Targeted monitoring for human pharmaceuticals in vulnerable source and final waters

A range of pharmaceuticals has been detected in soils, surface waters and groundwaters across the world. While the reported concentrations are generally low (i.e. sub μg l-1 in surface waters), the substances have been observed throughout the year across a variety of hydrological, climatic and land-use settings. As a result, questions have been raised over the potential for pharmaceuticals in surface waters to enter drinking water supplies and to affect consumers. In a previous Drinking Water Inspectorate (DWI) funded study, results from a simple exposure model were used alongside information on therapeutic doses of pharmaceuticals to identify pharmaceuticals that are likely to be of most concern in UK drinking water sources. However, this previous study was entirely desk-based and did not involve any experimental measurements of pharmaceutical concentrations. The current study was therefore performed to generate actual measurements on the occurrence of pharmaceuticals in source and treated waters in England. The study considered a range of pharmaceutical compounds and their metabolites that have either a) high predicted exposure concentrations; b) toxicological concerns; or c) a low predicted exposure to therapeutic dose ratio. An illicit drug and its major metabolite were also investigated. The study compounds (in total 17) covered a range of chemical classes and varied in terms of their physico-chemical properties. The study was done at four sites where concentrations in source water at the drinking water treatment abstraction point were predicted to be some of the greatest in England. The study therefore is likely to provide a ‘worst case’ assessment of potential human exposure to pharmaceuticals in drinking water in England and Wales. Ten of the 17 study compounds were detected in untreated source waters at sub-μg/l concentrations. Six of these compounds (namely, benzoylecgonine (a metabolite of cocaine), caffeine, carbamazepine (an antiepileptic medicine), carbamazepine epoxide (a metabolite of carbamazepine), ibuprofen and naproxen (both non-steroidal anti-inflammatory drugs) were also detected in treated drinking water. With the exception of carbamazepine epoxide, concentrations in treated drinking water were generally significantly lower than in source water. Even though England is a densely populated country and in some regions there is limited dilution of wastewater effluents, these observations, made at sites that were predicted to have some of the highest concentrations of pharmaceuticals in England and Wales, are in line with results from similar studies performed in other countries. Comparison of measured concentrations of the study compounds in drinking waters with information on therapeutic doses demonstrated that levels of these compounds in drinking water in England are many orders of magnitude lower than levels that are given to patients therapeutically. It would therefore appear that the low or non-detectable levels of pharmaceuticals and illicit drugs present in drinking waters in England and Wales do not pose an appreciable risk to human health

Antioxidant and Antiproliferative Activities of Heated Sterilized Pepsin Hydrolysate Derived from Half-Fin Anchovy (Setipinna taty)

In this paper we studied the antioxidant and antiproliferative activities of the heated pepsin hydrolysate from a marine fish half-fin anchovy (HAHp-H). Furthermore, we compared the chemical profiles including the amino acid composition, the browning intensity, the IR and UV-visible spectra, and the molecular weight distribution between the half-fin anchovy pepsin hydrolysate (HAHp) and HAHp-H. Results showed that heat sterilization on HAHp improved the 1,1-diphenyl-2-picryl-hydrazil (DPPH) radical-scavenging activity and reducing power. In addition, the antiproliferative activities were all increased for HAHp-H on DU-145 human prostate cancer cell line, 1299 human lung cancer cell line and 109 human esophagus cancer cell line. The contents of free amino acid and reducing sugar of HAHp-H were decreased (P < 0.05). However, hydrophobic amino acid residues and the browning intensity of HAHp-H were increased. FT-IR spectroscopy indicated that amide I and amide III bands of HAHp-H were slightly modified, whereas band intensity of amide II was reduced dramatically. Thermal sterilization resulted in the increased fractions of HAHp-H with molecular weight of 3000–5000 Da and below 500 Da. The enhanced antioxidant and antiproliferative activities of HAHp-H might be attributed to the Maillard reaction

Decabromodiphenylether trends in the European environment: bird eggs, sewage sludge and surficial sediments

Concern on relatively high levels and the potential bioaccumulation of decabromodiphenylether (BDE209) has led to a European 8-year monitoring program on trends in BDE209 concentrations in birds, sewage sludge and sediments from seven countries. BDE209 was analysed in four environmental matrices: sparrowhawk eggs (UK), glaucous gull eggs (Bear Island, Norway), sewage sludge (UK, Ireland and the Netherlands) and sediment (France, Germany, the Netherlands, UK and Ireland). BDE209 was detected in most of the glaucous gull and sparrow hawk eggs but neither increasing nor decreasing trends in these BDE209 levels were observed. An indication for debromination of BDE209 in sparrowhawk eggs was found. BDE209 concentrations in sediments ranged from very low ng/g (88 ng/g on an organic carbon (OC) basis) concentrations, in the rivers Elbe, Ems, Seine and the Outer Humber, to high μg/g (120 μg/g OC), in the Western Scheldt, Liverpool Bay and River Mersey. Apart from decreasing values in the Western Scheldt sediment no further decreases in BDE209 concentrations were observed over time, neither in sediment nor in sewage sludge showing that the voluntary emissions control program of the bromine industry only had a local effect. In contrast to the sewage sludge samples from the Netherlands (mean 355 ng/g dry weight (dw) or 1026 ng/g OC), the BDE209 concentrations in the UK increased at all sites from 2006 to 2011 (8092 ng/g dw or 22,367 ng/g OC). The BDE209 levels in several UK sediments and sewage sludge were still very high at the end of the program in 2012, most likely caused by frequent use of BDE209 in the textile industry. This may be indicative of the persistence of BDE209 and the limited degradation into lower brominated congeners in sediment, although it cannot be excluded that ongoing BDE209 emissions have played a role as well

Concurrent sampling of transitional and coastal waters by Diffusive Gradient in Thin-films (DGT) and spot sampling for trace metals analysis

This protocol was developed based on the knowledge acquired in the framework of the Interreg MONITOOL project (EAPA_565/2016) where extensive sampling campaigns were performed in transitional and coastal waters covering eight European countries. It provides detailed procedures and guidelines for the sampling of these waterbodies by concurrent collection of discrete water samples and the deployment of Diffusive Gradient in Thin-films (DGT) passive samplers for the measurement of trace metal concentrations. In order to facilitate the application of this protocol by end-users, it presents steps to follow in the laboratory prior to sampling campaigns, explains the procedures for field campaigns (including in situ measurement of supporting parameters) and subsequent sample processing in the laboratory in preparation for trace metal analyze by inductively coupled plasma-mass spectrometry (ICP-MS) and voltammetry. The protocol provides a systematic, coherent field sampling and sample preparation strategy that was developed in order to ensure comparability and reproducibility of the data obtained from each project Partner in different regions. • Standardization of the concurrent sampling of transitional and coastal waters by DGT passive samplers and spot sampling. • Robust procedures and tips based on existing international standards and comprehensive practical experience. • Links to demonstration videos produced within the MONITOOL project

St Helena marine water quality: Background conditions and development of assessment levels for coastal pollutants

St Helena is an isolated oceanic island located in the tropical South Atlantic, and knowledge of broadscale oceanography and productivity in its surrounding waters is limited. This study used model outputs (2007-2017), remote sensing data (1998-2017) and survey measurements (April 2018 and 2019) to determine background conditions for nutrients, chlorophyll and suspended particulate matter (SPM) in offshore waters and propose standards (thresholds) for assessing inshore water quality based on 50% deviation from seasonal (usually June to November) or annual averages. Seasonal thresholds were proposed for surface nitrate (average 0.18 mu M), phosphate (average 0.26 mu M), silicate (average 2.60 mu M), chlorophyll (average 0.45 mu g chl l(-1)), and SPM (average 0.96 mg l(-1)). Associated background values for most surface parameters (phosphate 0.17 mu M, silicate 1.57 mu M, chlorophyll 0.30 mu g chl l(-1); from model outputs and remote sensing) were slightly higher than offshore observations (April 2019). For nitrate, the average background value (0.12 mu M) was lower than the observed average (0.24 mu M). At depth (150-500 m), annual background values from model outputs were high (nitrate 26.8 mu M, phosphate 1.8 mu M, silicate 17.3 mu M). Observed water masses at depths >150 m, identified to be of Antarctic and Atlantic origin, were nutrient-rich (e.g., 16 mu M for nitrate, April 2019) and oxygen deficient (<4-6 mg l(-1)). A thermocline layer (between ca. 10 and 230 m), characterized by a sub-surface chlorophyll maximum (average 0.3-0.5 mu g chl l(-1)) near the bottom of the euphotic zone (ca. 100 m), is likely to sustain primary and secondary production at St Helena. For assessing inshore levels of chemical contaminants and fecal bacteria estimated from survey measurements, standards were derived from the literature. A preliminary assessment of inshore observations using proposed thresholds from surface offshore waters and relevant literature standards indicated concerns regarding levels of nutrients and fecal bacteria at some locations. More detailed modeling and/or field-based studies are required to investigate seasonal trends and nutrient availability to inshore primary producers and to establish accurate levels of any contaminants of interest or risk to the marine environment

Assessing variability in the ratio of metal concentrations measured by DGT-type passive samplers and spot sampling in European seawaters

The current study evaluates the effect of seawater physico-chemical characteristics on the relationship between the concentration of metals measured by Diffusive Gradients in Thin films (DGT) passive samplers (i.e., DGT-labile concentration) and the concentrations measured in discrete water samples. Accordingly, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to measure the total dissolved metal concentrations in the discrete water samples and the labile metal concentrations obtained by DGT samplers; additionally, lead and cadmium conditional labile fractions were determined by Anodic Stripping Voltammetry (ASV) and total dissolved nickel was measured by Cathodic Stripping Voltammetry (CSV). It can be concluded that, in general, the median ratios of DGT/ICP and DGT/ASV(CSV) were lower than 1, except for Ni (median ratio close to 1) and Zn (higher than 1). This indicates the importance of speciation and time-integrated concentrations measured using passive sampling techniques, which is in line with the WFD suggestions for improving the chemical assessment of waterbodies. It is the variability in metal content in waters rather than environmental conditions to which the variability of the ratios can be attributed. The ratios were not significantly affected by the temperature, salinity, pH, oxygen, DOC or SPM, giving a great confidence for all the techniques used. Within a regulatory context such as the EU Water Framework Directive this is a great advantage, since the simplicity of not needing to use corrections to minimize the effects of environmental variables could help in implementing DGTs within monitoring networks

Atypical cadherin MUCDHL and inflammatory bowel diseases : involvement in pathogeny, evolution and response to treatment

Les causes des Maladies Inflammatoire Chroniques Intestinales (MICI) restent mal comprises et il n’existe aucun traitement curatif. L’une des complications possibles des MICI est l’augmentation du risque de cancer colorectal (CCR). La cadhérine atypique MUCDHL pourrait être impliquée dans les MICI. Nous avons étudié le rôle de MUCDHL dans la pathogénie des MICI, ainsi que les mécanismes moléculaires qui restaurent son expression. Nous avons montré que l’expression de MUCDHL est diminuée dans la muqueuse intestinale inflammatoire. De plus, les 5-aminosalicylés, utilisés pour traiter les MICI et prévenir le CCR associé, augmentent son expression en stimulant celle de PPAR-γ et de CDX2 ou en inhibant celle de la β-caténine. Chez les souris Mucdhl -/-, l’absence de MUCDHL accélère et amplifie l’inflammation colique induite par le Dextran Sulfate de Sodium et retarde la réparation muqueuse. Nos données montrent l’implication de MUCDHL dans la physiopathologie des MICI et suggèrent qu’il pourrait constituer une cible thérapeutique d’intérêt.The pathogenesis of Inflammatory Bowel Diseases (IBD) remains poorly understood and there is currently no curative treatment. In addition, patients with colonic IBD are at increased risk of colorectal cancer (CRC). The atypical cadherin MUCDHL could be involved in IBD. We studied the role of MUCDHL in the pathogenesis of IBD, as well as the molecular mechanisms that restore its expression. We have shown that MUCDHL expression is decreased in the inflammatory intestinal mucosa. In addition, 5-aminosalicylates, used to treat IBD and prevent associated CRC, increase its expression by stimulating PPAR-γ and CDX2 or by inhibiting β-catenin. In Mucdhl -/- mice, the absence of MUCDHL accelerates and amplifies colonic inflammation induced by Dextran Sodium Sulfate and delays mucosal repair. Our data show MUCDHL's involvement in the pathophysiology of IBD and suggest that it could be a therapeutic target of interest

Atypical cadherin MUCDHL and inflammatory bowel diseases : involvement in pathogeny, evolution and response to treatment

Les causes des Maladies Inflammatoire Chroniques Intestinales (MICI) restent mal comprises et il n’existe aucun traitement curatif. L’une des complications possibles des MICI est l’augmentation du risque de cancer colorectal (CCR). La cadhérine atypique MUCDHL pourrait être impliquée dans les MICI. Nous avons étudié le rôle de MUCDHL dans la pathogénie des MICI, ainsi que les mécanismes moléculaires qui restaurent son expression. Nous avons montré que l’expression de MUCDHL est diminuée dans la muqueuse intestinale inflammatoire. De plus, les 5-aminosalicylés, utilisés pour traiter les MICI et prévenir le CCR associé, augmentent son expression en stimulant celle de PPAR-γ et de CDX2 ou en inhibant celle de la β-caténine. Chez les souris Mucdhl -/-, l’absence de MUCDHL accélère et amplifie l’inflammation colique induite par le Dextran Sulfate de Sodium et retarde la réparation muqueuse. Nos données montrent l’implication de MUCDHL dans la physiopathologie des MICI et suggèrent qu’il pourrait constituer une cible thérapeutique d’intérêt.The pathogenesis of Inflammatory Bowel Diseases (IBD) remains poorly understood and there is currently no curative treatment. In addition, patients with colonic IBD are at increased risk of colorectal cancer (CRC). The atypical cadherin MUCDHL could be involved in IBD. We studied the role of MUCDHL in the pathogenesis of IBD, as well as the molecular mechanisms that restore its expression. We have shown that MUCDHL expression is decreased in the inflammatory intestinal mucosa. In addition, 5-aminosalicylates, used to treat IBD and prevent associated CRC, increase its expression by stimulating PPAR-γ and CDX2 or by inhibiting β-catenin. In Mucdhl -/- mice, the absence of MUCDHL accelerates and amplifies colonic inflammation induced by Dextran Sodium Sulfate and delays mucosal repair. Our data show MUCDHL's involvement in the pathophysiology of IBD and suggest that it could be a therapeutic target of interest