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

Potential role of veterinary flea products in widespread pesticide contamination of English rivers

Little is known about the environmental fate or impact of pesticides used to control companion animal parasites. Using data from the Environment Agency, we examined the occurrence of fipronil, fipronil metabolites and imidacloprid in 20 English rivers from 2016 to 2018, as indicators of the potential contamination of waterways from their use as ectoparasiticides on pets. Water samples were collected by the Environment Agency as part of their chemical surveillance programme and analysed using Liquid Chromatography Mass Spectrometry / Quadrupole-Time-of-Flight Mass spectrometry (LC/Q-TOF-MS) methods. A total of 3861 chemical analyses were examined, and the significance and potential sources of this contamination were assessed. Fipronil, fipronil sulfone, fipronil sulfide (collectively known as fiproles) and imidacloprid were detected in 98.6%, 96.5%, 68.7% and 65.9% of samples, respectively. Across the river sites sampled, the mean concentrations of fipronil (17 ng/l, range <0.3–980 ng/l), and fipronil sulfone (6.5 ng/l, range <0.2–39 ng/l) were 5.3 and 38.1 times their chronic toxicity limits of 3.2 and 0.17 ng/l, respectively. Imidacloprid had a mean concentration of 31.7 ng/l (range <1–360 ng/l), which was below its chronic toxicity limit of 35 ng/l, however seven out of 20 sites exceeded that limit. Chronic risk quotients indicate a high environmental risk to aquatic ecosystems from fiproles, and a moderate risk from imidacloprid. Sites immediately downstream of wastewater treatment works had the highest levels of fipronil and imidacloprid, supporting the hypothesis that potentially significant quantities of pesticides from veterinary flea products may be entering waterways via household drains. These findings suggest the need for a reevaluation of the environmental risks associated with the use of companion animal parasiticide products, and the risk assessments that these products undergo prior to regulatory approval

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

Emerging organic contaminants in the river Ganga and key tributaries in the middle Gangetic Plain, India:Characterization, distribution &amp; 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

Proportional contributions to organic chemical mixture effects in groundwater and surface water

Semi-quantitative GC-MS and LC-MS measurements of organic chemicals in groundwater and surface waters were used to assess the overall magnitude and contribution of the most important substances to calculated mixture hazard. Here we use GC-MS and LC-MS measurements taken from two separate national monitoring programs for groundwater and surface water in England, in combination with chronic species sensitivity distribution (SSD) HC50 values published by Posthuma et al. (2019, Environ. Toxicol. Chem, 38, 905–917) to calculate individual substance hazard quotients and mixture effects using a concentration addition approach. The mixture analysis indicated that, as anticipated, there was an increased hazard from the presence of a cocktail of substances at sites compared to the hazard for any single chemical. The magnitude of the difference between the hazard attributed to the most important chemical and the overall mixture effect, however, was not large. Thus, the most toxic chemical contributed ≥ 20% of the calculated mixture effect in >99% of all measured groundwater and surface water samples. On the basis of this analysis, a 5 fold assessment factor placed on the risk identified for any single chemical would offer a high degree of in cases where implementation of a full mixture analysis was not possible. This finding is consistent with previous work that has assessed chemical mixture effects within field monitoring programs and as such provides essential underpinning for future policy and management decisions on how to effectively and proportionately manage mixture risks

Dietary proanthocyanidins promote localized antioxidant responses in porcine pulmonary and gastrointestinal tissues during Ascaris suum‐induced type 2 inflammation

Proanthocyanidins (PAC) are dietary polyphenols with putative anti‐inflammatory and immunomodulatory effects. However, whether dietary PAC can regulate type‐2 immune function and inflammation at mucosal surfaces remains unclear. Here, we investigated if diets supplemented with purified PAC modulated pulmonary and intestinal mucosal immune responses during infection with the helminth parasite Ascaris suum in pigs. A. suum infection induced a type‐2 biased immune response in lung and intestinal tissues, characterized by pulmonary granulocytosis, increased Th2/Th1 T cell ratios in tracheal‐bronchial lymph nodes, intestinal eosinophilia, and modulation of genes involved in mucosal barrier function and immunity. Whilst PAC had only minor effects on pulmonary immune responses, RNA‐sequencing of intestinal tissues revealed that dietary PAC significantly enhanced transcriptional responses related to immune function and antioxidant responses in the gut of both naïve and A. suum‐infected animals. A. suum infection and dietary PAC induced distinct changes in gut microbiota composition, primarily in the jejunum and colon, respectively. Notably, PAC consumption substantially increased the abundance of Limosilactobacillus reuteri. In vitro experiments with porcine macrophages and intestinal epithelial cells supported a role for both PAC polymers and PAC‐derived microbial metabolites in regulating oxidative stress responses in host tissues. Thus, dietary PAC may have distinct beneficial effects on intestinal health during infection with mucosal pathogens, while having a limited activity to modulate naturally‐induced type‐2 pulmonary inflammation. Our results shed further light on the mechanisms underlying the health‐promoting properties of PAC‐rich foods, and may aid in the design of novel dietary supplements to regulate mucosal inflammatory responses in the gastrointestinal tract.</p

Worst-case ranking of organic chemicals detected in groundwaters and surface waters in England

The Environment Agency has been using Gas Chromatography–Mass Spectrometry (GC–MS) and Accurate-mass Quadrupole Time-of-Flight (Q-TOF) / Liquid Chromatography-Mass Spectrometry (LC-MS) target screen analysis to semi-quantitatively measure organic substances in groundwater and surface water since 2009 for GC–MS and 2014 for LC-MS. Here we use this data to generate a worst-case “risk” ranking of the detected substances. Three sets of hazard values relating to effects on aquatic organisms, namely Water Framework Directive EQSs, NORMAN Network PNECs (hereafter NORMAN PNEC) and chronic Species Sensitivity Distribution (SSD) HC50s from Posthuma et al., (2019) were used for the assessment. These hazard values were compared to the highest measured concentration for each chemical to generate a worst-case hazard quotient (HQ). Calculated HQs for each metric were ranked, averaged and multiplied by rank for detection frequency to generate an overall ordering based on HQ and occurrence. This worst-case approach was then used to generate ranking lists for GC–MS and LC-MS detected substances in groundwater and surface water. Pesticides in the top 30 overall ranked list included more legacy pesticides in groundwater and more current use actives in surface water. Specific uses were linked to some high rankings (e.g. rotenone for invasive species control). A number of industrial and plastics associated chemicals were ranked highly in the groundwater dataset, while more personal care products and pharmaceuticals were highly ranked in surface waters. Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) compounds were commonly highly ranked in both environmental compartments. The approach confirmed high rankings for some substance (e.g. selected pesticides) from previous prioritization exercises, but also identified novel substance for consideration (e.g. some PFAS compounds and pharmaceuticals). Overall our approach provided a simple approach using readily accessible data to identify substances for further and more detailed assessment