The increasing consumption of pharmaceuticals, alongside their limited removal in wastewater treatment plants (WWTPs), have led to their ubiquitous occurrence in receiving aquatic environments. This ...study addresses the occurrence of 68 pharmaceuticals (PhACs) in the Ebro River Delta region (NE Spain), as well as their distribution in different environmental compartments, including surface water, sediments, biota (river biofilm and fish tissues), and field-collected plastic litter. In addition, their concentrations in serving WWTPs, as possible sources of environmental contamination, were also determined.
Our study confirmed the widespread occurrence of PhACs in riverine and, to a more limited extent, coastal environments. Most frequently detected PhACs belonged to analgesics/anti-inflammatories (e.g., ibuprofen) and psychiatric drugs (e.g., venlafaxine) therapeutic groups, followed by antihypertensives (e.g., valsartan) and antibiotics (e.g., azithromycin). Seasonal differences in cumulative levels of PhACs were reported for water and sediments (winter>summer). Despite spatial gradients were not clear along the river, a non-negligible contribution of upstream Ebro sites (reference area) was highlighted, which was unexpected based on the low anthropogenic pressure. Sediments represented a minor attenuation pathway for the selected PhACs, whereas they were more heavily accumulated in biota: fish liver (up to 166 ng/g dw), river biofilms (up to 108 ng/g dw), fish plasma (up to 63 ng/mL), and fish muscle (up to 31 ng/g dw).
These findings highlight the importance of biomonitoring in the characterization of polluted areas and prioritization of hazardous substances (e.g., psychiatric drugs) in aquatic systems, and a particular interest of fish plasma as non-destructive biomonitoring matrix. PhACs were also detected on plastic litter, demonstrating their role as environmental sinks for certain PhACs (e.g., analgesics/anti-inflammatories, psychiatric drugs). Overall, the widespread detection of PhACs in a variety of biotic and abiotic matrices from the lower Ebro River and Delta warns about their possible environmental implications.
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•No geographical variation in pharmaceutical pollution along lower Ebro River basin.•Analgesics/anti-inflammatories, psychiatric drugs and antihypertensives as most frequent in river water•Biomonitoring improves assessment of pharmaceutical contamination compared to grab water.•River biofilm, fish plasma (non-destructive) and liver more informative than fish muscle•Plastic litter as a passive sink of some pharmaceuticals
The current socio-economic, environmental and public health challenges that countries are facing clearly need common-defined strategies to inform and support our transition to a sustainable economy. ...Here, the technology-critical elements (which includes Ga, Ge, In, Te, Nb, Ta, Tl, the Platinum Group Elements and most of the rare-earth elements) are of great relevance in the development of emerging key technologies—including renewable energy, energy efficiency, electronics or the aerospace industry. In this context, the increasing use of technology-critical elements (TCEs) and associated environmental impacts (from mining to end-of-life waste products) is not restricted to a national level but covers most likely a global scale. Accordingly, the European COST Action TD1407: Network on Technology-Critical Elements (NOTICE)—from environmental processes to human health threats, has an overall objective for creating a network of scientists and practitioners interested in TCEs, from the evaluation of their environmental processes to understanding potential human health threats, with the aim of defining the current state of knowledge and gaps, proposing priority research lines/activities and acting as a platform for new collaborations and joint research projects. The Action is focused on three major scientific areas: (i) analytical chemistry, (ii) environmental biogeochemistry and (iii) human exposure and (eco)-toxicology.
Bisphenol A (BPA) is one of the main ubiquitous compounds released from plastics in the environment. This compound, considered an endocrine disruptor, poses a risk to aquatic wildlife and human ...population, being included in multiple environmental monitoring programmes. Following the regulations restricting BPA use in the last years, BPA-like chemicals have been produced and used as BPA substitutes. However, they are not commonly included in monitoring programs yet and their presence is thus misrepresented, despite showing similar endocrine disrupting potential. In this work, an analytical method for analysing bisphenol A and five of its analogues (Bisphenol S, B, F, AF and Tetrabromobisphenol A) is described, validated for water (riverine, sea and wastewater), sediment, and biota (fish and biofilm) and applied to monitor their presence in the Ebro River Delta (NE Spain). In addition, plastic litter was also collected to evaluate their role as potential source of bisphenols. All compounds except BPF were detected in the analysed samples. Wastewater treatment plants (WWTPs) were discarded as major sources of BPs into the natural aquatic environment, as no BPs were detected in treated effluents. Indeed, the high levels of BPs in the natural environment could be related with direct discharge of raw wastewater from small rural population nucleus. The analysis of riverine plastic leachates yielded 4 out of the 6 BPs analysed, strengthening the hypothesis that plastic debris are also a source of BPs in the natural environment. Whereas Bisphenol S and BPA were detected in water and, to a limited extent, in biota, less polar analogues (mainly BPAF and TBBPA) were not found in any of the water samples. Instead, these hydrophobic BPs were found in fish tissues and biofilm, pointing out plastics and microplastics as their possible vectors. Finally, biofilm demonstrated its potential as sentinel of chemical contamination in freshwater environment.
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•Bisphenols were studied in biotic and non-biotic fluvial compartments.•Polar bisphenols detected in all environmental compartments.•Less polar bisphenol analogues only found in fish tissues and fluvial biofilm.•Plastic litter pointed out as a source of bisphenol contamination in river.•Fluvial biofilm as a sentinel for bisphenols monitoring in the aquatic environment.
Coastal ecosystems are particularly vulnerable to terrestrial inputs from human-impacted areas. The prevalence of wastewater treatment plants, unable to remove contaminants such as pharmaceuticals ...(PhACs), leads to their continuous input into the marine environment. In this paper, the seasonal occurrence of PhACs in a semi-confined coastal lagoon (the Mar Menor, south-eastern Spain) was studied during 2018 and 2019 by evaluating their presence in seawater and sediments, and their bioaccumulation in aquatic organisms. Temporal variation in the contamination levels was evaluated by comparison to a previous study carried out between 2010 and 2011 before the cessation of permanent discharges of treated wastewater into the lagoon. The impact of a flash flood event (September 2019) on PhACs pollution was also assessed. A total of seven compounds (out of 69 PhACs analysed) were found in seawater during 2018–2019, with a limited detection frequency (<33%) and concentrations (up to 11 ng/L of clarithromycin). Only carbamazepine was found in sediments (ND–1.2 ng/g dw), suggesting an improved environmental quality in comparison to 2010–2011 (when 24 and 13 compounds were detected in seawater and sediments, respectively). However, the biomonitoring of fish and molluscs showed a still remarkable accumulation of analgesic/anti-inflammatory drugs, lipid regulators, psychiatric drugs and β-blocking agents, albeit not higher than in 2010. The flash flood event from 2019 increased the prevalence of PhACs in the lagoon, compared to the 2018–2019 sampling campaigns, especially in the upper water layer. After the flash flood the antibiotics clarithromycin and sulfapyridine yielded the highest concentrations ever reported in the lagoon (297 and 145 ng/L, respectively), alongside azithromycin in 2011 (155 ng/L). Flash flood events associated with sewer overflows and soil mobilisation, which are expected to increase under climate change scenarios, should be considered when assessing the risks posed by pharmaceuticals to vulnerable aquatic ecosystems in the coastal areas.
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•Lower pharmaceutical concentrations were found in Mar Menor lagoon (SE Spain) in 2018–2019 than in 2010–2011.•Reuse of WWTP effluents (since 2015) has likely contributed to the observed decrease in pharmaceutical levels.•A flash flood episode in 2019 increased the presence of pharmaceuticals in the upper seawater layer.•Biomonitoring more informative than grab water regarding pharmaceutical presence in the lagoon.
Concentrations of nitrate, nitrite, ammonium, phosphate and silicate were determined in river water, tidal water that floods the intertidal sediment (flooding water) and pore water of those sediments ...in the Northern Galician Rias of Ortigueira and Viveiro (NW Iberian Peninsula). The field surveys were done in the productive seasons of spring and summer 2008. Short-sediment cores and tidal flooding water were sampled at the intertidal area during the first 20min that the tide inundates the sampling site. Nutrient fluxes of rivers (Lourido and Landro) flowing into the rias were in the order of H4SiO4>NO3−>NH4+>HPO4−2 Nutrients input from those rivers were low relative to the nutrient discharge of the entire coastal area. Striking changes of nutrient concentrations in flooding and pore waters of intertidal sediments were observed in the short periods of tidal inundation. Nutrient fluxes driven by molecular diffusion and tide-induced transport across the sediment–water interface were quantified and compared to the nutrient river contribution. Diffusive fluxes ranged from 9.3 to 13.7nmol·cm−2·d−1 for nitrate and nitrite, −1.32 to 30.1nmol·cm−2·d−1 for ammonium, −0.01 to 0.49nmol·cm−2·d−1 for phosphate, and −13.2 to 0.2nmol·cm−2·d−1 for silicate. Tide-induced transport always exceeded diffusive fluxes, with differences reaching up to four orders of magnitude for silicate. The overall results of this study emphasize the relevance of tidal water movement in promoting the sediment–water exchange of nutrients in intertidal sub-ecosystems.
•Nutrient contributions to the water column of ria systems were studied.•Contributions due to diffusive fluxes and tide-induced transport were calculated.•Both sources are discussed for the first time in Atlantic Rias.•Importance of tidal flooding over intertidal sediments in ria systems is spotlighted.
A winter shelf-water upwelling evidence (February 2008) is described by first time in the Northern Galician Rias (NW Iberian Peninsula). On February 20, after 9 consecutive days of upwelling ...favorable conditions, inside the O Barqueiro Ria was observed the presence of seawater below 10
m depth which replaced the less saline water previously observed in January. This situation was in agreement with the analyzed Ekman transport close to the northern Galician coast. Salinity and temperature distribution revealed that the upwelled water inside the rias corresponds to shelf bottom seawater which is not associated with Eastern North Atlantic Central Water or the Iberian Poleward Current. In addition, TS diagram indicated a higher influence of upwelling eastward (Viveiro–Barqueiro–Ortigueira). Nutrient salts' concentrations also suggested the presence of seawater from subsurface origin with a small variation with regard to the winter mixing in this marine area. Plankton showed the existence of spring conditions related to solar radiation increase associated to upwelling favorable winds. Some species also corroborated the intrusion of shelf-water inside the ria. Results from the analysis of Ekman transport data from 1967 to 2007 revealed that this event cannot be considered an isolated episode. In fact, the number of days per month under upwelling favorable conditions in winter (January–March) was not negligible (8–10 days) showing that upwelling events along the northern Galician coast are also possible during winter.
Recent characterizations of atmospheric conditions favorable to upwelling events in the Western Cantabrian Sea have stressed the need to analyze the significance of the orientation of the coast on ...the phenomenon of upwelling. Surface-wind fields for the northwestern Galician marine area were provided by the QuikSCAT satellite and an SST map was elaborated using the NASA GHRSST satellite data. A cruise was conducted aboard the RV Lura in June 2009 during northern prevailing winds. Data of thermohaline variables, concentration of dissolved oxygen, dissolved inorganic nitrogen, chlorophyll, dissolved and particulate organic carbon and nitrogen and phytoplankton abundances were obtained. When the upwelling developed west of the Cape Ortegal was strong, the Eastern North Atlantic Central Water mixed with coastal water eastward of the Cape and the upwelled seawater reached the westernmost of the Northern Galician Rias, the Ria of Ortigueira. Incoming seawater was poor in nitrate and chlorophyll concentrations when compared to that of the upwelling events in the Western Galician Rias. The phytoplankton assemblages were typical of summer upwelling blooms in the latter Rias but phytoplankton biomass was lower in the Ria of Ortigueira and the species were indicatives of initial (inner ria under continental influence) and advanced (outer ria under upwelling inputs) stages of phytoplankton succession. The observed process arose when the upwelling edge-zone reaches a change of coastal orientation as may also occur in other upwelling regions.
The evolution of a warm water mass related to the Iberian Poleward Current (IPC) was characterized along the northern Galician shelf in November 2008 by means of Sea Surface Temperature and wind ...data. It was observed that under upwelling favorable conditions water temperature decreased along the northern coast and a temperature break appeared between Cape Vilano and Cape Ortegal showing a relaxation of the poleward intrusion. The effect of the IPC was also analyzed inside the Northern Galician Rias taking into account the hydrographical and biogeochemical properties measured on November 18. Water driven by the IPC was observed close to the mouth of the rias, around Cape Estaca de Bares, causing a nutrient salts decrease. Inside the rias a slight biological activity was found near surface resulting from fluvial contributions.
Summer upwelling and downwelling processes were characterized in the Northern Galician Rias during July and August 2008 by means of sampling carried out onboard R/V
Mytilus (CSIC) and R/V
Lura (IEO). ...Thermohaline variables, dissolved oxygen, nutrients, chlorophyll, phytoplankton, ciliates and zooplankton abundances were measured at sections located in the Rias of Viveiro, Barqueiro and Ortigueira and their adjacent shelves. Ekman transport was calculated from QuikSCAT satellite, upwelling intensity estimated with upwelling index from the average daily geostrophic winds, and SST maps obtained from NASA GHRSST satellite. Ekman transport and SST behaviour showed two different patterns: (i) offshore and upwelling favourable conditions on 13–22nd of July; (ii) onshore and downwelling favourable conditions from 23rd July to 19th August. During upwelling, TS diagram showed an intrusion of Eastern North Atlantic Central Water affecting the continental shelf but not the rias. Nutrient salt concentrations increased with depth, reaching their maximum values near the mouth of Ortigueira Ria. During downwelling, coastal water increased its temperature (18.5–19.8
°C) and was retained inside rias; nutrients were nearly depleted, except for the innermost ria (estuarine zone) due to fluvial nutrient inputs. In this inner area, the maximum of chlorophyll-
a (Barqueiro Ria) was observed. Low phytoplankton abundances were measured in both cases, even though a short increase in the plankton biomass was observed inside rias during upwelling, while under downwelling a small red tide of
Lingulodinium polyedrum was detected. During the upwelling period Northern Rias tend to be mesotrophic systems as revealed by nutrient concentrations, chlorophyll levels and plankton abundances. On the contrary, in similar situations, the Western Rias behaves as eutrophics.
In the Northern Galician shelf, the average of upwelling (downwelling) was 1.9±0.8 (2.1±1.0)
events
yr
−1 from May to September (1990–2008) considering at least one week with favourable wind conditions and
UI averages out of the range of ±500
m
3
s
−1
km
−1.
Tide-induced transport, diffuse fluxes and river inputs of arsenic, cobalt, chromium, manganese and nickel were studied in an estuarine zone located at the Ria of Ortigueira in the Galician coast of ...NW Spain to evaluate comparatively the magnitude of trace-element inputs in the estuarine ecosystem. Short-sediment cores and flooding water were collected at the intertidal area of La-Caleira Inlet in spring and summer 2008 during the first 50min of tidal inundation. High concentrations of dissolved chromium (up to 23nM) and nickel (256nM) were found in waters of the Lourido River during 2008. Chromium (up to 795mg·kg−1) and nickel (up to 533mg·kg−1) in surface sediments of the study area were also high, pointing to natural geological sources (Cape Ortegal Complex). Fluxes associated with molecular diffusion and tide-induced transport across the sediment–water interface were quantified and compared to the river contribution. Mean fluxes from the Lourido River were 0.03μmol·m−2·d−1 for As, 0.02μmol·m−2·d−1 for Co, 0.43μmol·m−2·d−1 for Cr, 0.72μmol·m−2·d−1 for Mn and 5.98μmol·m−2·d−1 for Ni. Diffusive fluxes were negative which indicates the flow of trace elements towards the sediment −0.47±0.12μmol·m−2·d−1 for As; −0.007±0.001μmol·m−2·d−1 for Co; −0.003±0.009μmol·m−2·d−1 for Cr; −5.44±1.65μmol·m−2·d−1 for Mn; and −0.02±0.05μmol·m−2·d−1 for Ni. Tide-induced transport of trace metals was up to four orders of magnitude greater than diffusive fluxes. The contributions of trace elements to the estuarine zone from fluvial and benthic origin were quantified, emphasizing the importance of tide-induced transport in estuarine systems.
•Importance of tidal flooding over intertidal sediments in ria systems was tested.•Metal contributions due to diffusion and advection in Atlantic rias were quantified.•Geological complexes contribute with metal enrichment to the coastal environment.•Ortegal Complex causes an enrichment of Cr–Ni in shelf sediments of Galician rias.
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