Antibiotics in the Basque coast (N Spain): Occurrence in waste and receiving waters, and risk assessment (2017-2020).

The study of the presence of antibiotics in the aquatic environment is a preliminary step to analyse their possible harmful effects on aquatic ecosystems. In order to monitor their occurrence in the aquatic environment, the European Commission established in 2015, 2018, and 2020 three Watch Lists of substances for Union-wide monitoring (Decisions (EU) 2015/495, 2018/840, and 2020/1161), where some antibiotics within the classes of macrolides, fluoroquinolones and penicillins were included. In the Basque coast, northern Spain, three macrolide antibiotics (erythromycin, clarithromycin, azithromycin) and ciprofloxacin were monitored quarterly from 2017 to 2020 (covering a period before and after the COVID19 outbreak), in water samples collected from two Waste Water Treatment Plants (WWTPs), and three control points associated with receiving waters (transitional and coastal water bodies). This work was undertaken for the Basque Water Agency (URA). The three macrolide antibiotics in water showed a frequency of quantification >65 % in the Basque coast, with higher concentrations in the WWTP emission stations than in receiving waters. Their frequency of quantification decreased from 2017 to 2020, as did the consumption of antibiotics in Spanish primary care since 2015. Ciprofloxacin showed higher frequencies of quantification in receiving waters than in wastewaters, but the highest concentrations were observed in the WWTP emission stations. Although consumption of fluoroquinolones (among which is ciprofloxacin) in primary care in the Basque Country has decreased in recent years, this trend was not observed in the waters sampled in the present study. On the other hand, concentrations of clarithromycin, azithromycin, and ciprofloxacin in receiving waters exceeded their respective Predicted No-Effect Concentrations, so they could pose an environmental risk. These substances are widely used in human and animal medicine, so, although only ciprofloxacin is included in the third Watch List, it would be advisable to continue monitoring macrolides in the Basque coast as well.

Pharmaceuticals in a Mediterranean Basin: The influence of temporal and hydrological patterns in environmental risk assessment.

Occurrence of pharmaceuticals in the aquatic environment is nowadays a well-established issue that has become a matter of both scientific and public concern. Tons of different classes of pharmaceuticals find their way to the environment at variable degrees, after their use and excretion through wastewater and sewage treatment systems. The main goal of this study was to correlate the dynamics and the environmental risk of pharmaceuticals with different temporal and hydrological patterns, at the Guadiana Basin (South of Portugal). Water samples were collected bimonthly during 2017 (classified as a drought year) and 2018 (post-drought year) in: Zebro, Álamos and Amieira (intermittent hydrological streams), and Lucefécit (perennial hydrological stream). The pharmaceuticals quantified in higher concentrations, out of 27 investigated, were diclofenac (up to 4806 ng L-1), ibuprofen (3161 ng L-1), hydrochlorothiazide (2726 ng L-1) and carbamazepine (3223 ng L-1). Zebro and Álamos presented the highest contamination by this group of environmental hazardous substances, which may be correlated with the presence of wastewater treatment plants upstream the sampling point of each stream. Furthermore, the highest concentrations occurred mainly during the dry period (2017), when the flow was nearly inexistent in Zebro, and in Álamos after the first heavy rainfalls. In specific periods, the high concentrations of pharmaceuticals detected may induce risk for the organisms of lowest trophic levels, damaging the balance of the ecosystems at these streams. The risk quotient optimised approach (RQf) integrating exposure, toxicity and persistence factors, ranks the pharmaceuticals investigated in terms of risk for the aquatic ecosystems as follows: diclofenac, ibuprofen and carbamazepine (high risk), clarithromycin (moderate risk), acetaminophen, ofloxacin and bezafibrate (endurable risk), and hydrochlorothiazide (negligible risk).

Comparative measurement and quantitative risk assessment of alcohol consumption through wastewater-based epidemiology: An international study in 20 cities.

Quantitative measurement of drug consumption biomarkers in wastewater can provide objective information on community drug use patterns and trends. This study presents the measurement of alcohol consumption in 20 cities across 11 countries through the use of wastewater-based epidemiology (WBE), and reports the application of these data for the risk assessment of alcohol on a population scale using the margin of exposure (MOE) approach. Raw 24-h composite wastewater samples were collected over a one-week period from 20 cities following a common protocol. For each sample a specific and stable alcohol consumption biomarker, ethyl sulfate (EtS) was determined by liquid chromatography coupled to tandem mass spectrometry. The EtS concentrations were used for estimation of per capita alcohol consumption in each city, which was further compared with international reports and applied for risk assessment by MOE. The average per capita consumption in 20 cities ranged between 6.4 and 44.3L/day/1000 inhabitants. An increase in alcohol consumption during the weekend occurred in all cities, however the level of this increase was found to differ. In contrast to conventional data (sales statistics and interviews), WBE revealed geographical differences in the level and pattern of actual alcohol consumption at an inter-city level. All the sampled cities were in the "high risk" category (MOE<10) and the average MOE for the whole population studied was 2.5. These results allowed direct comparisons of alcohol consumption levels, patterns and risks among the cities. This study shows that WBE can provide timely and complementary information on alcohol use and alcohol associated risks in terms of exposure at the community level.

Pharmaceuticals and pesticides in reclaimed water: Efficiency assessment of a microfiltration-reverse osmosis (MF-RO) pilot plant.

Water reuse is becoming a common practice in several areas in the world, particularly in those impacted by water scarcity driven by climate change and/or by rising human demand. Since conventional wastewater treatment plants (WWTPs) are not able to efficiently remove many organic contaminants and pathogens, more advanced water treatment processes should be applied to WWTP effluents for water reclamation purposes. In this work, a pilot plant based on microfiltration (MF) followed by reverse osmosis (RO) filtration was applied to the effluents of an urban WWTP. Both the WWTP and the pilot plant were investigated with regards to the removal of a group of relevant contaminants widely spread in the environment: 28 pharmaceuticals and 20 pesticides. The combined treatment by the MF-RO system was able to quantitatively remove the target micropollutants present in the WWTP effluents to values either in the low ng/L range or below limits of quantification. Monitoring of water quality of reclaimed water and water reclamation sources is equally necessary to design the most adequate treatment procedures aimed to water reuse for different needs.

Assessment of multi-chemical pollution in aquatic ecosystems using toxic units: compound prioritization, mixture characterization and relationships with biological descriptors.

Chemical pollution is typically characterized by exposure to multiple rather than to single or a limited number of compounds. Parent compounds, transformation products and other non-targeted compounds yield mixtures whose composition can only be partially identified by monitoring, while a substantial proportion remains unknown. In this context, risk assessment based on the application of additive ecotoxicity models, such as concentration addition (CA), is rendered somewhat misleading. Here, we show that ecotoxicity risk information can be better understood upon consideration of the probabilistic distribution of risk among the different compounds. Toxic units of the compounds identified in a sample fit a lognormal probability distribution. The parameters characterizing this distribution (mean and standard deviation) provide information which can be tentatively interpreted as a measure of the toxic load and its apportionment among the constituents in the mixture (here interpreted as mixture complexity). Furthermore, they provide information for compound prioritization tailored to each site and enable prediction of some of the functional and structural biological variables associated with the receiving ecosystem. The proposed approach was tested in the Llobregat River basin (NE Spain) using exposure and toxicity data (algae and Daphnia) corresponding to 29 pharmaceuticals and 22 pesticides, and 5 structural and functional biological descriptors related to benthic macroinvertebrates (diversity, biomass) and biofilm metrics (diatom quality, chlorophyll-a content and photosynthetic capacity). Aggregated toxic units based on Daphnia and algae bioassays provided a good indication of the pollution pattern of the Llobregat River basin. Relative contribution of pesticides and pharmaceuticals to total toxic load was variable and highly site dependent, the latter group tending to increase its contribution in urban areas. Contaminated sites' toxic load was typically dominated by fewer compounds as compared to cleaner sites where more compounds contribute.

Analysis of the occurrence and risk assessment of polar pesticides in the Llobregat River Basin (NE Spain).

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (on-line SPE-LC-ESI-MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L(-1), respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L(-1), were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.

Environmental risk assessment of pharmaceuticals in rivers: relationships between hazard indexes and aquatic macroinvertebrate diversity indexes in the Llobregat River (NE Spain).

Continuous input of pharmaceuticals into rivers, through wastewater treatment systems, may cause adverse effects on the aquatic ecosystems of the receiving waterbodies, due to the intrinsic biological activity of these compounds. To investigate this issue, we have carried out an Environmental Risk Assessment in the lower part of the Llobregat River basin (NE Spain). The survey was carried out along three campaigns in 7 sampling points, located in the main river and in one of its tributaries (Anoia River). In each sample, 29 commonly used pharmaceuticals, belonging to different therapeutical classes (analgesics and non-steroidal anti-inflammatories (NSAIDs), lipid regulators, psychiatric drugs, anti-histamines, anti-ulcer agents, antibiotics and beta-blockers) have been determined. Simultaneously, the macroinvertebrate community status of the same points has been also studied. Hazard quotient indexes have been estimated for the most representative compounds as the ratio between concentrations and EC(50) reported values, for three bioassays commonly used in environmental toxicology, namely, fish, Daphnia and algae. Hazard indexes are obtained for each sample by summing up the hazard quotients of all the compounds present, and taking its average along the three sampling campaigns. In general, hazard quotients tend to increase when going downstream. Only those points located most upstream of the two rivers can be qualified under low risk for the three bioassays. The most sensitive bioassay seems to be algae, followed by Daphnia and fish. Log-transformed hazard indexes show fairly good inverse correlations (r=-0.58 to -0.93, p<0.05) with Shannon diversity indexes of macroinvertebrates, determined from both densities and biomasses. Best correlations are obtained for Daphnia based hazard indexes, as expected from its taxonomical proximity to macroinvertebrates. The abnormal correlation behaviour found in one point located in the Anoia River is explained by the presence of other previously reported pollutants of industrial origin, generated by the nearby existing industry.