusion of EOCs data). Data on specific compounds, and associated meta-data, are compiled and reviewed. The two most frequently detected EOCs, carbamazepine and caffeine, occurred in groundwater at concentrations of up to 2.3 and 14.8 µg/L, respectively. The most frequently reported category of compounds were 'Pharmaceuticals'; a highly studied group with 135 compounds identified within 31 of the 39 studies. In Europe, the majority of reviewed studies (23) were at a regional scale, looking specifically at EOCs in a specific city or aquifer. The use of analytical methods is not uniform across Europe, and this inevitably influences the current assessment of EOCs in groundwater. A correlation between the number of compounds analysed for, and the number detected in groundwater highlights the need for further studies, especially larger-scale studies throughout Europe. For the development of EU and national regulation, further work is required to understand the occurrence and impacts of EOCs in groundwater throughout Europe and elsewhere.

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.

Terrestrial water load and groundwater fluctuation in the Bengal Basin.

Groundwater-level fluctuations represent hydraulic responses to changes in groundwater storage due to aquifer recharge and drainage as well as to changes in stress that include water mass loading and unloading above the aquifer surface. The latter 'poroelastic' response of confined aquifers is a well-established phenomenon which has been demonstrated in diverse hydrogeological environments but is frequently ignored in assessments of groundwater resources. Here we present high-frequency groundwater measurements over a twelve-month period from the tropical, fluvio-deltaic Bengal Aquifer System (BAS), the largest aquifer in south Asia. The groundwater level fluctuations are dominated by the aquifer poroelastic response to changes in terrestrial water loading by processes acting over periods ranging from hours to months; the effects of groundwater flow are subordinate. Our measurements represent the first direct, quantitative identification of loading effects on groundwater levels in the BAS. Our analysis highlights the potential limitations of hydrogeological analyses which ignore loading effects in this environment. We also demonstrate the potential for employing poroelastic responses in the BAS and across other tropical fluvio-deltaic regions as a direct, in-situ measure of changes in terrestrial water storage to complement analyses from the Gravity and Climate Experiment (GRACE) mission but at much higher resolution.

Groundwater quality in the alluvial aquifer system of northwest India: New evidence of the extent of anthropogenic and geogenic contamination.

Groundwater depletion has been widely studied in northwest India, but water quality concerns are still poorly constrained. In this study, we explore the hydrochemistry of the top 160m of the aquifer system, through detailed field studies in the Bist-Doab region, considering both anthropogenic and geogenic controls. A detailed comparison is made between sites dominated by urban and agricultural landuse. Salinity, nitrate, chloride and lead concentrations are significantly higher in the shallow (0-50m) groundwater system due to surface anthropogenic contaminant loading from agricultural and urban sources. The widespread occurrence of oxic groundwater within the aquifer system means that denitrification potential is limited and also enhances the mobility of selenium and uranium in groundwater. Geogenic trace elements (e.g. As, Se, F), are generally found at concentrations below WHO guideline drinking water values, however elevated U concentrations (50-70µg/L) are found within the deeper part of the aquifer and shallow urban aquifers associated with higher bicarbonate waters. Higher concentration of Se (10-40µg/L) are found exclusively in the shallow groundwater system where Se is mobilised from soils and transported to depth in the shallow aquifer due to the prevailing oxidising aquifer conditions. New evidence from a range of environmental tracers shows elevated concentrations of anthropogenic contaminants in the deeper part of the aquifer (50-160m deep) and demonstrates vulnerability to vertical migration of contaminants. Continued intensive groundwater abstraction from >100m deep means that water quality risks to the deep aquifer system need to be considered together with water quantity constraints.

Hydrogeological typologies of the Indo-Gangetic basin alluvial aquifer, South Asia.

The Indo-Gangetic aquifer is one of the world's most important transboundary water resources, and the most heavily exploited aquifer in the world. To better understand the aquifer system, typologies have been characterized for the aquifer, which integrate existing datasets across the Indo-Gangetic catchment basin at a transboundary scale for the first time, and provide an alternative conceptualization of this aquifer system. Traditionally considered and mapped as a single homogenous aquifer of comparable aquifer properties and groundwater resource at a transboundary scale, the typologies illuminate significant spatial differences in recharge, permeability, storage, and groundwater chemistry across the aquifer system at this transboundary scale. These changes are shown to be systematic, concurrent with large-scale changes in sedimentology of the Pleistocene and Holocene alluvial aquifer, climate, and recent irrigation practices. Seven typologies of the aquifer are presented, each having a distinct set of challenges and opportunities for groundwater development and a different resilience to abstraction and climate change. The seven typologies are: (1) the piedmont margin, (2) the Upper Indus and Upper-Mid Ganges, (3) the Lower Ganges and Mid Brahmaputra, (4) the fluvially influenced deltaic area of the Bengal Basin, (5) the Middle Indus and Upper Ganges, (6) the Lower Indus, and (7) the marine-influenced deltaic areas.

L'aquifère de l'Indus et du Gange est une des ressources en eau transfrontalière la plus importante au monde et un des aquifères le plus exploité au monde. Pour mieux comprendre le système aquifère, des typologies ont été caractérisées pour cet aquifère ; elles intègrent pour la première fois un jeu de données disponibles sur l'ensemble du bassin de l'Indus et du Gange à une échelle transfrontalière, et apportent une conceptualisation alternative de ce système aquifère. Traditionnellement considéré et cartographié comme un simple aquifère homogène aux propriétés aquifères similaires et comme une ressource d'eau souterraine à l'échelle transfrontalière, les typologies mettent en évidence des différences significatives spatiales de la recharge, de la perméabilité, de la capacité de stockage et de la chimie des eaux souterraines sur l'ensemble du système aquifère à une échelle transfrontalière. Ces changements sont systématiques coïncidant aux changements à large échelle de la sédimentologie de l'aquifère alluvial du Pléistocène et de l'Holocène, du climat et des pratiques récentes d'irrigation. Sept typologies de l'aquifère sont présentées, chacune ayant un ensemble distinct de défis et d'opportunités pour le développement des eaux souterraines et une résilience différente à l'exploitation et au changement climatique. Les sept typologies sont: (1) la marge de piedmont, (2) Le haut Indus et le Ganges moyen supérieur, (3) le Ganges inférieur et le Brahmapoutre moyen, (4) la zone deltaïque du bassin du Bengale sous influence fluviale, (5) l'Indus moyen et le Ganges supérieur, (6) l'Indus inférieur, et (7) la zone deltaïque sous influence marine.

El acuífero Indo-Gangético es uno de los recursos hídricos transfronterizos más importantes y el acuífero más explotado del mundo. Para comprender mejor el sistema acuífero, por primera vez se han caracterizado tipologías para el acuífero, integrando los conjuntos de datos existentes a través de la cuenca hidrográfica Indo-Ganges a una escala transfronteriza, y proporcionando una conceptualización alternativa de este sistema acuífero. Tradicionalmente consideradas y cartografiadas como un solo acuífero homogéneo de propiedades acuíferas y recursos de agua subterránea comparables a escala transfronteriza, las tipologías iluminan diferencias espaciales significativas en la recarga, permeabilidad, almacenamiento y química del agua subterránea a través del sistema acuífero a esta escala transfronteriza. Estos cambios son mostrados por ser sistemáticos, coincidentes con cambios en gran escala en la sedimentología del acuífero aluvial del Pleistoceno y del Holoceno, en el clima y en las prácticas recientes de riego. Se presentan siete tipologías del acuífero, cada una con un conjunto distinto de desafíos y oportunidades para el desarrollo del agua subterránea y una diferente resiliencia a la extracción y al cambio climático. Las siete tipologías son: (1) el margen del piedemonte, (2) el Indus superior y el Ganges superior-medio, (3) el Ganges inferior y el Brahmaputra medio, (4) el área deltaica fluvialmente influenciada de la cuenca de Bengala, (5) el Ganges superior, (6) el Indo Inferior, y (7) las áreas deltaicas con influencia marina.

O aquífero do Indo-Gangético é um dos recursos hídricos transfronteiriços mais importantes do mundo, e o mais explorado. Para melhor entender o sistema aquífero, tipologias foram caracterizadas para o aquífero, que integram pela primeira vez bancos de dados existentes sobre a bacia de abastecimento Indo-Gangética em uma escala transfornteiriça, e fornecem uma conceptualização alternativa desse sistema aquífero. Tradicionalmente considerado e mapeado como um aquífero homogêneo de propriedades aquíferas comparáveis e recursos subterrâneos em escala transfronteiriça, as tipologias elucidam diferenças espaciais significantes na recarga, permeabilidade, armazenamento, e química das águas subterrâneas pelo aquífero nessa escala transfronteiriça. Essas mudanças aparentam ser sistemáticas, concorrentes com mudanças em larga escala na sedimentologia do aquífero aluvial do Pleistoceno e Holoceno, clima e práticas recentes de irrigação. Sete tipologias do aquífero são apresentadas, cada uma tendo conjuntos de desafios e oportunidades distintos para o desenvolvimento das águas subterrâneas e uma resiliência diferente nas mudanças de extração e clima. As sete tipologias são: (1) a margem piemonte, (2) O Alto Indo e o Alto-médio Ganges, (3) O Baixo Ganges e o Médio Brahmaputra, (4) a área deltaica influenciada fluvialmente da Bacia de Bengala, (5) o Médio Indo e o Alto Ganges, (6) o Baixo Indo, e (7) as áreas deltaicas com influencia marinha.

Urban groundwater quality in sub-Saharan Africa: current status and implications for water security and public health.

Groundwater resources are important sources of drinking water in Africa, and they are hugely important in sustaining urban livelihoods and supporting a diverse range of commercial and agricultural activities. Groundwater has an important role in improving health in sub-Saharan Africa (SSA). An estimated 250 million people (40% of the total) live in urban centres across SSA. SSA has experienced a rapid expansion in urban populations since the 1950s, with increased population densities as well as expanding geographical coverage. Estimates suggest that the urban population in SSA will double between 2000 and 2030. The quality status of shallow urban groundwater resources is often very poor due to inadequate waste management and source protection, and poses a significant health risk to users, while deeper borehole sources often provide an important source of good quality drinking water. Given the growth in future demand from this finite resource, as well as potential changes in future climate in this region, a detailed understanding of both water quantity and quality is required to use this resource sustainably. This paper provides a comprehensive assessment of the water quality status, both microbial and chemical, of urban groundwater in SSA across a range of hydrogeological terrains and different groundwater point types. Lower storage basement terrains, which underlie a significant proportion of urban centres in SSA, are particularly vulnerable to contamination. The relationship between mean nitrate concentration and intrinsic aquifer pollution risk is assessed for urban centres across SSA. Current knowledge gaps are identified and future research needs highlighted.

Les ressources en eaux souterraines sont des sources importantes d'eau potable en Afrique, et elles sont d'une énorme importance pour les êtres vivants en milieu urbain et pour le soutien d'une gamme diversifiée d'activités commerciales et agricoles. Les eaux souterraines jouent un rôle important en améliorant la santé en Afrique sub-saharienne (ASS). 250 millions de personnes environ (40% du total) vivent dans des centres urbains à travers l'ASS. L'ASS a connu une expansion rapide de ses populations urbaines depuis les années 1950, avec une augmentation à la fois des densités de population et de leur extension géographique. Les estimations prévoient un doublement de la population urbaine de l'ASS entre 2000 et 2030. L'état qualitatif des ressources en eau souterraine urbaines peu profondes est souvent très pauvre du fait de l'insuffisance de la gestion des déchets et de la protection de la ressource, et pose un risque sanitaire significatif pour les utilisateurs, alors que des ressources plus profondes captées par forage fournissent souvent une source importante d'eau potable de bonne qualité. Etant donné la croissance de la demande future de cette ressource limitée, ainsi que le changement climatique potentiel dans cette région dans le futur, une compréhension détaillée de la quantité et la qualité de cette ressource est exigée pour son utilisation durable. Cet article fournit une évaluation complète de l'état qualitatif, à la fois microbien et chimique, des eaux souterraines urbaines en ASS à travers une gamme de contextes hydrogéologiques et de différents types de point d'eaux souterraines. Les terrains du sous-sol de faible emmagasinement, qui sont situés sous une proportion significative de centres urbains en ASS, sont particulièrement vulnérables à la contamination. Le rapport entre la concentration moyenne en nitrate et le risque intrinsèque de pollution des aquifères est évalué pour les centres urbains de l'ASS. Des lacunes actuelles en matière de connaissances sont identifiées et les besoins de recherches futurs sont mis en évidence.

Los recursos hídricos subterráneos son una fuente importante de agua potable en África y son sumamente importantes para mantener los medios de subsistencia urbanos y para apoyar una amplia gama de actividades comerciales y agrícolas. El agua subterránea tiene un papel importante en la mejora de la salud en el África Subsahariana (SSA). Se calcula que 250 millones de personas (40% del total) viven en centros urbanos en el África Subsahariana. El SSA ha experimentado una rápida expansión en las poblaciones urbanas desde la década de 1950, con el aumento de la densidad de población, así como la ampliación de la cobertura geográfica. Las estimaciones sugieren que la población urbana en África Subsahariana se duplicará entre 2000 y 2030. El estado de calidad del agua subterránea somera es a menudo muy pobre debido a la gestión inadecuada de los desechos y de la protección de las fuentes, representando un riesgo significativo para los usuarios, mientras que los pozos más profundos proporcionan una fuente importante de agua potable de buena calidad. Dado el crecimiento de la demanda futura de este recurso finito, así como los cambios potenciales en el clima futuro en esta región, una comprensión detallada de su cantidad y calidad es necesaria para utilizar este recurso de manera sostenible. Este artículo ofrece una evaluación integral del estado de la calidad del agua, tanto microbiana como química, del agua subterránea urbana en el SSA a lo largo de una serie de terrenos hidrogeológicos y diferentes tipos de puntos de agua subterránea. Los basamentos de bajo almacenamiento, que subyacen a una proporción significativa de los centros urbanos del África Subsahariana, son particularmente vulnerables a la contaminación. Se evalúa la relación entre la concentración media de nitratos y el riesgo intrínseco de contaminación acuífera para los centros urbanos a través de la SSA. Se identifican las deficiencias actuales de conocimientos y se destacan las necesidades de futuras investigaciones.

As águas subterrâneas são fontes importantes de água para consumo na África, e são amplamente importantes para sustentar o modo de vida urbano e dar suporte a uma amplitude diversa de atividades comerciais e agrícolas. As águas subterrâneas têm um papel importante no desenvolvimento da saúde na África subsaariana (ASS). São estimadas 250 milhões de pessoas (40% do total) vivendo nos centros urbanos na ASS. ASS tem vivenciado uma rápida expansão na população urbana desde os anos 50, com aumento das densidades populacionais assim como expansão da cobertura geográfica. As estimativas sugerem que a população urbana na ASS dobrará entre 2000 e 2030. As condições de qualidade dos aquíferos livres em áreas urbanas estão frequentemente muito pobres por causa do gerenciamento de perdas e proteção das fontes inadequados, e apresenta um risco significativo à saúde dos usuários, enquanto poços mais profundos frequentemente fornecem fontes importantes de água potável de boa qualidade. Dado o crescimento na demanda futura desse recurso finito, assim como mudanças potenciais no clima futuro da região, um entendimento detalhado da sua quantidade e qualidade é necessário para o uso sustentável deste recurso. Esse estudo fornece uma avaliação compreensiva das condições de qualidade da água, tanto microbiológica quanto química, das águas subterrâneas urbanas na ASS por uma gama de terrenos hidrogeológicos e diferentes tipos pontuais de águas subterrâneas. Terrenos de menor armazenamento de base, que fundamentam uma porção significante dos centros urbanos da ASS, são particularmente vulneráveis a contaminação. A relação entre a concentração média de nitrato e o risco intrínseco de poluição do aquífero é avaliado para os centros urbanos na ASS. Lacunas do conhecimento atual foram identificadas e destaca-se a necessidade de pesquisas futuras.

Hydrochemical profiles in urban groundwater systems: New insights into contaminant sources and pathways in the subsurface from legacy and emerging contaminants.

It has long been known that groundwaters beneath urban areas carry a fingerprint from urban activities but finding a consistent tracer for anthropogenic influence has proved elusive. The varied sources of urban contaminants means that a single consistent and inexpensive means of tracing the fate of urban contaminants is not generally possible and multiple tracers are often required to understand the contaminant sources and pathways in these complex systems. This study has utilized a combination of micro-organic (MO) contaminants and inorganic hydrochemistry to trace recharge pathways and quantify the variability of groundwater quality in multi-level piezometers in the city of Doncaster, UK. A total of 23 MOs were detected during this study, with more compounds consistently detected during higher groundwater table conditions highlighting the importance of sampling under different hydrological conditions. Four of the compounds detected are EU Water Framework Directive priority substances: atrazine, simazine, naphthalene and DEHP, with a maximum concentration of 0.18, 0.03, 0.2, 16µg/l respectively. Our study shows that the burden of the banned pesticide atrazine persists in the Sherwood Sandstone and is detected at two of the three study sites. Emerging contaminants are seen throughout the borehole profiles and provide insights into transient pathways for contaminant migration in the sub-surface. Long term changes in inorganic hydrochemistry show possible changes in contaminant input or the dissolution of minerals. Nitrate was detected above 50mg/l but on the whole nitrate concentrations have declined in the intervening years either due to a reduction of nitrate application at the surface or a migration of peak nitrate concentrations laterally or to greater depth. This study shows that multiple tracers together with multi-level piezometers can give a better resolution of contaminant pathways and variable flow regimes within the relatively uncomplicated aquifer of the Sherwood Sandstone compared with single long screened wells.

Macronutrient status of UK groundwater: Nitrogen, phosphorus and organic carbon.

Groundwater is a large, slowly changing pool of the macronutrients nitrogen (N), phosphorus (P) and dissolved organic carbon (DOC), with impacts on receptors, surface waters, dependent wetlands and coastal marine ecosystems. Sources of N to groundwater include fertilisers, animal wastes and septic effluents. N species are well-quantified in groundwater and NO3-N has a wide range of median values (0-12mg/L). The highest concentrations are in the Chalk of East Anglia and Humberside and the Permo-Triassic Sandstone (PTS) of Staffordshire. The highest concentrations of NH4-N are found in confined aquifers. N concentrations have increased with time peaking during the 1980s. Changes in practice have led to the reduction observed in rapidly-responding aquifers. For the Chalk, where the unsaturated zone is thick, improvements may not be seen for decades. P is less well-characterised in UK groundwater reflecting the lack of historical interest in groundwater P, although it can be significant in some aquifer matrices. Groundwater P concentrations are elevated in sandstone formations compared to other lithology and highest in the PTS of the Midlands and northern England (median values>50µg/L). Overall half of the aquifers studied in the UK have median TDP>50µg/L, with values of up to 100µg/L under some urban areas, such as Manchester and Liverpool as well as the Lee Valley. P concentrations in arable areas are variable (20-100µg/L), whereas under semi-natural conditions they are lower (20-50µg/L). There is little information on P trends in groundwater. Most DOC is derived from soils, playing an important part in redox processes. The aquifer matrix can contain high OC and contribute significantly to groundwater DOC. Median values range between 0.4 and 9mg/L, but rarely exceed 5mg/L, except in the Chalk of Yorkshire and Humberside and PTS of Liverpool which have long legacies of anthropogenic pollution.

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.

Temporal variability of micro-organic contaminants in lowland chalk catchments: New insights into contaminant sources and hydrological processes.

This paper explores the temporal variation of a broad suite of micro organic (MO) compounds within hydrologically linked compartments of a lowland Chalk catchment, the most important drinking water aquifer in the UK. It presents an assessment of results from relatively high frequency monitoring at a well-characterised site, including the type and concentrations of compounds detected and how they change under different hydrological conditions including exceptionally high groundwater levels and river flow conditions during 2014 and subsequent recovery. This study shows for the first time that within the Chalk groundwater there can be a greater diversity of the MOs compared to surface waters. Within the Chalk 26 different compounds were detected over the duration of the study compared to 17 in the surface water. Plasticisers (0.06-39µg/L) were found to dominate in the Chalk groundwater on 5 visits (38.4%) accounting for 14.5% of detections but contributing highest concentrations whilst other compounds dominated in the surface water. Trichloroethene and atrazine were among the most frequently detected compounds. The limit for the total pesticide concentration detected did not exceed EU/UK prescribed concentration values for drinking water. Emerging organic compounds such as caffeine, which currently do not have water quality limits, were also detected. The low numbers of compounds found within the hyporheic zone highlight the role of this transient interface in the attenuation and breakdown of the MOs, and provision of an important ecosystem service.

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.

Are sanitation interventions a threat to drinking water supplies in rural India? An application of tryptophan-like fluorescence.

Open defecation is practised by over 600 million people in India and there is a strong political drive to eliminate this through the provision of on-site sanitation in rural areas. However, there are concerns that the subsequent leaching of excreta from subsurface storage could be adversely impacting underlying groundwater resources upon which rural populations are almost completely dependent for domestic water supply. We investigated this link in four villages undergoing sanitary interventions in Bihar State, India. A total of 150 supplies were sampled for thermotolerant (faecal) coliforms (TTC) and tryptophan-like fluorescence (TLF): an emerging real-time indicator of faecal contamination. Sanitary risk inspections were also performed at all sites, including whether a supply was located within 10 m of a toilet, the recommended minimum separation. Overall, 18% of water supplies contained TTCs, 91% of which were located within 10 m of a toilet, 58% had TLF above detection limit, and sanitary risk scores were high. Statistical analysis demonstrated TLF was an effective indicator of TTC presence-absence, with a possibility of TTCs only where TLF exceeded 0.4 µg/L dissolved tryptophan. Analysis also indicated proximity to a toilet was the only significant sanitary risk factor predicting TTC presence-absence and the most significant predictor of TLF. Faecal contamination was considered a result of individual water supply vulnerability rather than indicative of widespread leaching into the aquifer. Therefore, increasing faecal contamination of groundwater-derived potable supplies is inevitable across the country as uptake of on-site sanitation intensifies. Communities need to be aware of this link and implement suitable decentralised low-cost treatment of water prior to consumption and improve the construction and protection of new supplies.

Tracing enteric pathogen contamination in sub-Saharan African groundwater.

Quantitative PCR (qPCR) can rapidly screen for an array of faecally-derived bacteria, which can be employed as tracers to understand groundwater vulnerability to faecal contamination. A microbial DNA qPCR array was used to examine 45 bacterial targets, potentially relating to enteric pathogens, in 22 groundwater supplies beneath the city of Kabwe, Zambia in both the dry and subsequent wet season. Thermotolerant (faecal) coliforms, sanitary risks, and tryptophan-like fluorescence, an emerging real-time reagentless faecal indicator, were also concurrently investigated. There was evidence for the presence of enteric bacterial contamination, through the detection of species and group specific 16S rRNA gene fragments, in 72% of supplies where sufficient DNA was available for qPCR analysis. DNA from the opportunistic pathogen Citrobacter freundii was most prevalent (69% analysed samples), with Vibrio cholerae also perennially persistent in groundwater (41% analysed samples). DNA from other species such as Bifidobacterium longum and Arcobacter butzleri was more seasonally transient. Bacterial DNA markers were most common in shallow hand-dug wells in laterite/saprolite implicating rapid subsurface pathways and vulnerability to pollution at the surface. Boreholes into the underlying dolomites were also contaminated beneath the city highlighting that a laterite/saprolite overburden, as occurs across much of sub-Saharan aquifer, does not adequately protect underlying bedrock groundwater resources. Nevertheless, peri-urban boreholes all tested negative establishing there is limited subsurface lateral transport of enteric bacteria outside the city limits. Thermotolerant coliforms were present in 97% of sites contaminated with enteric bacterial DNA markers. Furthermore, tryptophan-like fluorescence was also demonstrated as an effective indicator and was in excess of 1.4µg/L in all contaminated sites.

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.

In situ tryptophan-like fluorometers: assessing turbidity and temperature effects for freshwater applications.

Tryptophan-like fluorescence (TLF) is an indicator of human influence on water quality as TLF peaks are associated with the input of labile organic carbon (e.g. sewage or farm waste) and its microbial breakdown. Hence, real-time measurement of TLF could be particularly useful for monitoring water quality at a higher temporal resolution than available hitherto. However, current understanding of TLF quenching/interference is limited for field deployable sensors. We present results from a rigorous test of two commercially available submersible tryptophan fluorometers (ex ∼ 285, em ∼ 350). Temperature quenching and turbidity interference were quantified in the laboratory and compensation algorithms developed. Field trials were then undertaken involving: (i) an extended deployment (28 days) in a small urban stream; and, (ii) depth profiling of an urban multi-level borehole. TLF was inversely related to water temperature (regression slope range: -1.57 to -2.50). Sediment particle size was identified as an important control on the turbidity specific TLF response, with signal amplification apparent <150 NTU for clay particles and <650 NTU for silt particles. Signal attenuation was only observed >200 NTU for clay particles. Compensation algorithms significantly improved agreement between in situ and laboratory readings for baseflow and storm conditions in the stream. For the groundwater trial, there was an excellent agreement between laboratory and raw in situ TLF; temperature compensation provided only a marginal improvement, and turbidity corrections were unnecessary. These findings highlight the potential utility of real time TLF monitoring for a range of environmental applications (e.g. tracing polluting sources and monitoring groundwater contamination). However, in situations where high/variable suspended sediment loads or rapid changes in temperature are anticipated concurrent monitoring of turbidity and temperature is required and site specific calibration is recommended for long term, surface water monitoring.

Using chemical, microbial and fluorescence techniques to understand contaminant sources and pathways to wetlands in a conservation site.

Nutrients and faecal contaminants can enter wetland systems in a number of ways, with both biological and potentially human-health implications. In this study we used a combination of inorganic chemistry, dissolved organic matter (DOM) fluorescence and Escherichia coli and total coliform (TC) count techniques to study the sources and multiple pathways of contamination affecting a designated sand dune site of international conservation importance, surrounded by agricultural land. Analysis of stream samples, groundwater and dune slack wetlands revealed multiple input pathways. These included riverbank seepage, runoff events and percolation of nutrients from adjacent pasture into the groundwater, as well as some on-site sources. The combined techniques showed that off-site nutrient inputs into the sand dune system were primarily from fertilisers, revealed by high nitrate concentrations, and relatively low tryptophan-like fulvic-like ratios<0.4Ramanunits (R.U.). The E. coli and TC counts recorded across the site confirm a relatively minor source of bacterial and nutrient inputs from on-site grazers. Attenuation of the nutrient concentrations in streams, in groundwater and in run-off inputs occurs within the site, restoring healthier groundwater nutrient concentrations showing that contaminant filtration by the sand dunes provides a valuable ecosystem service. However, previous studies show that this input of nutrients has a clear adverse ecological impact.