Polar organic micropollutants in the coastal environment of different marine systems
Introduction
Polar anthropogenic organic micropollutants such as pharmaceuticals, corrosion inhibitors, biocides, and stimulants are frequently detected in raw sewage and wastewater treatment plant (WWTP) effluents (Loos et al., 2013a, Margot et al., 2013). Therefore, these compounds are omnipresent in the aquatic environment including groundwater (Loos et al., 2010, Reh et al., 2013) and surface water (Loos et al., 2009, Hughes et al., 2013) and, consequently, discharged on large scale into marine environments. Regarding the corrosion inhibitors 1H-benzotriazole and tolyltriazole, Wolschke et al. (2011) calculated an annual input into the North Sea of ∼60 t by the River Rhine alone. Xu et al. (2013) determined the concentrations of nine selected antibiotics in the Pearl River and concluded that a total of 193 t a−1 is transported by the Pearl River to the South China Sea. In addition to riverine contributions, micropollutants are also released by atmospheric input, direct discharge of raw and treated domestic and industrial wastewater, shipping, harbor and port activities, offshore oil exploration, and aquaculture (EEA, 2011). Depending on the persistency of a compound and the water exchange and evaporation rate in the receiving water body, a compound may significantly accumulate in marine and especially coastal environments. This was demonstrated by Biselli et al. (2000) who compared the concentrations of antifouling agents in German marinas of the North and Baltic Sea and attributed the significantly lower concentrations in North Sea marinas to their higher water exchange rate.
The European Water Framework Directive (EC, 2000) sets environmental objectives for the proper quality of inland, surface, transitional, coastal, and ground waters. Moreover, the Marine Strategy Framework Directive (MSFD) (EC, 2008) establishes a framework, within the member states shall take the necessary measures to achieve and maintain good environmental status in the marine environment by developing strategies to monitor, protect, and restore the marine environment and reduce inputs, pressures or impacts of human activities in each marine region. The very recently published report regarding the first phase of the MSFD stated that “pollution in the marine environment has decreased in some places but levels of nutrients and certain hazardous substances are overall still above acceptable limits. Oxygen depletion, as a result of nutrient pollution, is particularly serious in the Baltic and Black Seas.” (EC, 2014) and it was concluded that more efforts need to be made to meet the objective of reaching good environmental status until 2020.
In view of the above and considering observable detrimental effects in the environment caused by complex mixtures of chemicals (EEA, 2011, Kortenkamp et al., 2009), intensive global monitoring studies covering a large variety of different substances representing various contamination sources are implied. Loos et al. (2013b) monitored 67 micropollutants in the Northern Adriatic Sea 16 km offshore from Venice (Italy) and detected 45 above the limit of quantification. Among the compounds detected in highest concentrations were caffeine, tolyltriazole, 1H-benzotriazole, and terbuthylazine. Of the 108 target compounds monitored by Klosterhaus et al. (2013) in San Francisco Bay, 32 were detected at least at one and 12 at all five sampling locations. Among the compounds with 100% detection frequency were valsartan, sulfamethoxazole, carbamazepine, caffeine, gemfibrozil, and atenolol. The French Mediterranean coast was investigated by Munaron et al. (2012) and again, caffeine, carbamazepine, and terbuthylazine were among the most abundant compounds. These are recent examples demonstrating the wide distribution of anthropogenic organic micro-pollutants in marine environments. However, comprehensive data sets in coastal or open marine waters are still relatively scarce and mostly isolated studies covering very specific and relatively small areas, usually represented by limited sampling locations, can be found in the literature.
In this work monitoring data represented by more than 150 samples collected from the shorelines of the Baltic Sea (Germany), Northern Adriatic Sea (Italy), Aegean Sea and Dardanelles (Greece & Turkey), San Francisco Bay (USA), Pacific Ocean (from Muir Beach to Monterey Bay; USA), Mediterranean Sea (Israel), and Balearic Sea (Spain) are presented. The monitoring study was conducted from 2009 to 2011. Water samples were analyzed for various classes of micropollutants such as non-steroidal anti-inflammatory drugs (NSAIDs), stimulants, antihypertensives, iodinated X-ray contrast media, antibiotics, lipid regulators, antiallergics, anticonvulsants, sedatives, antidepressants, herbicides, biocides, corrosion inhibitors, one gastric acid regulator, one antipsychotic, one breast cancer drug, and selected transformation products of compounds from the aforementioned classes. The aim of this study is to provide an overview regarding the occurrence of polar anthropogenic organic micropollutants in coastal environments, the identification of the most abundant compounds and sources, and the observed concentration ranges.
Section snippets
Water sampling and sample pre-treatment
Locations, sampling periods, and the number of seawater samples are presented in Table 1. Grab samples were taken from beach areas, seaside promenades or long piers (maximum distance to the coastline ∼200 m). Sampling locations of selected areas are presented in Fig. 1, Fig. 2, Fig. 3, Fig. 4. The water samples were collected in 0.5 L (clear glass, screw cap) glass bottles and kept in a portable refrigerator (4 °C) or cooling box during transportation or shipping to the laboratory. Solid phase
Results and discussion
The results of the monitoring studies are presented in Table 3, Table 4. In Fig. 5 compounds with detection frequencies >10% in all analyzed samples are presented. The wide distribution of polar organic micropollutants in the coastal environment is clearly demonstrated. There was only one sample (Pacific Ocean) where none of the analytes were detected. Of the monitored 53 compounds the following 10 were not detected above the MQL in any sample: 4-nitro-SMX (<1 ng L−1), atenolol acid (<4 ng L−1),
Conclusions
The here presented results underline the presence of polar organic micropollutants from various contamination sources in coastal environments and the potential temporal and spatial complexity of occurring micropollutant-mixtures in coastal marine ecosystems. The highest individual concentration was observed for the readily biodegradable compound caffeine. Its high detection frequency (95.4%) demonstrates the widespread and direct impact of untreated wastewater and clearly highlights the
Acknowledgments
This work was supported by grants under the DAAD programme for the promotion of the exchange and scientific cooperation between Greece and Germany (“IKYDA 2010”) entitled “Emerging pollutants as indicators of quality status in marine environments. A comparative study between Mediterranean and Baltic Sea”. We gratefully thank Carlos Ayora, Athanasios Bessis, Martin Nottebohm, Constantini Samara, Athanasios Soupilas, and Evangelia Terzopoulou for their assistance in sampling.
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