Spatial and seasonal controls on dissolved organic matter composition in shallow aquifers under the rapidly developing city of Patna, India.

The distribution and composition of dissolved organic matter (DOM) affects numerous (bio)geochemical processes in environmental matrices including groundwater. This study reports the spatial and seasonal controls on the distribution of groundwater DOM under the rapidly developing city of Patna, Bihar (India). Major DOM constituents were determined from river and groundwater samples taken in both pre- and post-monsoon seasons in 2019, using excitation-emission matrix (EEM) fluorescence spectroscopy. We compared aqueous fluorescent DOM (fDOM) composition to satellite-derived land use data across the field area, testing the hypothesis that the composition of groundwater DOM, and particularly the components associated with surface-derived ingress, may be controlled, in part, by land use. In the pre-monsoon season, the prominence of tryptophan-like components likely generated from recent biological activity overwhelmed the humic-like and tyrosine-like fluorescence signals. Evidence from fluorescence data suggest groundwater in the post-monsoon season is composed of predominantly i) plant-derived matter and ii) anthropogenically influenced DOM (e.g. tryptophan-like components). Organic tracers, as well as Eh and Cl-, suggest monsoonal events mobilise surface-derived material from the unsaturated zone, causing dissolved organic carbon (DOC) of more microbial nature to infiltrate to >100 m depth. A correlation between higher protein:humic-like fluorescence and lower vegetation index (NDVI), determined from satellite-based land use data, in the post-monsoon season, indicates the ingression of wastewater-derived OM in groundwater under the urban area. Attenuated protein:humic-like fluorescence in groundwater close to the river points towards the mixing of groundwater and river water. This ingress of surface-derived OM is plausibly exacerbated by intensive groundwater pumping under these areas. Our approach to link the composition of aqueous organics with land use could easily be adapted for similar hydrogeochemical settings to determine the factors controlling groundwater DOM composition in various contexts.

Emerging organic contaminants in springs of the highly karstified Dinaric region.

Emerging organic contaminants (EOCs) have become of increasing interest due to concerns about their impact on humans and the wider environment. Karst aquifers are globally widespread, providing critical water supplies and sustaining rivers and ecosystems, and are particularly susceptible to pollution. However, EOC distributions in karst remain quite poorly understood. This study looks at the occurrence of EOCs in the Croatian karst, which is an example of the "classical" karst, a highly developed type of karst that occurs throughout the Dinaric region of Europe. Samples were collected from 17 karst springs and one karst lake used for water supply in Croatia during two sampling campaigns. From a screen of 740 compounds, a total of 65 compounds were detected. EOC compounds from the pharmaceutical (n = 26) and agrochemical groups (n = 26) were the most frequently detected, while industrials and artificial sweeteners had the highest concentrations (range 8-440 ng/L). The number of detected compounds and the frequency of detection demonstrate the vulnerability of karst to EOC pollution. Concentrations of 5 compounds (acesulfame, sucralose, perfluorobutane sulfonate, emamectin B1b, and triphenyl phosphate) exceeded EU standards and occurred at concentrations that are likely to be harmful to ecosystems. Overall, most detections were at low concentrations (50 % <1 ng/L). This may be due to high dilution within the exceptionally large springs of the Classical karst, or due to relatively few pollution sources within the catchments. Nevertheless, EOC fluxes are considerable (10 to 106 ng/s) due to the high discharge of the springs. Temporal differences were observed, but without a clear pattern, reflecting the highly variable nature of karst springs that occurs over both seasonal and short-term timescales. This research is one of a handful of regional EOC investigations in karst groundwater, and the first regional study in the Dinaric karst. It demonstrates the need for more frequent and extensive sampling of EOCs in karst to protect human health and the environment.

Emerging organic contaminants in the River Ganga and key tributaries in the middle Gangetic Plain, India: Characterization, distribution & controls.

The presence and distribution of emerging organic contaminants (EOCs) in freshwater environments is a key issue in India and globally, particularly due to ecotoxicological and potential antimicrobial resistance concerns. Here we have investigated the composition and spatial distribution of EOCs in surface water along a ∼500 km segment of the iconic River Ganges (Ganga) and key tributaries in the middle Gangetic Plain of Northern India. Using a broad screening approach, in 11 surface water samples, we identified 51 EOCs, comprising of pharmaceuticals, agrochemicals, lifestyle and industrial chemicals. Whilst the majority of EOCs detected were a mixture of pharmaceuticals and agrochemicals, lifestyle chemicals (and particularly sucralose) occurred at the highest concentrations. Ten of the EOCs detected are priority compounds (e.g. sulfamethoxazole, diuron, atrazine, chlorpyrifos, perfluorooctane sulfonate (PFOS), perfluorobutane sulfonate, thiamethoxam, imidacloprid, clothianidin and diclofenac). In almost 50% of water samples, sulfamethoxazole concentrations exceeded predicted no-effect concentrations (PNECs) for ecological toxicity. A significant downstream reduction in EOCs was observed along the River Ganga between Varanasi (Uttar Pradesh) and Begusarai (Bihar), likely reflecting dilution effects associated with three major tributaries, all with considerably lower EOC concentrations than the main Ganga channel. Sorption and/or redox controls were observed for some compounds (e.g. clopidol), as well as a relatively high degree of mixing of EOCs within the river. We discuss the environmental relevance of the persistence of several parent compounds (notably atrazine, carbamazepine, metribuzin and fipronil) and associated transformation products. Associations between EOCs and other hydrochemical parameters including excitation emission matrix (EEM) fluorescence indicated positive, significant, and compound-specific correlations between EOCs and tryptophan-, fulvic- and humic-like fluorescence. This study expands the baseline characterization of EOCs in Indian surface water and contributes to an improved understanding of the potential sources and controls on EOC distribution in the River Ganga and other large river systems.

Pesticides and their metabolites in European groundwater: Comparing regulations and approaches to monitoring in France, Denmark, England and Switzerland.

Pesticides, i.e. plant protection products (PPP), biocides and their metabolites, pose a serious threat to groundwater quality and groundwater dependent ecosystems. Across large parts of Europe these compounds are monitored in groundwater to ensure compliance with the European Water Framework Directive (WFD), the Groundwater Directive (GWD) and Drinking water Directive (DWD). European regulation concerning the placing of PPP on the market includes groundwater monitoring as a higher tier of the regulatory procedure. Nevertheless, the lists of compounds to be monitored vary from one directive to another and between countries. The implementation of monitoring strategies for these directives and other national drivers, differs across Europe. This is illustrated using case studies from France, Denmark (EU member states), England (part of the EU up to January 2020) and Switzerland (associated country). The collection of data (e.g. monitoring design and analytical approaches) and dissemination at national and European level and the scale of data reporting to EU is country-specific. Data generated by the implementation of WFD and DWD can be used for retrospective purposes in the context of PPP registration whereas the post-registration monitoring data generated by the product applicants are generally only directly available to the regulators. This lack of consistency and strategic coordination between thematic regulations is partly compensated by national regulations. This paper illustrates the benefits of a common framework for regulation in Europe but shows that divergent national approaches to monitoring and reporting on pesticides in groundwater makes the task of assessment across Europe challenging.

Environmental tracers and groundwater residence time indicators reveal controls of arsenic accumulation rates beneath a rapidly developing urban area in Patna, India.

Groundwater security is a pressing environmental and societal issue, particularly due to significantly increasing stressors on water resources, including rapid urbanization and climate change. Groundwater arsenic is a major water security and public health challenge impacting millions of people in the Gangetic Basin of India and elsewhere globally. In the rapidly developing city of Patna (Bihar) in northern India, we have studied the evolution of groundwater chemistry under the city following a three-dimensional sampling framework of multi-depth wells spanning the central urban zone in close proximity to the River Ganges (Ganga) and transition into peri-urban and rural areas outside city boundaries and further away from the river. Using inorganic geochemical tracers (including arsenic, iron, manganese, nitrate, nitrite, ammonium, sulfate, sulfide and others) and residence time indicators (CFCs and SF6), we have evaluated the dominant hydrogeochemical processes occurring and spatial patterns in redox conditions across the study area. The distribution of arsenic and other redox-sensitive parameters is spatially heterogenous, and elevated arsenic in some locations is consistent with arsenic mobilization via reductive dissolution of iron hydroxides. Residence time indicators evidence modern (<~60-70 years) groundwater and suggest important vertical and lateral flow controls across the study area, including an apparent seasonal reversal in flow regimes near the urban center. An overall arsenic accumulation rate is estimated to be ~0.003 ± 0.003 µM.yr-1 (equivalent to ~0.3 ± 0.2 µg.yr-1), based on an average of CFC-11, CFC-12 and SF6-derived models, with the highest rates of arsenic accumulation observed in shallow, near-river groundwaters also exhibiting elevated concentrations of nutrients including ammonium. Our findings have implications on groundwater management in Patna and other rapidly developing cities, including potential future increased groundwater vulnerability associated with surface-derived ingress from large-scale urban abstraction or in higher permeability zones of river-groundwater connectivity.

Assessing groundwater salinity across Africa.

In Africa groundwater is the principal source of drinking water (https://washdata.org/) and has significant potential to improve food production as a source of irrigation water. Although volumes of stored groundwater are high when compared to surface water, not all the available groundwater is suitable for irrigation. One of the principal factors that limit the development of groundwater is salinity, but quantitative evidence regarding the scale of salinization in Africa has been lacking. This paper presents an initial analysis of the extent of groundwater salinization in Africa, bringing together groundwater salinity data (n = 12,255) from across the continent. In our dataset c.80% of the samples have electrical conductivity values less than 2000 µS/cm. Samples with high conductivity values of more than 2000 µS/cm are restricted to limited geological and climatic environments. The data reveals salinity does not affect the water security status of most countries in Africa. However, salinity compounds water insecurity issues in arid low groundwater recharge environments. The paper discusses the role of anthropogenic processes such as river valley water resources development, extensive groundwater pumping, inter-basin groundwater transfer, and irrigation in altering the salinity of groundwater bodies. The paper further elucidates the origin of groundwater salinity by critically reviewing the natural and human-induced factors that control the salinization of the various groundwater bodies across Africa. Existing case studies reveal several causes of salinization, including i) human-induced salinization, ii) climate and hydrological change-induced paleo groundwater salinity, iii) rock dissolution, and iv), saltwater encroachment.

Quantifying the dynamics of sub-daily to seasonal hydrological interactions of Ganges river with groundwater in a densely populated city: Implications to vulnerability of drinking water sources.

Groundwater resources in South Asian cities are facing immense stress due to over-extraction leading to environmental, social and economic instabilities. The perennial mega rivers of Himalayas form the lifeline for South Asia, underpinning food and water security for a large population both directly and indirectly through exchange with groundwater systems. The present study delineates the spatio-temporal variation in patterns and processes of sub-hourly to annual-scale hydrological exchanges between the Ganges and its adjoining highly exploited aquifer in a urban-peri urban reach. Multivariate statistical analyses established river water-groundwater interaction in this region with ~40% loading of first principal component, i.e river water during monsoon on the shallow aquifer. The part of the aquifer detached from the main confined aquifer show an influence of precipitation (the second principal component) with loading of ~90%. Again the part of the aquifer suffering infiltration of local surface water bodies show effect of precipitation with a second principal loading of ~80%. Fourier transformation is used in the hydrograph to remove influence of heavy urbanization on the hydrographs. This study proves that the phenomenon of infiltrating river water during monsoon plays a primary role in controlling aquifer storage although contaminating the aquifer simultaneously. However, during pre and post-monsoon the flow path reversal helps in maintaining river baseflow. Cross-correlation between the river and piezometric series show increased delay of pressure head propagation of the infiltrating river waterfront, with increasing distance. These observations are also substantiated by stable isotope signatures. The present study provides an understanding of potential groundwater vulnerability resulting from waste water and irrigational contamination through river water intrusion which would eventually lead the government to implement proper water and environmental management policies towards availability of long-term sustainable water resources for the residents.

Emerging organic contaminants in groundwater under a rapidly developing city (Patna) in northern India dominated by high concentrations of lifestyle chemicals.

Aquatic pollution from emerging organic contaminants (EOCs) is of key environmental importance in India and globally, particularly due to concerns of antimicrobial resistance, ecotoxicity and drinking water supply vulnerability. Here, using a broad screening approach, we characterize the composition and distribution of EOCs in groundwater in the Gangetic Plain around Patna (Bihar), as an exemplar of a rapidly developing urban area in northern India. A total of 73 EOCs were detected in 51 samples, typically at ng.L-1 to low µg.L-1 concentrations, relating to medical and veterinary, agrochemical, industrial and lifestyle usage. Concentrations were often dominated by the lifestyle chemical and artificial sweetener sucralose. Seventeen identified EOCs are flagged as priority compounds by the European Commission, World Health Organisation and/or World Organisation for Animal Health: namely, herbicides diuron and atrazine; insecticides imidacloprid, thiamethoxam, clothianidin and acetamiprid; the surfactant perfluorooctane sulfonate (and related perfluorobutane sulfonate, perfluorohexane sulfonate, perfluorooctanoic acid and perfluoropentane sulfonate); and medical/veterinary compounds sulfamethoxazole, sulfanilamide, dapson, sulfathiazole, sulfamethazine and diclofenac. The spatial distribution of EOCs varies widely, with concentrations declining with depth, consistent with a strong dominant vertical flow control. Groundwater EOC concentrations in Patna were found to peak within ∼10 km distance from the River Ganges, indicating mainly urban inputs with some local pollution hotspots. A heterogeneous relationship between EOCs and population density likely reflects confounding factors including varying input types and controls (e.g. spatial, temporal), wastewater treatment infrastructure and groundwater abstraction. Strong seasonal agreement in EOC concentrations was observed. Co-existence of limited transformation products with associated parent compounds indicate active microbial degradation processes. This study characterizes key controls on the distribution of groundwater EOCs across the urban to rural transition near Patna, as a rapidly developing Indian city, and contributes to the wider understanding of the vulnerability of shallow groundwater to surface-derived contamination in similar environments.

Changes in global groundwater organic carbon driven by climate change and urbanization.

Climate change and urbanization can increase pressures on groundwater resources, but little is known about how groundwater quality will change. Here, we use a global synthesis (n = 9,404) to reveal the drivers of dissolved organic carbon (DOC), which is an important component of water chemistry and substrate for microorganisms that control biogeochemical reactions. Dissolved inorganic chemistry, local climate and land use explained ~ 31% of observed variability in groundwater DOC, whilst aquifer age explained an additional 16%. We identify a 19% increase in DOC associated with urban land cover. We predict major groundwater DOC increases following changes in precipitation and temperature in key areas relying on groundwater. Climate change and conversion of natural or agricultural areas to urban areas will decrease groundwater quality and increase water treatment costs, compounding existing constraints on groundwater resources.

A baseline assessment of emerging organic contaminants in New Zealand groundwater.

Emerging organic contaminants (EOCs) are manufactured compounds, used for a range of purposes, that are a rising concern for freshwater quality, human and aquatic health. Their occurrence in groundwater has been demonstrated in several international surveys. We conducted the first baseline survey on EOC occurrence in New Zealand groundwater, using a wide-screening approach (723 compounds) and a novel stratified to mean residence time (MRT) randomised design to inform future monitoring. A total of 61 sites were sampled: 51 baseline sites from the State of the Environment (SOE) network in the Waikato region and 10 targeted sites located in the vicinity of known EOC sources for comparison. EOCs were detected at 91% of the baseline sites at concentrations ranging from 0.1 to 11,000 ng·L-1. Multiple groups of EOCs were encountered: pesticides (48 compounds), pharmaceuticals (11), industrial (10), preservatives/food additives (3) and personal care products (1). Similar diversity and concentration range of EOCs were observed at the targeted sites, with the addition of drugs of abuse and life-style compounds. EOC detections occurred across young (1-11 yrs. MRT), intermediate (11-50 yrs. MRT) and old (50-250 yrs. MRT) groundwaters with higher concentrations and more types of EOCs detected at sites in the youngest age category. Concentrations of the 73 compounds detected at baseline sites were comparable to those found in overseas groundwaters with 28 compounds measured at concentrations greater than the EU maximum admissible concentration for pesticides. We used the survey results to: review current pesticide monitoring; propose complementary monitoring; identify potential EOC groundwater tracers and identify compounds for which cost-effective national laboratory capability is needed. The Waikato survey results demonstrated ubiquitous occurrence of unmonitored, unregulated EOCs in groundwater and limitations in using targeted approaches to establish monitoring.

Prioritization Approaches for Substances of Emerging Concern in Groundwater: A Critical Review.

Risks from emerging contaminants (ECs) in groundwater to human health and aquatic ecology remain difficult to quantify. The number of ECs potentially found in groundwater presents challenges for regulators and water managers regarding selection for monitoring. This study is the first systematic review of prioritization approaches for selecting ECs that may pose a risk in groundwater. Online databases were searched for prioritization approaches relating to ECs in the aquatic environment using standardized key word search combinations. From a total of 672, 33 studies met the eligibility criteria based primarily on the relevance to prioritizing ECs in groundwater. The review revealed the lack of a groundwater specific contaminant prioritization methodology in spite of widely recognized differences between groundwater and surface water environments with regard to pathways to receptors. The findings highlight a lack of adequate evaluation of methodologies for predicting the likelihood of an EC entering groundwater and knowledge gaps regarding the occurrence and fate of ECs in this environment. The review concludes with a proposal for a prioritization framework for ECs in groundwater monitoring that enables priority lists to be updated as new information becomes available for substances with regard to their usage, physicochemical properties, and hazards.

Tracking changes in the occurrence and source of pharmaceuticals within the River Thames, UK; from source to sea.

There is a growing interest in the occurrence and sources of pharmaceutical substances in the environment. This paper reports the first detailed transect of pharmaceutical occurrence along the River Thames, UK, from source to sea, undertaken during a period of high flow in 2016. In 37 samples a total of 41 pharmaceuticals and 2 lifestyle compounds (cocaine and sucralose) were detected. Total concentration of pharmaceuticals ranged from 0.0012 µg/l to 10.24 µg/l with a median of 2.6 µg/l. Sucralose concentrations varied from <0.01 to 5.9 µg/l with a median concentration of 1.93 µg/l and was detected in every sample except the groundwater-dominated sources of the Thames. Antimicrobials, including those on the surface water watch list (erythromycin, clarithromycin and azithromycin) were detected in every site downstream of the Thames source. Diclofenac, recently on the surface water watch list, was detected in 97% of Thames samples and above the proposed EQS of 0.1 µg/l in 12 samples. Distinct increases in concentration and number of pharmaceuticals were found downstream of the Oxford, Mogdon and Hogsmill wastewater treatment works (WWTW) but were more subdued downstream of the Crossness and Beckton WWTW due to the tidal nature of the Thames and combined sewer outflows. Sucralose was found to be an excellent tracer of wastewaters (treated and untreated) and can be used as a proxy for many pharmaceuticals. Paracetamol and ibuprofen were tracers of untreated wastewater inputs to the Thames due to their high biodegradation within WWTWs.

Tryptophan-like fluorescence as a measure of microbial contamination risk in groundwater.

Microbial water quality is frequently assessed with a risk indicator approach that relies on Escherichia coli. Relying exclusively on E. coli is limiting, particularly in low-resource settings, and we argue that risk assessments could be improved by a complementary parameter, tryptophan-like fluorescence (TLF). Over two campaigns (June 2016 and March 2017) we sampled 37 water points in rural Kwale County, Kenya for TLF, E. coli and thermotolerant coliforms (total n = 1082). Using three World Health Organization defined classes (very high, high, and low/intermediate), risk indicated by TLF was not significantly different from risk indicated by E. coli (p = 0.85). However, the TLF and E. coli risk classifications did show disagreement, with TLF indicating higher risk for 14% of samples and lower risk for 13% of samples. Comparisons of duplicate/replicate results demonstrated that precision is higher for TLF (average relative percent difference of duplicates = 14%) compared to culture-based methods (average RPD of duplicates ≥ 26%). Additionally, TLF sampling is more practical because it requires less time and resources. Precision and practicality make TLF well-suited to high-frequency sampling in low resource contexts. Interpretation and interference challenges are minimised when TLF is measured in groundwaters, which typically have low dissolved organic carbon, relatively consistent temperature, negligible turbidity and pH between 5 and 8. TLF cannot be used as a proxy for E. coli on an individual sample basis, but it can add value to groundwater risk assessments by improving prioritization of sampling and by increasing understanding of spatiotemporal variability.

Real-time detection of faecally contaminated drinking water with tryptophan-like fluorescence: defining threshold values.

We assess the use of fluorescent dissolved organic matter at excitation-emission wavelengths of 280nm and 360nm, termed tryptophan-like fluorescence (TLF), as an indicator of faecally contaminated drinking water. A significant logistic regression model was developed using TLF as a predictor of thermotolerant coliforms (TTCs) using data from groundwater- and surface water-derived drinking water sources in India, Malawi, South Africa and Zambia. A TLF threshold of 1.3ppb dissolved tryptophan was selected to classify TTC contamination. Validation of the TLF threshold indicated a false-negative error rate of 15% and a false-positive error rate of 18%. The threshold was unsuccessful at classifying contaminated sources containing <10 TTC cfu per 100mL, which we consider the current limit of detection. If only sources above this limit were classified, the false-negative error rate was very low at 4%. TLF intensity was very strongly correlated with TTC concentration (ρs=0.80). A higher threshold of 6.9ppb dissolved tryptophan is proposed to indicate heavily contaminated sources (≥100 TTC cfu per 100mL). Current commercially available fluorimeters are easy-to-use, suitable for use online and in remote environments, require neither reagents nor consumables, and crucially provide an instantaneous reading. TLF measurements are not appreciably impaired by common intereferents, such as pH, turbidity and temperature, within typical natural ranges. The technology is a viable option for the real-time screening of faecally contaminated drinking water globally.

Terrestrial dissolved organic matter distribution in the North Sea.

The flow of terrestrial carbon to rivers and inland waters is a major term in the global carbon cycle. The organic fraction of this flux may be buried, remineralized or ultimately stored in the deep ocean. The latter can only occur if terrestrial organic carbon can pass through the coastal and estuarine filter, a process of unknown efficiency. Here, data are presented on the spatial distribution of terrestrial fluorescent and chromophoric dissolved organic matter (FDOM and CDOM, respectively) throughout the North Sea, which receives organic matter from multiple distinct sources. We use FDOM and CDOM as proxies for terrestrial dissolved organic matter (tDOM) to test the hypothesis that tDOM is quantitatively transferred through the North Sea to the open North Atlantic Ocean. Excitation emission matrix fluorescence and parallel factor analysis (EEM-PARAFAC) revealed a single terrestrial humic-like class of compounds whose distribution was restricted to the coastal margins and, via an inverse salinity relationship, to major riverine inputs. Two distinct sources of fluorescent humic-like material were observed associated with the combined outflows of the Rhine, Weser and Elbe rivers in the south-eastern North Sea and the Baltic Sea outflow to the eastern central North Sea. The flux of tDOM from the North Sea to the Atlantic Ocean appears insignificant, although tDOM export may occur through Norwegian coastal waters unsampled in our study. Our analysis suggests that the bulk of tDOM exported from the Northwest European and Scandinavian landmasses is buried or remineralized internally, with potential losses to the atmosphere. This interpretation implies that the residence time in estuarine and coastal systems exerts an important control over the fate of tDOM and needs to be considered when evaluating the role of terrestrial carbon losses in the global carbon cycle.

Role of Humic Acid in the Stability of Ag Nanoparticles in Suboxic Conditions.

Stability and temporal changes in size distributions have been observed for citrate- (cit) and polyvinylpyrrolidone- (PVP) capped silver nanoparticles (AgNPs), in the presence or absence of sulfide and natural organic matter (NOM, as humic acid), while under suboxic conditions. There were substantial differences in the influence of the two capping agents, with PVP-AgNPs showing few or no significant changes in apparent stability or particle size distribution under the conditions examined, while the apparent size distributions of citrate-capped AgNPs changed rapidly. Sulfide and humic acid each individually caused immediate increases in cit-AgNP size distributions, which were then relatively stable over 60-145 days. This may be due to sulfide bridging and cation bridging, respectively. However, in competition, it was the influence of the humic acid that dominated that of the sulfide. These observations have implications for environmental fate and toxicity of AgNP. The increased stability in the presence of even low concentrations of NOM may limit the rapidity of Ag dispersal but may also concentrate the dose received by organisms, which subsequently ingest the stabilized particles.

Mains water leakage: Implications for phosphorus source apportionment and policy responses in catchments.

Effective strategies to reduce phosphorus (P)-enrichment of aquatic ecosystems require accurate quantification of the absolute and relative importance of individual sources of P. In this paper, we quantify the potential significance of a source of P that has been neglected to date. Phosphate dosing of raw water supplies to reduce lead and copper concentrations in drinking water is a common practice globally. However, mains water leakage (MWL) potentially leads to a direct input of P into the environment, bypassing wastewater treatment. We develop a new approach to estimate the spatial distribution and time-variant flux of MWL-P, demonstrating this approach for a 30-year period within the exemplar of the River Thames catchment in the UK. Our analyses suggest that MWL-P could be equivalent to up to c.24% of the P load entering the River Thames from sewage treatment works and up to c.16% of the riverine P load derived from agricultural non-point sources. We consider a range of policy responses that could reduce MWL-P loads to the environment, including incorporating the environmental damage costs associated with P in setting targets for MWL reduction, alongside inclusion of MWL-P within catchment-wide P permits.

A national-scale assessment of micro-organic contaminants in groundwater of England and Wales.

A large variety of micro-organic (MO) compounds is used in huge quantities for a range of purposes (e.g. manufacturing, food production, healthcare) and is now being frequently detected in the aquatic environment. Interest in the occurrence of MO contaminants in the terrestrial and aquatic environments continues to grow, as well as in their environmental fate and potential toxicity. However, the contamination of groundwater resources by MOs has a limited evidence base compared to other freshwater resources. Of particular concern are newly 'emerging contaminants' such as pharmaceuticals and lifestyle compounds, particularly those with potential endocrine disrupting properties. While groundwater often has a high degree of protection from pollution due to physical, chemical and biological attenuation processes in the subsurface compared to surface aquatic environments, trace concentrations of a large range of compounds are still detected in groundwater and in some cases may persist for decades due to the long residence times of groundwater systems. This study provides the first national-scale assessment of micro-organic compounds in groundwater in England and Wales. A large set of monitoring data was analysed to determine the relative occurrence and detected concentrations of different groups of compounds and to determine relationships with land-use, aquifer type and groundwater vulnerability. MOs detected including emerging compounds such as caffeine, DEET, bisphenol A, anti-microbial agents and pharmaceuticals as well as a range of legacy contaminants including chlorinated solvents and THMs, petroleum hydrocarbons, pesticides and other industrial compounds. There are clear differences in MOs between land-use types, particularly for urban-industrial and natural land-use. Temporal trends of MO occurrence are assessed but establishing long-term trends is not yet possible.

A multi-stable isotope framework to understand eutrophication in aquatic ecosystems.

Eutrophication is a globally significant challenge facing aquatic ecosystems, associated with human induced enrichment of these ecosystems with nitrogen (N) and phosphorus (P). However, the limited availability of inherent labels for P and N has constrained understanding of the triggers for eutrophication in natural ecosystems and appropriate targeting of management responses. This paper proposes and evaluates a new multi-stable isotope framework that offers inherent labels to track biogeochemical reactions governing both P and N in natural ecosystems. The framework couples highly novel analysis of the oxygen isotope composition of phosphate (δ(18)OPO4) with dual isotope analysis of oxygen and N within nitrate (δ(15)NNO3, δ(18)ONO3) and with stable N isotope analysis in ammonium (δ(15)NNH4). The River Beult in England is used as an exemplar system for initial evaluation of this framework. Our data demonstrate the potential to use stable isotope labels to track the input and downstream fate of nutrients from point sources, on the basis of isotopic differentiation for both P and N between river water and waste water treatment work effluent (mean difference = +1.7‰ for δ(18)OPO4; +15.5‰ for δ(15)NNH4 (under high flow); +7.3‰ for δ(18)ONO3 and +4.4‰ for δ(15)NNO3). Stable isotope data reveal nutrient inputs to the river upstream of the waste water treatment works that are consistent with partially denitrified sewage or livestock sources of nitrate (δ(15)NNO3 range = +11.5 to +13.1‰) and with agricultural sources of phosphate (δ(18)OPO4 range = +16.6 to +19.0‰). The importance of abiotic and metabolic processes for the in-river fate of N and P are also explored through the stable isotope framework. Microbial uptake of ammonium to meet metabolic demand for N is suggested by substantial enrichment of δ(15)NNH4 (by 10.2‰ over a 100 m reach) under summer low flow conditions. Whilst the concentration of both nitrate and phosphate decreased substantially along the same reach, the stable isotope composition of these ions did not vary significantly, indicating that concentration changes are likely driven by abiotic processes of dilution or sorption. The in-river stable isotope composition and the concentration of P and N were also largely constant downstream of the waste water treatment works, indicating that effluent-derived nutrients were not strongly coupled to metabolism along this in-river transect. Combined with in-situ and laboratory hydrochemical data, we believe that a multi-stable isotope framework represents a powerful approach for understanding and managing eutrophication in natural aquatic ecosystems.

Isotopic Fingerprint for Phosphorus in Drinking Water Supplies.

Phosphate dosing of drinking water supplies, coupled with leakage from distribution networks, represents a significant input of phosphorus to the environment. The oxygen isotope composition of phosphate (δ(18)OPO4), a novel stable isotope tracer for phosphorus, offers new opportunities to understand the importance of phosphorus derived from sources such as drinking water. We report the first assessment of δ(18)OPO4 within drinking water supplies. A total of 40 samples from phosphate-dosed distribution networks were analyzed from across England and Wales. In addition, samples of the source orthophosphoric acid used for dosing were also analyzed. Two distinct isotopic signatures for drinking water were identified (average = +13.2 or +19.7‰), primarily determined by δ(18)OPO4 of the source acid (average = +12.4 or +19.7‰). Dependent upon the source acid used, drinking water δ(18)OPO4 appears isotopically distinct from a number of other phosphorus sources. Isotopic offsets from the source acid ranging from -0.9 to +2.8‰ were observed. There was little evidence that equilibrium isotope fractionation dominated within the networks, with offsets from temperature-dependent equilibrium ranging from -4.8 to +4.2‰. While partial equilibrium fractionation may have occurred, kinetic effects associated with microbial uptake of phosphorus or abiotic sorption and dissolution reactions may also contribute to δ(18)OPO4 within drinking water supplies.