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

https://doi.org/10.1016/j.scitotenv.2020.142344Get rights and content

Highlights

  • More than 200 emerging contaminants monitored in three Mediterranean River Basins

  • Three environmental compartments (water, sediments, biota) investigated

  • River basin “hot spots” characterized through ecotoxicological risk assessment

  • River basin specific pollutants identified

Abstract

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.

Introduction

There is extensive and intensive use of chemicals in our developed, highly technological society. For instance, under the provision of the REACH regulation (European Commission, 2006) more than 100,000 chemical substances have been currently registered by the European Chemicals Agency (ECHA, 2019). Significant scientific evidence has led to the recognition that their improper use and release may result in undesirable and harmful side-effects on both the human and ecosystem health (López-Pacheco et al., 2019; Malaj et al., 2014; Ginebreda et al., 2014). Mediterranean rivers are largely different from Northern and Central European rivers in terms of the hydrological regime (e.g. extreme hydrological events like droughts and floods), climate conditions (e.g. ambient temperature, solar irradiation), socio-economics (e.g. land-use changes, tourism, kinds of crops, water abstractions, urban and industrial releases, etc.), all of which leads to differences in the relative importance of the environmental pressures, in the classes and levels of the pollutants found and their environmental fate, etc. Water scarcity might increase the effects of water pollution on the receiving ecosystems (Petrovic et al., 2011) because of lowered dilution capacity of chemicals (Sabater et al., 2019) and combining its effects on the biological communities with other co-occurring environmental stressors (nutrients, altered discharge, dissolved organic matter, etc.) (Sabater et al., 2016). In this context, our study aims at providing both raw chemical occurrence data found in the monitoring of the three Mediterranean rivers (i.e., Adige, Sava, and Evrotas) together with the assessment of their ecotoxicological risk potentially affecting the receiving freshwater ecosystems. The three rivers surveyed, located in the northern Mediterranean basin, cover a broad range of characteristics in terms of basin area, discharge, land uses, or anthropogenic pressures (see Section 2.1).

Environmental chemical water monitoring seeks to provide the necessary data required for preserving the aquatic environment against the adverse effects caused by anthropogenic chemical pollution. In the regulatory context, chemical monitoring plays a key role in the Water Framework Directive (WFD) (EC Directive, 2000/60/EC) for the characterization and control of the so-called ‘chemical and ecological status’ of the water bodies. Despite the huge number of compounds present in environmental samples, only a few of them are covered by the WFD and daughter directives (EC Directive, 2013/39/EU), the so-called ‘priority substances’ for which environmental quality standards (EQS) are set up. Since this is insufficient, in this survey more than 200 organic compounds were monitored encompassing both emerging and regulated pollutants in three different environmental compartments, namely, water, sediments, and biota (fish). The micropollutants analyzed included relevant groups like pharmaceuticals, personal care products, perfluorinated compounds, polar pesticides, pyrethroids, persistent organic pollutants, and brominated flame retardants. On the other hand, according to the same regulations (WFD Article 4 and Annex V), water authorities must identify river basin specific pollutants (RBSP) of concern to ensure the good chemical and ecological status of the water bodies. This can be done using existing prioritization procedures based on the ecotoxicological risk of every single compound identified (Von der Ohe et al., 2011; Dulio and Von der Ohe, 2013; Dulio and Slobodnik, 2015; Kuzmanovic et al., 2015; Kuzmanović et al., 2016).

Though our study is aligned with the WFD principles, it goes beyond and fits the concept of advanced monitoring (Altenburger et al., 2019) that recommends the combined use of information on the occurrence of chemicals and their potentially adverse biological effects to properly assess the potential impact of contamination in the receiving aquatic ecosystems. Under such approach, overarching aims addressed in the study were: (a) the identification of the main pollutants occurring in the three rivers surveyed, considering their partition behavior amongst the environmental compartments (water, sediments, and biota); (b) the characterization of the spatial distribution of the pollutants monitored in each of the three river basins, with emphasis on the location of the main “hot-spots”; (c) the assessment of the ecotoxicological risk associated to the joint occurrence of many chemicals at every site monitored, and (d) the identification and prioritization the river basin specific pollutants (RBSP) in terms of the potential ecotoxicological risk posed to the aquatic ecosystems.

The study presented in this paper was carried out under the EU FP7 project GLOBAQUA (Navarro-Ortega et al., 2015).

Section snippets

Description of the basins

A brief overview of the three river basins under study, namely the Adige, the Sava, and the Evrotas (Fig. 1), is provided below.

Distribution of compounds amongst the environmental compartments

To have some insight on the distribution of the compounds analyzed amongst the three environmental compartments (water, sediments, and fish), we plotted in Fig. 2 the respective mean concentrations of the different compounds vs. their octanol-water partition constant (Kow), which captures the compound's distribution behavior between the water phase and a hydrophobic phase like sediment or biota. Logarithms of the Kow (log Kow) spanned from ca. -3 to 14, with the minimum and maximum values

Conclusions

In the present article, we have described and interpreted the results of an extensive chemical monitoring survey carried out in three Mediterranean rivers, namely the Adige, Evrotas, and Sava Rivers.

The three basins are very different, both in terms of geophysical conditions (drainage area, climate, and hydrology) and anthropogenic pressures and impacts (agricultural, urban, and industrial). This was evident in the respective pollution profiles found, as described in the previous sections.

CRediT authorship contribution statement

Marianne Köck-Schulmeyer: Data curation, Project administration, Writing - original draft. Antoni Ginebreda: Conceptualization, Writing - original draft. Mira Petrovic: Investigation, Writing - review & editing. Monica Giulivo: Investigation. Òscar Aznar-Alemany: Investigation. Ethel Eljarrat: Investigation, Writing - review & editing. Jennifer Valle-Sistac: Investigation. Daniel Molins-Delgado: Investigation. M. Silvia Diaz-Cruz: Investigation, Writing - review & editing. Luis Simón

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work has been supported by the European Communities EU 7th Framework Programme Funding under Grant agreement no. 603629-ENV-2013-6.2.1-Globaqua and partly by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-01404) and by the Spanish Ministry of Science, Innovation and Universities (Projects CEX2018-000794-S and IBERAQUA-NET RED2018-102737-T). Special thanks are due to all partners of the GLOBAQUA consortium and the peer review panel for ensuring quality results and a

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