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 g/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

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

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

A combined geochemical and hydrological approach for understanding macronutrient sources

This study employed complementary geochemical techniques and distributed hydrological modelling to investigate multiple sources of catchment macronutrients and characterise their changes in contrasting storm and baseflow conditions. This approach was demonstrated for the Beult catchment in the county of Kent (England), a designated Site of Special Scientific Interest (SSSI) indentified as failing to meet water quality standards for key nutrients under the Water Framework Directive. Significant changes in nutrient stoichiometry and bioavailability are observed for surface waters under contrasting flow regimes. Soluble reactive phosphorus (SRP) concentrations are approximately twice as high during baseflow compared to high flow, while the inverse is true for particulate, colloidal and dissolved hydrolysable phosphorus, dissolved organic carbon and nitrate. Nitrogen (N):phosphorus (P) ratios are lower during baseflow for most surface waters impacted by diffuse sources of pollution. Fluorescence indices of dissolved organic matter (DOM) show that waste water inputs may be locally important sources of more complex low molecular weight DOM, particularly during baseflow. Nitrate N and O isotope signatures, combined with other dissolved chemical tracers, confirm the dominance of wastewater N inputs at sites downsteam of sewerage treatment works during baseflow, with a shift towards the soil N pool in surface waters across the catchment during high flow. Distributed hydrological modelling using the Grid-to-Grid model reveal areas with the greatest runoff also export higher N and P concentrations, and hence deliver a greater flux of macronutrients, while forested areas with low nutrient concentrations reduce runoff and nutrient fluxes. During periods of high runoff, nested sampling indicates that nutrient fluxes scale with catchment area. This combined approach enables a more thorough assessment of the macronutrient sources and dynamics, better informing management options in nutrient impacted catchments

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 (δ18OPO4), 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 δ18OPO4 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 δ18OPO4 of the source acid (average = +12.4 or +19.7‰). Dependent upon the source acid used, drinking water δ18OPO4 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 δ18OPO4 within drinking water supplies

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 (δ18OPO4) with dual isotope analysis of oxygen and N within nitrate (δ15NNO3, δ18ONO3) and with stable N isotope analysis in ammonium (δ15NNH4). 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 δ18OPO4; +15.5‰ for δ15NNH4 (under high flow); +7.3‰ for δ18ONO3 and +4.4‰ for δ15NNO3). 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 (δ15NNO3 range = +11.5 to +13.1‰) and with agricultural sources of phosphate (δ18OPO4 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 δ15NNH4 (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

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 = 1,082). 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

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

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 monitorin

The potential for citizen science to improve the reach of sanitary inspections

To achieve Sustainable Development Goals (SDGs) 6, universal and equitable access to safe and affordable drinking-water quality and sanitation for all, and 10, to reduce inequality within and among countries, additional and urgent work is required. Efforts to achieve these Goals in the context of small drinking-water supplies, which are the furthest behind in regards to progress, are of particular need. Reasons for this disparity in progress include the remoteness of access to small drinking-water supplies and the lack of technical and financial capacity for monitoring supplies. The World Health Organization promote the use of Sanitary inspection (SI) as an on-site assessment of risk. Despite the potential to increase the body of knowledge and information on supplies in a region, there has been limited research into the role of citizen science and SIs. To meet SDG targets, we need to improve the reach of SIs. This study uses a mixed methods approach of quantitative on-site SI data collection and remote SI data collection via photographic images, together with qualitative data collection, collected by non-expert students, who are citizens of Malawi, as well as a panel of experts in the field of SI. Results indicate that, although further research into the topic is required prior to widescale implementation, the potential exists for citizens to conduct SI, with remote expert verification of the results using photographic images of supplies. Further documentation or guidance is required to support citizens in this process. The results highlight a critical gap in the availability of appropriate documentation for unprotected spring sources which is urgently required. The use of citizen science for SI data collection is in its infancy. However, this study indicates that there is potential to explore the use of citizen science in this area, which will contribute to achieving SDGs 6 and 10