Identification of contaminants of concern in the upper Tagus river basin (central Spain). Part 2: Spatio-temporal analysis and ecological risk assessment.

This study provides a description of the water quality status in the tributaries of the upper Tagus River and a preliminary risk assessment for freshwater organisms. A wide range of physico-chemical parameters, nutrients, metals and organic contaminants (20 pesticides, and 32 point source chemicals, mainly pharmaceuticals) were monitored during spring, summer and autumn of 2016. Monitoring of organic contaminants was performed using conventional grab sampling and passive samples (POCIS). The variation of the different groups of parameters as regards to land use and sampling season was investigated. The prioritization of organic and inorganic contaminants was based on the toxic unit (TU) approach, using toxicity data for algae, invertebrates and fish. Finally, the compliance with the Environmental Quality Standards (EQS) set as part of the Water Framework Directive (WFD) was evaluated for the listed substances. This study shows that the land use characteristics had a large influence on the spatial distribution of the contaminants and other water quality parameters, while temporal trends were only significant for physico-chemical parameters, and marginally significant for insecticides. Acute toxicity is likely to occur for some metals (copper and zinc) in the most impacted sites (TU values close to or above 1). Low acute toxicity was determined for organic contaminants (individual compounds and mixtures) on the basis of grab samples. However, the assessment performed with POCIS samples identified diuron, chlorpyrifos and imidacloprid as potentially hazardous compounds. Several contaminant mixtures that may cause chronic toxicity and that should be considered in future regional chemical monitoring plans were identified. Our study also shows that some metals and pesticides exceeded the WFD regulatory thresholds and that only 30% of the sampled sites had a good chemical status. Further research is needed to identify chemical emission sources and to design proper abatement options in the Tagus river basin.

The role of freshwater copepods in the environmental risk assessment of caffeine and propranolol mixtures in the surface water bodies of Spain.

In this study we aimed at assessing: (i) the environmental risk posed by mixtures of caffeine and propranolol to the freshwater ecosystems of Spain; (ii) the sensitivity of freshwater copepod species to the two compounds; (iii) if the toxicity of caffeine and propranolol to freshwater copepods contributes to the environmental risk posed by the two compounds in the freshwater bodies of Spain. The environmental risk was computed as the ratio of MECs (i.e. the measured environmental concentrations) to PNECs (i.e. the respective predicted no-effect concentrations). The effects of caffeine and propranolol on the freshwater cyclopoid Diacyclops crassicaudis crassicaudis were tested both individually and in binary mixtures. Propranolol posed an environmental risk in some but not in all the surface water ecosystems of Spain investigated in this study, while caffeine posed an environmental risk to all the investigated freshwater bodies, both as single compound and in the mixture with propranolol. Propranolol was the most toxic compound to D. crassicaudis crassicaudis, while caffeine was non-toxic to this species. The CA model predicted the toxicity of the propranolol and caffeine mixture for this species. D. crassicaudis crassicaudis was much less sensitive than several other aquatic species to both compounds. The sensitivity of D. crassicaudis crassicaudis does not increase the environmental risk posed by the two compounds in the freshwater bodies of Spain, however, further testing is recommended since the effect of toxicants on freshwater copepods can be more pronounced under multiple stressors and temperature increasing due to climate change.