THE OCCURRENCE OF PRIORITY PAHs, NONYLPHENOL AND OCTYLPHENOL IN INLAND AND COASTAL WATERS IN ATHENS AND MYTILENE, GREECE EXTENDED ABSTRACT

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1 Proceedings of the 9 th International Conference on Environmental Science and Technology Rhodes island, Greece, 1 3 September 2005 THE OCCURRENCE OF PRIORITY PAHs, NONYLPHENOL AND OCTYLPHENOL IN INLAND AND COASTAL WATERS IN ATHENS AND MYTILENE, GREECE M. KANAKI, A. NIKOLAOU, C.A. MAKRI, D.F. LEKKAS Water and Air Quality Laboratory, Department of Environmental Studies, University of the Aegean, University Hill, Mytilene, Greece nnikol@aegean.gr EXTENDED ABSTRACT Polycyclic Aromatic Hydrocarbons (PAHs) as well as nonylphenol (NP) and octylphenol (OP) are substances of major environmental interest because of their adverse health effects on organisms, including endocrine disrupting activity. Seven PAHs, NP and OP have been included in the priority list of substances regulated by 2000/60/EC Water Framework Directive. PAHs, NP and OP have been detected in various environmental compartments in many countries. PAHs are released into the environment through natural and anthropogenic combustion processes as well as from industrial activities. NP and OP may also be present in industrial effluents, but their major source is surfactants. The present work regards the investigation of the occurrence of the seven priority PAHs, NP and OP in surface waters in Athens and Mytilene, Greece. Samples were collected and analyzed seasonally for one year from the four reservoirs supplying water to the drinking water treatment plants of Athens: Mornos, Marathonas, Yliki and Evinos. Samples were also collected from inland waters of Mytilene island (rivers Mylopotamos and Evergetoulas), and from coastal waters in Mytilene area (five sampling points). The determination of PAHs, NP and OP was conducted by means of gas chromatography-mass spectrometry (GC-MS) method. The results have shown that in most cases the waters studied are free from PAHs, possibly because of lack of PAHs release sources nearby the particular areas, or due to the adsorption of PAHs on sediments. NP occurred at low levels in several cases, while OP was detected only in one sample. Key words: priority substances, polycyclic aromatic hydrocarbons (PAHs), nonylphenol, octylphenol, surface water, GC-MS A-653

2 1. INTRODUCTION Seven Polycyclic Aromatic Hydrocarbons (PAHs), nonylphenol (NP) and octylphenol (OP) have been included in the priority list of the Water Framework Directive 2000/60/EC [1]. The investigation of the occurrence of these substances in water is of particular importance, because they have adverse effects on the environment and human health; NP and OP are endocrine disrupting chemicals, which can mimic natural hormones in aquatic organisms, causing adverse effects on their reproductive system [2-3]. PAHs can also be considered as potential endocrine disrupting chemicals [4-5]. PAHs are released to the atmosphere mainly through natural and anthropogenic combustion processes and can enter the water cycle via precipitation. They have been determined worldwide in many environmental matrices. In Greece, Mandalakis et al [6], reported PAH measurements in the atmosphere of Athens and Voutsa et al [7] in suspended articles, fly ash and soil of Northern Greece. NP and OP may exist in water due to the degradation of alkylphenol polyethoxylates, which are widely used surfactants [8]. They have been detected in many countries: Spain, UK, Switzerland, Germany, Japan, Taiwan, USA, Canada, in the surface waters, in sediments and in fish. In surface waters, concentrations up to 644 µg/l and 0.47 µg/l have been reported for NP and OP respectively [8]. Some categories of priority substances of the Directives 76/464/EEC and 2000/60/EC, including volatile organic compounds, insecticides and herbicides have been investigated in Greek surface waters, [9,10], and the results have shown the occurrence of some of these substances in several water bodies, at low levels. The objective of the present work was to investigate the occurrence of PAHs, NP and OP especially in the surface waters supplying water to the major water treatment plants of Athens, Greece. Samples were collected seasonally, four times per year, for a period of one year, to evaluate seasonal variation of the levels of pollutants. Samples from coastal water and inland water in the island of Mytilene, Greece, were also collected and analyzed in autumn 2004 and in spring MATERIALS AND METHODS 2.1. Sampling In the area of Athens, three sampling points were established in Mornos water body (Eisodos, Giona, Kokkinos), two sampling points in Yliki (Eisodos and Mouriki), one in Marathonas and one in Evinos. Also samples were collected from the raw water entering the water treatment plants Galatsi, Menidi, Aspropyrgos and Polydendri. In the area of Mytilene, the sampling points for coastal water were Dei (area nearby the electricity power industry), Limani (port of Mytilene), Marina (marina of Mytilene, under construction), Xenia (nearby the University of the Aegean), and Airport. The sampling points for inland water were in the rivers Mylopotamos and Evergetoulas, which are two of the largest rivers of the island but normally they have water flow only from the beginning of autumn until the end of spring. Four sampling campaigns were conducted for the inland waters of Athens area (May 2004, September 2004, January 2005 and March 2005) and two sampling campaigns for the coastal and inland waters of Mytilene area (October 2004 and March 2005). Samples were collected in 1-L amber glass bottles and, kept at 4 o C, were transported to the Water and Air Quality Laboratory, where they were analyzed within one week. A-654

3 2.2. Analytical procedure The determination of PAHs, NP and OP was performed by liquid-liquid extraction - gas chromatography - mass spectrometry (LLE-GC-MS) [11]. The sample preparation procedure included addition of sodium sulfate (Merck) (5 g) in 1-L sample, liquid-liquid extraction initially with dichloromethane (Merck, for organic trace analysis) (20 ml) and afterwards with n-pentane (Merck, for organic trace analysis) (20 ml). The extracts were combined and, after addition of sodium sulfate (5 g) for drying, were evaporated to dryness in a water bath at 50 o C. The analytes were reconstituted with 1 ml dichloromethane. 1 µl of the final extract was injected into the gas chromatograph. A Hewlett Packard 5890 Series II gas chromatograph connected to a Hewlett Packard HP5971 MSD mass spectrometer was used. The GC-MS system was supported from the HP G1034C software. The column used for the chromatographic separation of the compounds was 30 m x 0.32 mm i.d. x 0.25 µm i.d. fused silica capillary DB-5MS. Helium (ECD) was used as the carrier gas and the injection technique was split/splitless. The MS was operated in SIM mode (Selected Ion Monitoring) [11], in order to enhance sensitivity. The oven temperature program was 50 ο C for 4 min, 20 ο C /min to 170 ο C, 8 ο C /min to 270 ο C. The carrier gas flow was 1.2 ml/min and the injector temperature 200 ο C. The analytical quality control scheme of the method included regular analyses of blank samples and spiked samples with known amounts of certified standards of PAHs, NP and OP (Supelco). The detection limits of the method ranged from to 0.05 µg/l [11]. A GC-MS chromatogram of an extract of a spiked water sample is shown in Figure 1. Figure 1: GC-MS chromatogram of PAHs, NP and OP (spiked water sample, 1 µg/l) (1. OP, 2. Anthracene, 3. NP, 4. Fluoranthene, 5. Benzo[b]fluoranthene, 6. Benzo[k] fluoranthene, 7. Benzo[a]pyrene, 8. Indeno[1,2,3-c,d]pyrene, 9. Benzo [g,h,i]perylene) A-655

4 3. RESULTS AND DISCUSSION The results of the analyses of the samples are presented in Table 1 for the inland waters of Athens area and in Table 2 for the coastal waters and inland waters of Mytilene area. The overall pollution status of the inland waters of Athens area (which supply water to the major water treatment plants of Athens) regarding the studied substances is low; none of the substances were detected during the first three sampling campaigns. During the fourth sampling campaign, in March 2005, anthracene was the only PAH detected in Mornos-Giona (0.33 µg/l) and in Aspropyrgos (0.19 µg/l). Also, NP occurred, in all sampling points except Evinos, at concentrations ranging from 0.08 to 2.54 µg/l. This concentration range is rather low compared to the values reported in the literature for surface waters [8]. The activities that could lead to possible release of priority substances in the investigated area are mostly agricultural (grazing and related waste), and waste disposal and some limited industrial activity in the settlements nearby the water bodies. Another source of PAHs could be the National Road that is located at small distance from the particular areas. PAHs adsorb easily onto sediments, and this can be the reason that in most cases the analyzed water samples were free from PAHs. This phenomenon also occurs during water treatment (coagulation/flocculation and sedimentation), therefore PAHs were not detectable in treated water samples from the water treatment plants of Athens which were also analyzed. Regarding the coastal water samples from Mytilene area, anthracene, benzo-a-pyrene, NP and OP were detected, only during the second sampling campaign (March 2005). Anthracene was detected only in the port (0.26 µg/l) and in the marina -which is near the port- (0.06 µg/l) of Mytilene, and benzo-a-pyrene (0.35 µg/l) only in the port of Mytilene. OP was detected only in the airport area (0.39 µg/l), while NP occurred in all five seawater samples, with highest concentration (0.86 µg/l) in the sample from the marina under construction. In the samples from inland waters of Mytilene, benzo-a-pyrene and NP were detected only in water from river Evergetoulas, at concentrations 0.22 and 0.21 µg/l respectively. The source of NP could be from activities in the nearby settlement, while benzo-a-pyrene may have been transported through precipitation or surface runoff pathways from agricultural areas. Overall, the surface waters (inland and coastal) in Athens and Mytilene areas, were in most cases free of PAHs, NP and OP, according to the results of the present study. This could be due to the adsorption onto sediments. The analysis of these priority substances in sediments from the same sampling areas could confirm this assumption. Since the adsorbed priority substances may be released in water when the conditions become favorable, and pose risk to environmental and water quality, investigation of the adsorption processes is a subject of interest for further research. A-656

5 Table 1. Concentrations of PAHs, NP and OP (µg/l) in the inland water samples in Athens area (Detection limits µg/l, nd: not detected) Sampling point Anthracene Fluoranthene NP OP Benzo-a-pyrene Sampling period Mornos-Eisodos nd nd nd nd nd nd nd nd nd nd nd 0.16 nd nd nd nd nd nd nd nd Mornos-Kokkinos nd nd nd nd nd nd nd nd nd nd nd 0.41 nd nd nd nd nd nd nd nd Mornos-Giona nd nd nd 0.33 nd nd nd nd nd nd nd 0.48 nd nd nd nd nd nd nd nd Evinos nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Yliki-Eisodos nd nd nd nd nd nd nd nd nd nd nd 0.27 nd nd nd nd nd nd nd nd Yliki-Mouriki nd nd nd nd nd nd nd nd nd nd nd 0.37 nd nd nd nd nd nd nd nd Marathonas nd nd nd nd nd nd nd nd nd nd nd 0.18 nd nd nd nd nd nd nd nd Polydendri nd nd nd nd nd nd nd nd nd nd nd 0.11 nd nd nd nd nd nd nd nd Menidi nd nd nd nd nd nd nd nd nd nd nd 0.19 nd nd nd nd nd nd nd nd Aspropyrgos nd nd nd 0.19 nd nd nd nd nd nd nd 2.54 nd nd nd nd nd nd nd nd Galatsi nd nd nd nd nd nd nd nd nd nd nd 0.08 nd nd nd nd nd nd nd nd Benzo-b-fluoranthene Benzo (k) fluoranthene Benzo (g,h,i) perylene Indeno(1,2,3-cd)pyrene Sampling period Mornos-Eisodos nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Mornos-Kokkinos nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Mornos-Giona nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Evinos nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Yliki-Eisodos nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Yliki-Mouriki nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Marathonas nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Polydendri nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Menidi nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Aspropyrgos nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Galatsi nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Table 2. Concentrations of PAHs, NP and OP (µg/l) in the coastal and inland water samples in Mytilene (Detection limits µg/l, nd: not detected) Sampling point Anthracene Fluoranthene NP OP Benzo-a pyrene Benzo-b-fluor Benzo-k-fluor Benzo(ghi)pe Indenopyrene Sampling period Dei nd nd nd nd nd 0.08 nd nd nd nd nd nd nd nd nd nd nd nd Limani nd 0.06 nd nd nd 0.08 nd nd nd 0.35 nd nd nd nd nd nd nd nd Marina nd 0.26 nd nd nd 0.86 nd nd nd nd nd nd nd nd nd nd nd nd Xenia nd nd nd nd nd 0.12 nd nd nd nd nd nd nd nd nd nd nd nd Airport nd nd nd nd nd 0.08 nd 0.39 nd nd nd nd nd nd nd nd nd nd Evergetoulas nd nd nd nd nd 0.21 nd nd nd 0.22 nd nd nd nd nd nd nd nd Mylopotamos nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd A-657

6 4. CONCLUSIONS The occurrence of the seven priority PAHs, NP and OP was investigated in inland and coastal waters in Athens and Mytilene, Greece. Samples were collected and analyzed seasonally for one year from the four reservoirs supplying water to the drinking water treatment plants of Athens. Samples from inland and coastal waters in Mytilene area were also analyzed. The results have shown that in most cases the waters studied are free from PAHs, NP and OP, possibly because of lack of PAHs release sources nearby the particular areas, or due to the adsorption of PAHs on sediments. NP occurred at low levels in several cases, anthracene and benzo-a-pyrene in a limited number of cases and OP was detected only in one sample. 5. REFERENCES 1. EC (2000), Directive of the European Parliament and of the Council 2000/60/EC establishing a framework for community action in the field of water policy, Official Journal C513, 23/10/ Purdom C.E., Hardiman P.A., Bye V.J., Eno N.C., Tyler C.R. and Sumpter J.P. (1994), Estrogenic effects of effluents from sewage treatment works, Chem. Ecol., 8, Sumpter J.P. and Jobling S. (1995), Vitellogenesis as a biomarker for estrogenic contamination of the aquatic environment, Environ. Health Perspect., 103, Depledge M.H., Billinghurst Z. (1999), Ecological Significance of Endocrine Disruption in Marine Invertebrates, Mar. Pollut. Bull., 39, Lagana A., Bacaloni A., De Leva I., Faberi A., Fago G. and Marino A. (2004), Analytical methodologies for determining the occurrence of endocrine disrupting chemicals in sewage treatment plants and natural waters, Analytica Chimica Acta, Mandalakis N., Tsapakis M., Tsoga A. and Stephanou E.G. (2002), Gas particle concentrations and distribution of aliphatic hydrocarbons, PAHs, PCBs and PCDD/Fs in the atmosphere of Athens (Greece), Atmos. Environ., 36, Voutsa D., Terzi H., Muller L., Samara C. and Kouimtzis Th. (2004), Profile analysis of organic micropollutants in the environment of a coal burning area, NW Greece, Chemosphere, 55, 4, Ying G.-G., Williams B. and Kookana R. (2002), Environmental fate of alkylphenols and alkylphenol ethoxylates-a review, Environment International, 28, Lekkas T. (2000a) National program for pollution reduction from the substances of List II, candidates for List I, C176, 14/07/1982/EEC, according to article 7 of the 76/464/EEC Directive, Water and Air Quality Laboratory, University of the Aegean, Mytilene. 10. Lekkas T. (2000b): National program for pollution reduction from the substances of List II (Metals), candidates for List I, C176, 14/07/1982/EEC, according to article 7 of the 76/464/EEC Directive, Water and Air Quality Laboratory, University of the Aegean, Mytilene. 11. Nikolaou A., Kanaki M. and Lekkas T. (2004), Development of a simple method for the simultaneous determination of nonylphenol, octylphenol, DEHP and PAHs in water samples, 4th Aegean Analytical Chemistry Days, 29 September-3 October 2004, Kusadasi, Turkey. A-658

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