Determination of 54 pesticides in waters of the Iberian Douro River estuary and risk assessment of environmentally relevant mixtures using theoretical approaches and Artemia salina and Daphnia magna bioassays

- Fifty-four pesticides were quantified in the Douro River estuary;
- Twelve pesticides were above the 2013/39/EU Directive limits;
- A two-tiered approach indicated potential risk to invertebrates;
- Environmental mixtures induced mortality to Artemia salina and Daphnia magna.

As a case study, the estuary of the international Douro River (Iberian Peninsula) was sampled over a year (2010) at six sampling sites to determine the presence of 56 pesticides of different categories (insecticides, herbicides, and fungicides). 96% of measured pesticides were detected in 79% of the quantified samples. Individual average pesticide concentrations ranged from 39 to 1 265 ng/L, indicating a ubiquitous presence of the selected compounds; moreover, twelve pesticides were above the 2013/39/EU Directive limits. Due to its highly impacted profile, a theoretical hazard assessment was done considering the average and maximum environmental mixtures of all measured pesticides to identify the most sensitive trophic level. For both environmental mixtures, the theoretical approach suggested that invertebrates were the most sensitive group. Therefore, short-time exposure assays using both invertebrates Artemia salina and Daphnia magna, were done using the referred mixtures. Data demonstrated significant toxic effects ─ high mortality rate and abnormal swimming behaviour ─ of the exposed animals. Both approaches (theoretical and experimental) support the analytical results, alerting for an intervention on this estuarine environment and of other comparable.

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