Risk assessment based prioritization of 200 organic micropollutants in 4 Iberian rivers
Introduction
The use of chemicals by our technological society is continuously growing both in total amount as well as in a number of different substances among which organic chemicals play a major role. According to the European Inventory of Commercial Chemical Substances (EINECS), the number of substances commercially available in Europe is ca. 100,000 compounds and similar figures hold for the USA (Arnot et al., 2006, Muir and Howard, 2007). Depending on their intrinsic physical–chemical properties, volume and mode of use (Guillén et al., 2012) many of these compounds may find their way into the aquatic environment either from the point or diffuse sources (Schwarzenbach et al., 2006) where they can affect freshwater ecosystems. In fact, chemical pollution is recognized as one of the major causes of their impairment (Vörösmarty et al., 2010). As regards chemical pollution, there are two aspects that seem of special concern. First, many of these pollutants are continuously and steadily released into the environment in low but measurable concentrations (Barceló and Petrovic, 2007). Second, the long-term environmental and health effects of many of the compounds that are found in the environment are still unknown, especially because they occur in the in the form of complex chemical mixtures rather than alone.
Owing to the growing public awareness on the need of protecting both ecosystems and human health from the risks associated with chemical pollution, an increasingly important body of regulations has raised in the last years, especially in developed countries. In this context, the elaboration of lists of chemical substances based on a risk assessment procedure plays a major role. For instance, the Water Framework Directive (WFD), which aims the achievement of good ecological and chemical status of European water bodies by the year of 2015. To achieve good chemical status water bodies must meet the Environmental Quality Standards (EQS) for 45 so-called priority substances (PS) and priority hazardous substances (PHS) from previous legislation (European Commission, 2011). Furthermore, under the WFD, EU member states are obliged to set quality standards for river basin-specific pollutants discharged in each water body and to take action to meet those quality standards by 2015 as part of ecological status.
Advances in environmental analytical chemistry (Barceló and Petrovic, 2007) have shown that regulated and monitored chemicals are only a small fraction of all the chemicals present in the environment (Petrovic et al., 2011). Recently, attention has been directed to several families of contaminants (i.e., pharmaceuticals, personal care products, endocrine disrupting compounds, perfluorinated compounds, pesticides, etc.) that are biologically active but still unregulated (Pal et al., 2010), collectively referred to as Emerging Organic Contaminants (EOCs) (Kuster et al., 2008) and which have been detected in aquatic systems worldwide (Focazio et al., 2008, Fromme et al., 2002, Kolpin et al., 2002, Leong et al., 2007, Loos et al., 2009, Ternes, 1998, Silva et al., 2011).
Due to the great number of chemical compounds potentially occurring in the environment, there is a need to prioritize them for management optimization purposes (Daginnus et al., 2011, von der Ohe et al., 2011). Therefore, identifying the chemicals of concern for a given river basin requires performing a suitable combination of monitoring and reliable assessment of risk. Risk assessment procedures consider both the potential hazard effect of a given substance and its exposure level (Daginnus et al., 2011, Guillén et al., 2012). While exposure can be obtained either from measurement (monitoring) or modeling, hazard is derived from its intrinsic properties. Typically, these encompass persistence, bioaccumulation and toxicity (referred to as PBT approach). However, in practice, due to the aforementioned continuous introduction into the environment of many compounds persistence becomes less relevant (i.e., many pollutants are ubiquitous in the environment due to their continuous input). On the other hand, bioaccumulation and toxicity are often correlated. For that reason, many risk-assessment procedures are focused on ecotoxicity as a hazard measure, while persistence and bioaccumulation are disregarded.
Since risk assessment depends both on the occurrence and effects of the compounds concerned, a reliable ecotoxicity based prioritization exercise should ideally fulfill the following requirements: (i) it should include ecotoxicity data corresponding to test organisms associated with different trophic levels, so that the effects on the real ecosystem are likely reflected, and (ii) it should be based on comprehensive and on-site monitoring, so that exposure levels are representative of the catchment under study. We like to emphasize the latter point since the pollution pattern (and hence the associated priority pollutants) is strongly dependent on local conditions such as climate, hydrology, land-use and economical activities; (von der Ohe et al., 2011, Vörösmarty et al., 2010, Acuña et al., 2014).
Whereas there are a number of prioritization exercises based on western and northern European and US rivers (Daginnus et al., 2011, Kumar and Xagoraraki, 2010, Slobodnik et al., 2012, Smital et al., 2013), they are much less abundant for Mediterranean rivers and limited to regulated compounds (López-Doval et al., 2012) or are focused on certain families (Ginebreda et al., 2010, Vazquez-Roig et al., 2012). In this context, the aims of this study were (a) to perform an environmental risk assessment for ca. 200 organic micropollutants including both emerging and WFD priority contaminants monitored in four rivers located in the Mediterranean side of the Iberian Peninsula, namely, the Ebro, Llobregat, Júcar and Guadalquivir rivers; (b) to prioritize them for each of the four river basins studied, taking into account their observed concentration levels together with their ecotoxicological potential. To this end, standard test data corresponding to three organisms (algae, invertebrates and fish) representative of different trophic levels were used, as recommended by the WFD. The results of this work might contribute to the knowledge of river basin-specific pollutants (RBSP) for Iberian rivers concerned as that is one of the requirements of the WFD, also the importance of emerging pollutants is compared to priority pollutants in terms ecological risk.
Section snippets
Study area
Four Iberian river basins (Fig. 1) were studied as representatives of Mediterranean streams. The main features of the studied rivers (Ebro, Llobregat, Jucar and Guadalquivir) such as catchment area, river length annual precipitation, population density, etc., vary greatly between this four river basins (Table 1). Mediterranean rivers are characterized by low summer flow and large floods in autumn and winter seasons as a consequence of Mediterranean climate (Gasith and Resh, 1999). In comparison
Occurrence
The concentration ranges of different classes of measured compounds (pharmaceuticals, hormones, personal care compounds, pesticides, perfluorinated compounds, industrial compounds and drugs of abuse) were showing differences between studied rivers and years 2010 and 2011 (Fig. 2). Among the different groups of compounds, industrial organic chemicals (IOCs) were found in the highest concentrations in all four studied rivers. The maximum concentration of IOCs was measured in Llobregat river (ΣIOCs
Conclusions
A general prioritization exercise has been done based on a Ranking Index. Although it has been applied to three common ecotoxicity indicators, it can be easily extended to any other in vivo or in vitro assay, providing there are data for all compounds.
Generally, there is a lack of systematic ecotoxicity data for many compounds, and the need of filling this gap is crucial for ecological risk assessment purposes.
Emerging contaminants like pharmaceuticals were measured at many sites in studied
Acknowledgements
This work was funded by the Spanish Ministry of Economy and Competitiveness project Consolider-Ingenio 2010 SCARCE CSD2009-00065 and by the Generalitat de Catalunya (Consolidated Research Groups “2014 SGR 418–Water and Soil Quality Unit” and 2014 SGR 291–ICRA). Damia Barcelo acknowledges the support of the Visiting Professor Program of the King Saud University. Maja Kuzmanovic acknowledges the AGAUR fellowship from the Generalitat de Catalunya. Very special thanks to Jagoš Radović and Božo
References (56)
- et al.
Challenges and achievements of LC-MS in environmental analysis: 25 years on
TrAC Trends Anal Chem
(2007) - et al.
Water quality and assessment under scarcity: prospects and challenges in Mediterranean watersheds
J Hydrol
(2010) - et al.
SPEAR indicates pesticide effects in streams—comparative use of species- and family-level biomonitoring data
Environ Pollut
(2009) - et al.
Patterns of presence and concentration of pesticides in fish and waters of the júcar river (eastern spain)
J Hazard Mater
(2014) - et al.
A review of personal care products in the aquatic environment: environmental concentrations and toxicity
Chemosphere
(2011) - et al.
Occurrence of acidic pharmaceuticals and personal care products in Turia River Basin: from waste to drinking water
Sci Total Environ
(2014) - et al.
A national reconnaissance for pharmaceuticals and other organic wastewater contaminants in the United States—II) Untreated drinking water sources
Sci Total Environ
(2008) - et al.
Occurrence of phthalates and bisphenol A and F in the environment
Water Res
(2002) - et al.
Fully automated determination of nine ultraviolet filters and transformation products in natural waters and wastewaters by on-line solid phase extraction-liquid chromatography-tandem mass spectrometry
J Chromatogr A
(2013) - et al.
Environmental risk assessment of pharmaceuticals in rivers: relationships between hazard indexes and aquatic macroinvertebrate diversity indexes in the Llobregat River (NE Spain)
Environ Int
(2010)
Prioritization of chemicals in the aquatic environment based on risk assessment: analytical, modeling and regulatory perspective
Sci Total Environ
Dissipation of insecticides in a Mediterranean soil in the presence of wastewater and surfactant solutions. A kinetic model approach
Water Res
Effects of the fungicide prochloraz on the sexual development of zebrafish (Danio rerio)
Comp Biochem Physiol C Toxicol Pharmacol
Pharmaceuticals, personal care products and endocrine-disrupting chemicals in U.S. surface and finished drinking waters: a proposed ranking system
Sci Total Environ
Analysis and occurrence of pharmaceuticals, estrogens, progestogens and polar pesticides in sewage treatment plant effluents, river water and drinking water in the Llobregat river basin (Barcelona, Spain)
J Hydrol
Contamination levels of selected organochlorine and organophosphate pesticides in the Selangor River, Malaysia between 2002 and 2003
Chemosphere
Ranking of chemical substances based on the Japanese Pollutant Release and Transfer Register using partial order theory and random linear extensions
Chemosphere
EU-wide survey of polar organic persistent pollutants in European river waters
Environ Pollut
Analysis of monitoring programmes and their suitability for ecotoxicological risk assessment in four Spanish basins
Sci Total Environ
Aquatic ecotoxicity of the selective serotonin reuptake inhibitor sertraline hydrochloride in a battery of freshwater test species
Ecotoxicol Environ Saf
Occurrence and modeling of pharmaceuticals on a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions
Sci Total Environ
Impacts of emerging organic contaminants on freshwater resources: review of recent occurrences, sources, fate and effects
Sci Total Environ
Combined scenarios of chemical and ecological quality under water scarcity in Mediterranean rivers
TrAC Trends Anal Chem
The Iberian Rivers
Effects of pesticides on community structure and ecosystem functions in agricultural streams of three biogeographical regions in Europe
Sci Total Environ
Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain
Chemosphere
Identification of river basin specific pollutants and derivation of environmental quality standards: a case study in the Slovak Republic
TrAC Trends Anal Chem
Measurement of pollutant toxicity to fish, II-Utuizing and applying bioassay results
Water Res
Cited by (139)
Screening of priority antibiotics in Chinese seawater based on the persistence, bioaccumulation, toxicity and resistance
2023, Environment InternationalFunctional characterization of an efficient ibuprofen-mineralizing bacterial consortium
2023, Journal of Hazardous MaterialsNanomaterials for the removal of organic pollutants from agrofood wastewaters
2023, Advanced Technologies in Wastewater Treatment: Food Processing Industry