Priority and emerging organic microcontaminants in three Mediterranean river basins: Occurrence, spatial distribution, and identification of river basin specific pollutants.

There is a worldwide growing use of chemicals by our developed, industrialized, and technological society. More than 100,000 chemical substances are thus commonly used both by industry and households. Depending on the amount produced, physical-chemical properties, and mode of use, many of them may reach the environment and, notably, the aquatic receiving systems. This may result in undesirable and harmful side-effects on both the human and the ecosystem's health. Mediterranean rivers are largely different from Northern and Central European rivers in terms of hydrological regime, climate conditions (e.g. air temperature, solar irradiation, precipitation), and socio-economics (e.g. land use, tourism, crop types, etc.), with all these factors leading to differences in the relative importance of the environmental stressors, in the classes and levels of the pollutants found and their environmental fate. Furthermore, water scarcity might be critical in affecting water pollution because of the lowered dilution capacity of chemicals. This work provides raw chemical data from different families of microcontaminants identified in three selected Mediterranean rivers (the Sava, Evrotas, and Adige) collected during two sampling campaigns conducted in 2014 and 2015 in three different matrices, namely, water, sediments, and biota (fish). More than 200 organic micropollutants were analyzed, including relevant groups like pharmaceuticals, personal care products, perfluorinated compounds, pesticides, pyrethroid insecticides, flame retardants, and persistent organic pollutants. Data obtained were summarized with some basic statistics for all compound families and matrices analyzed. Observed occurrence and spatial patterns were interpreted both in terms of compound physical-chemical properties and local environmental pressures. Finally, their spatial distribution was examined and their ecotoxicological risk in the water phase was assessed. This allowed locating, at each basin, the most polluted sites ("hot spots") and identifying the respective river basin specific pollutants (RBSPs), prioritizing them in terms of the potential ecotoxicological risk posed to the aquatic ecosystems.

Contamination patterns and attenuation of pharmaceuticals in a temporary Mediterranean river.

The contamination patterns and fate of pharmaceutically active compounds (PhACs) were investigated in the Evrotas River (Southern Greece). This is a temporary river with differing levels of water stress and water quality impairment in a number of its reaches. Three sampling campaigns were conducted in order to capture different levels of water stress and water quality. Four sampling sites located on the main channel of the Evrotas River were sampled in July 2015 (moderate stream flow), and June and September 2016 (low stream flow). Discharge of urban wastewater has been determined as the main source of pollution, with PhACs, nutrients and other physicochemical parameters considerably increasing downstream the wastewater treatment plant (WWTP) of Sparta city. Due to the pronounced hydrological variation of the Evrotas River, generally, the highest concentrations of PhACs have been detected during low flow conditions. Simultaneously, low flow resulted in an increased water travel time and consequently longer residence time that accounted for the higher attenuation of most PhACs. The average decrease in total concentration of PhACs within the studied waterbody segment (downstream of Sparta city) increased from 22% in July 2015 to 25% in June 2016 and 77% in September 2016. The PhACs with the highest average concentration decrease throughout the sampling campaigns were hydrochlorothiazide, followed by sotalol, carbamazepine, valsartan, and naproxen.

Diatom responses to sewage inputs and hydrological alteration in Mediterranean streams.

We analyzed the conjoint effects of sewage inputs and hydrological alteration on the occurrence of teratological forms and on the assemblage composition of stream benthic diatoms. The study was performed in 11 Mediterranean streams which received treated or untreated urban sewage (Impact sites, I), whose composition and morphological anomalies were compared to upstream unaffected (Control, C) sites. The impact sites had high concentrations of ammonium, phosphorus, and pharmaceutical compounds (antibiotics, analgesics, and anti-inflammatories), particularly in those receiving untreated sewage. Impact sites had a higher proportion of teratological forms as well as a prevalence of diatom taxa tolerant to pollution. The differences in the diatom assemblage composition between the paired C and I sites were the largest in the impacted sites that received untreated sewage inputs as well as in the systems with lower dilution capacity. In these sites, the diatom assemblage was composed by a few pollution-tolerant species. Mediterranean river systems facing hydrological stress are highly sensitive to chemical contamination, leading to the homogenization of their diatom assemblages.

Impact of urban chemical pollution on water quality in small, rural and effluent-dominated Mediterranean streams and rivers.

The impact and occurrence of wastewater (treated and untreated) derived pharmaceutically active compounds (PhACs) have been investigated in small, rural and effluent-dominated tributaries of the lower Ebro River located in the North-Eastern Spain (Catalonia). We have observed the predominant effect of stream flow and consequently dilution factor on the concentration levels of detected PhACs that combined with the absence of wastewater treatment plants (WWTP) resulted in 12 times higher concentrations in streams with direct discharge of untreated wastewater. Non-steroidal anti-inflammatory drugs (NSAIDs) were the most ubiquitous compounds, in terms of both individual concentration and frequency of detection. In the sites impacted by raw wastewater, acetaminophen and ibuprofen showed the highest concentrations among all analyzed PhACs, reaching concentrations up to 7.78µgL-1 and 2.66µgL-1, respectively. However, PhACs detected in the sites impacted by treated wastewater showed generally lower concentration levels and frequencies of detection. Also, effluent-dominated streams showed higher concentration levels of PhACs due to a generally lower stream flows and small dilution factors. However, concentration levels of detected PhACs were dependent on the hydraulic travel time and distance from the discharge point and related with the in-stream attenuation. As a result, this study highlights the combined impact of hydrological and chemical stressors on the water quality of the rural Mediterranean aquatic ecosystems.

Wastewater pollution differently affects the antibiotic resistance gene pool and biofilm bacterial communities across streambed compartments.

Wastewater discharges introduce antibiotic residues and antibiotic-resistant bacteria (ARB) into surface waters. Both inputs directly affect the streambed resistome, either by exerting a selective pressure that favour the proliferation of resistant phenotypes or by enriching the resident communities with wastewater-associated ARB. Here, we investigated the impact of raw and treated urban wastewater discharges on epilithic (growing on rocks) and epipsammic (growing on sandy substrata) streambed biofilms. The effects were assessed by comparing control and impact sites (i) on the composition of bacterial communities; (ii) on the abundance of twelve antibiotic resistance genes (ARGs) encoding resistance to ß-lactams, fluoroquinolones, sulphonamides, tetracyclines, macrolides and vancomycin, as well as the class 1 integron-integrase gene (intI1); (iii) on the occurrence of wastewater-associated bacteria, including putative pathogens, and their potential linkage to target ARGs. We measured more pronounced effects of raw sewage than treated wastewater at the three studied levels. This effect was especially noticeable in epilithic biofilms, which showed a higher contribution of wastewater-associated bacteria and ARB than in epipsammic biofilms. Comparison of correlation coefficients obtained between the relative abundance of both target ARGs and operational taxonomic units classified as either potential pathogens or nonpathogens yielded significant higher correlations between the former category and genes intI1, sul1, sul2 and ermB. Altogether, these results indicate that wastewater-associated micro-organisms, including potential pathogens, contribute to maintain the streambed resistome and that epilithic biofilms appear as sensitive biosensors of the effect of wastewater pollution in surface waters.

Contamination sources and distribution patterns of pharmaceuticals and personal care products in Alpine rivers strongly affected by tourism.

Knowledge regarding the impact of tourism on the emergence of pharmaceuticals and personal care products (PPCPs) in Alpine river waters is limited and scarce. Therefore, a study on the occurrence patterns and spatiotemporal variability of 105 PPCPs in an Alpine river basin located in the Trentino-Alto Adige region (North-Eastern Italy) has been conducted. We observed that the total concentration of analyzed PPCPs was generally higher in all sampling sites during winter than in the summer. The analysis of tourist data revealed that during both sampling campaigns the number of tourists was lower in the downstream sites in comparison with the upstream area of the basin (Val di Sole). Particularly, sampling sites located near important tourist resorts have shown the highest abundance of the PPCPs during winter, being analgesics/anti-inflammatories, antihypertensives and antibiotics the most abundant pharmaceutically active compounds (PhACs). Diclofenac showed the highest concentration amongst PhACs, reaching concentrations up to 675ngL-1 in the sampling site situated downstream of the Tonale wastewater treatment plant (WWTP). Antihypertensives were found at concentrations >300ngL-1, while antibiotics were quantified up to 196ngL-1, respectively. Amongst personal care products (PCPs), the most abundant compound was octyl-dimethyl-p-aminobenzoic acid (ODPABA) with concentrations reaching up to 748ngL-1 in the sampling site situated within the Rotaliana district. In general, concentrations and detection frequencies were higher in water than in the sediment samples. The most frequently detected PhACs in sediments from both sampling campaigns were antibiotics, while amongst PCPs in sediments, octocrylene (OC) showed the highest concentration in both sampling campaigns. As a result, this study highlights the potential impact of tourism on the water quality of the Alpine aquatic ecosystems.