Desalination 215 (2007) 223236

Pesticides, volatile and semivolatile organic compounds in the inland surface waters of Cyprus
D. Fattaa*, C. Michaelb, St. Canna-Michaelidoub, M. Christodoulidoub, N. Kythreotoua, M. Vasqueza
a

Department of Civil and Environmental Engineering, Laboratory of Environmental Engineering, University of Cyprus, GAIA, 75, Kallipoleos, 1678 Nicosia, Cyprus Tel. +357-22892275; Fax +357-22892295; email: dfatta@ucy.ac.cy b Department of Environmental Chemistry, Ecotoxicology, Pesticides and Radioactivity, State General Laboratory, 44, Kimonos, 1451 Nicosia, Cyprus
Received 4 August 2006; revised accepted 25 October 2006

Abstract The pollution of the surface waters of Cyprus from priority compounds which are included in the EU Directive 76/464/EEC was evaluated. The Directive deals with the pollution caused by certain dangerous substances discharged into the aquatic environment of the Community. In the framework of the reporting obligations of Cyprus towards EU, a study was carried out for the Environment Service of Cyprus by the University of Cyprus in collaboration with the State General Laboratory. 19 out of the 59 surface water bodies of the country were investigated. 30 substances of List I, List I candidates and List II were examined. The analytical determination was performed by a Gas Chromatography Electron Capture Detection for organochlorine insecticides, by Gas Chromatography Flame Thermionic Detector for the chlorotriazine herbicides and organophosphate insecticides and finally by on line purge and trap technique followed by Gas Chromatography Electron Capture Detection/ Photoionization Detection for the volatiles and semivolatiles organic compounds. Toluene, 1,1,1-trichloroethane, 1,2-dichloropropane, vinyl chloride and 1,4-dichlorobenzene were the most frequently found among VOCs and SVOCs. In some cases non-compliance was observed for hexachlorobutadiene, hexachlorobenzene and 1,2,4trichlorobenzene. The most commonly encountered organochlorine insecticides were hexachlorobenzene and heptachlor. This paper summarizes the work carried out, the methodologies applied and provides a discussion on the results found. Keywords: Cyprus surface waters; Pesticides; Volatile and semivolatile compounds; GC-FTD; GC-ECD; On-line purge and trap GC-ECD/PID

*Corresponding author. A special issue devoted to and inspired by WaT3R, MEDA WATER International Conference on Sustainable Water Management, Rational Water Use, Wastewater Treatment and Reuse, Marrakech, Morocco, 810 June 2006.
0011-9164/06/$ See front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.0000.00.000

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1. Introduction Until recently, all water resources available in Cyprus came from rainfall. Based on a long series of observations, the mean annual precipitation, including snowfall, amounts to approximately 500 mm, whereas during the past 30 years this amount was reduced to 460 mm. The amount of water, which corresponds to the total surface of the Government controlled area, totals 2670 MCM whereas only 14% or 370 MCM is available for development since the remaining 86% returns to the atmosphere through evapotranspiration. Geographically speaking, rainfall is unevenly distributed in Cyprus, with maximum precipitation falling on the two mountainous masses and minimum precipitation observed in the eastern plain and the coastal areas. The variation in rainfall is not only regional but also annual and often two or three consecutive dry years are observed. The mean annual quantity of 370 MCM of water is distributed between surface and groundwater in the ratio 1.75:1 respectively. Concerning surface water, although the capacity of all the main dams is 273.6 MCM, the average annual amount of water available for use is estimated to be about 101.5 MCM. During the dry year of 2000, for example, the contribution to irrigation of all dams was only 28.5 MCM. Out of the 101.5 MCM, 82 are used within Government Projects, 14.5 for domestic use (after treatment) and 5 for ecological areas [1]. The monitoring and the protection of the quality of the available water in Cyprus are absolutely essential. In the framework of the protection of surface waters and according to 76/464/EEC Directive, substances posing health risks to human and to the aquatic environment are divided, in two lists [2]. Member states of the European Community are required to eliminate pollution caused by substances belonging to List I, and to reduce pollution caused by substances belonging to List II of the Directive. In Cyprus, determination of a number of these substances is being performed

since 2000. However, in May 2004 when Cyprus joined EU, it was required to investigate these substances in surface waters and to prepare a report for the European Union. Most of the substances investigated fall within two broad categories: pesticides and volatile and semivolatile organic compounds. Pesticide usage in the world today has been growing at a significant rate in great efforts to increase crop yields in many countries. While the application of these compounds can protect crop production in the agriculture operations and help control infestations in residential areas, their persistence in the environment and their presence in surface water runoff and groundwater is a concern for community water supplies and recreational water bodies. It has been found in the past that natural organic matter, which is commonly found in ground waters and surface waters, can bind many organic and inorganic compounds [3]. The overall impact of a pesticide depends on its behaviour in the environment, on its ecotoxicity and on the amounts applied. According to Margni et al. [4], for human, health food intakes, results in the highest toxic exposure, about 103105 times higher than that induced by drinking water or inhalation. The concentration and type of pesticides found in surface waters depend on the season of the year, the physicochemical properties of the pesticides such as their solubility in water, their capacity to be retained in the soil, their persistence, and other factors including the topography of the land and the frequency of rain. A lot of studies have been carried out during the last several years which have proved the presence of such substances but also the presence of other priority substances such as volatile and semivolatile compounds that are also included in the Water Framework Directive 2000/60/EC, in surface waters, ground waters but also in drinking water [510]. In regards to the analysis, several methods have been developed and applied for the pretreatment and the analytical determination of pesticides and also for volatile and semivolatile

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organic compounds so far. Sabik and Jeannot [11], determined some organonitrogen pesticides in large volumes of surface water by liquidliquid and solid-phase extraction using gas chromatography with nitrogenphosphorus detection and liquid chromatography with atmospheric pressure chemical ionization mass spectrometry. Vassilakis et al. [12], determined a variety of chemical classes of pesticides in surface and ground waters by off-line solid-phase extraction, gas chromatography with electron-capture and nitrogenphosphorus detection, and highperformance liquid chromatography with postcolumn derivatization and fluorescence detection. Carabias-Martinez et al. [13], determined a number of herbicides and their metabolites in surface and ground waters by solid-phase extraction and liquid chromatography. Stoob et al. [14], implemented a fully automated online solid phase extraction coupled directly to liquid chromatography-tandem mass spectrometry for the determination of acidic pesticides in surface waters. Mezcua et al. [15], applied ultra performance liquid chromatographytandem mass spectrometry for the analysis of priority pesticides in groundwater. Ahmadi et al. [16], determined organophosphorus pesticides in water samples by single drop microextraction

and gas chromatography-flame photometric detector. Wolska et al. [17], determined volatile and semivolatile organohalogen traces in surface water by direct aqueous injection GC-ECD. Leon et al. [18], analysed 35 priority semivolatile compounds in water by stir bar sorptive extractionthermal desorption-gas chromatography-mass spectrometry. Pyle et al. [19], analysed volatiles and semivolatiles in drinking water by microextraction and thermal desorption. In the present study, the following techniques have been implemented for the determination of the compounds already described: (1) liquidliquid extraction gas chromatography with ECD detection, (2) solid-phase extraction gas chromatography with FTD detection and (3) on-line purge and trap gas chromatography with ECD/PID. In Cyprus, the selection of the investigated compounds followed a study for the possible existence in the Cyprus surface waters of compounds belonging to the List I and List II of 76/464/EEC Directive. The initial identification of compounds covered the examination of the possible discharges of the Cyprus chemical industries and urban wastewater treatment plants and the use of toxic compounds which are imported [20]. Based on the findings of this study, the compounds listed in Table 1 were investigated.

Table 1 Chemical categories of the substances under examination (the number in parenthesis indicates the code number set by 76/464/EEC) Organochlorine insecticides Aldrin (1), DDT (46), Dieldrin (71), Endrin (77), Heptachlor (82), Hexachlorobenzene (83) Chlorotriazine herbicides Simazine (106), Atrazine (131) Organophosphate insecticides Azinphos-ethyl (5), Azinphos-methyl (6), Fenthion (81), Parathion (100) Volatile and semivolatile organic compounds Chlorobenzene (20), Chloroform (23), 2-Chlorotoluene (38), 1,2-Dichlorobenzene (53), 1,3-Dichlorobenzene (54), 1,4-Dichlorobenzene (55), 1,2-Dichloroethane (59), 1,2-Dichloropropane (65), Ethylbenzene (79), Hexachlorobutadiene (84), Hexachloroethane (86), Naphthalene (96), 1,1,2,2-Tetrachloroethane (110), Toluene (112), 1,2,4-Trichlorobenzene (118), 1,1,1-Trichloroethane (119), 1,1,2-Trichloroethane (120), Vinyl chloride (128)

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This paper presents the results of this study and also the results of the previous monitoring programs that have been performed from 2000 until 2005 in respect to a number of List I and II substances. The study has been undertaken by the University of Cyprus in collaboration with the State General Laboratory for the Environment Service of the Ministry of Agriculture, Natural Resources and Environment. 2. Materials and methods 2.1. Water bodies under investigation A list of the surface water bodies and the coding used by the Department of Water Development in Cyprus that have been investigated in regards to the organic compounds listed in Table 1, is shown in Fig. 1. The figure also provides information on the region boundaries of the country, the watershed boundaries, the station identification codes, the location of the stream gauging stations and also the location of the streams and major dams. 2.2. Sampling and preservation During the period between autumn 2003 and spring 2005, 7 seasonal samplings had been performed. Three samples were collected from the same location at each water body. The samples were collected at 1-m depth under the surface water. Around 133 samples were analysed for each group of substances giving in total 399 samples. 2.2.1. Organochlorine insecticides Each sample was collected in 1-L glass bottles pre-rinsed with acetone and then with hexane. One milliliter of HgCl2 1% was added to the samples for preservation. During transportation the samples were kept at <10C and away from light. Extraction took place preferably immediately after sampling but not later than 7 days of

holding time at 8C. The holding time after extraction was 14 days (samples kept in a freezer). 2.2.2. Chlorotriazine herbicides and organophosphate insecticides Each sample for these measurements was collected in 2.5-L glass bottles pre-rinsed with acetone and then with hexane. One milliliter of HgCl2 1% was added to the samples for preservation. During transportation the samples were kept at <10C and away from light. The samples were extracted within 7 days. The holding time after extraction was 1428 days (samples kept in a freezer). 2.2.3. Volatile and semivolatile organic compounds Each sample was collected in 250-mL glass bottles which had been washed with tap water and then with distilled water, heated at 105C for 1 h and kept in an area free of organic solvent vapors. Fifteen drops of HCl 1:1 were added to the samples for preservation. During transportation the samples were kept at <10C. In the laboratory the samples were kept at 4C until their analysis (for maximum 14 days). 2.3. Extraction and analysis 2.3.1. Organochlorine insecticides The reference method that was followed is based on EPA Method 508 [21]. A measured volume (600 mL) of the sample was transferred in a separatory funnel of 1 L. Five grams of NaCl were added and the funnel was shaken well until NaCl was completely dissolved. Fifty milliliters of CH2Cl2 were added and the funnel was shaken vigorously for 2 min with periodic venting to release excess pressure. Then the organic phase was allowed to separate from the water phase for a minimum of 10 min. The organic phase was

No SIC 1124-931-95 1138-894-55 1138-894-60 1226-858-60 1226-826-90 1283-018-10 1872-513-60 1873-524-60 1873-514-95 1882-507-50 1895-506-40 1897-510-50 1923-695-85 1925-694-95 Garyllis Mersino 17 18 19 Kryos Kouris Kouris 1943-675-80 1943-675-90 1962-628-90 1964-646-90 1964-636-95 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Yialiadhes Evretou Dam (outlet) Limnitis Saw Mill Pano Lefkara Kornos Dhipotamos Dam Vavla Layia Kalavasos Phinikaria U/S Yermasogia Dam U/S Polemidhia Dam U/S Polemidhia Dam Khalassa U/S Kouris Dam Khalassa Stavros tis Psokas Stavrostis Psokas Limnitis Syrkatis Mylou Mylou Maroni Vasilikos Vasilikos Yermasogia Skarphos Xeros

RIVER (STREAM) Dhiarizos Xeros

NAME OF STATION Philousa Xeros Asprokremmos Dam

Region boundary Watershed boundary Region number with watershed number Region number Station identification code Stream gauging station

Example: 1113-614-95

SIC = Station Identification Code

1.3. 2 1113-614-95

D. Fatta et al. / Desalination 215 (2007) 223236

Stream and major dam

1: Station code no 1: Region no 1: Watershed no 3: Sub watershed no 614: Village code 95: Observation site

Fig. 1. Information on the watersheds, streams, dams, stream gauging stations and station identification codes in Cyprus.

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then collected and transferred in a spherical flask of 250 mL. The extraction procedure was repeated a second time, combining then the extracts in the flask. Five grams of anhydrous Na2SO4 were added in the extract in the flask. The flask was shaken and then was left to sit for 15 min. The methylene chloride was decanted into another flask of 500 mL. The remaining sodium sulfate was rinsed with two portions of 25 mL CH2Cl2 and the rinses were decanted in a flask of 500 mL. The sample was then evaporated to 1 mL using a rotary evaporator. Ten milliliters of n-hexane (Lab-Scan) were added and then the extract was again evaporated to 1 mL. This was repeated for a second time. The volume was then adjusted to 5 mL with hexane. Two milliliters of this sample was diluted to 5-mL with hexane after having added 1 mL of Stock IS. The instrumentation used consisted of a GC Shimadzu 14A with an auto injector AOC-14 and C-R4AX Chromatopac. The system is able to support 2 columns and 2 ECD detectors. The columns were SPB 5, fused silica, 30 m, 0.53 mm ID and 1.5 m film thickness and DB-608, fused silica, 30 m, 0.53 mm and 1.5 m film thickness. Helium carrier gas flow was established at 30 cm/sec linear velocity. The temperature was programmed from 60C (5 min) to 200C (5 min) at 10C/min and then to 250C (5 min) at 2C/min and finally to 270C (24 min) at 3C/min. The injector temperature was 250C and the 2 detectors temperature 300C. The injection volume was 4 L splitless mode with a 3 min delay. 2.3.2. Chlorotriazine herbicides and organophosphate insecticides The reference method that was followed is based on EPA Method 507 [22]. A solid phase extraction procedure was applied before GC-FTD analysis. Solid phase extraction using SPE discs of 47 mm diameter and 0.5 thickness, containing 500 mg of the bonded phase (octadecyl-C18-bonded silica), was used for

sample preparation. SPE discs were conditioned with 10 mL of acetone (R.A. from Lab-Scan) for 3 h. Methanol modifier (5 mL, R.A. from Lab-Scan) was added to the 2-L samples (n = 2) to allow better extraction. The samples were acidified with H2SO4 1:1 (v/v) to pH < 3. Twelve grams (1 cm) of glass beads were poured on the disc already placed in the conventional Millipore apparatus and both were washed with 10 mL of dichloromethane (DCM, R.A. from Lab-Scan) for 3 min with the vacuum off. The disc was not allowed to become dry as recommended [2325]. The sample was mixed well and allowed to percolate through the discs at a flow rate of 50 mL/min under vacuum. After sample extraction, the compounds trapped in the disc were collected using 2 10 mL of solvent mixture dichloromethane ethyl acetate (1:1, v/v, R.A. from Lab-Scan) as eluting solvent. The eluted fractions were evaporated to 4 mL on a rotary evaporator (35C). After careful evaporation of the solvent to 0.5 mL in a gentle stream of nitrogen (nitrogen purity >99%), the residue was dissolved in 1 mL of n-hexane and the solution was evaporated to a final volume of 1 mL for GC injection. For the measurement a GC Shimadzu 17A equipped with a Flame Thermionic Detector (FTD) was used. For the GC the following program was used: From 60C (5 min) to 210C (5 min) at 15C/min and to 300C (3 min) at 5C/min. The injection temperature was 250C and the detector temperature was 300C. The volume of injection was 4 L. Other information related to the method includes: splitless mode for 1min, flow of the helium carrier gas: 8 mL/min. The column used for the chromatographic separation was an SPB-5 (Supelco), fused silica, 30 m 0.53 mm ID. 2.3.3. Volatile and semivolatile organic compounds Highly volatile organic compounds with low water solubility are extracted (purged) from the

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sample matrix by bubbling an inert gas through an aqueous sample. Purged sample components are trapped in a tube containing suitable sorbent materials. When purging is complete, the sorbent tube is heated and backflushed with helium to thermally desorb trapped sample components onto a capillary gas chromatography (GC) column. The column is temperature programmed to separate the method analytes which are then detected. A series configuration of a high temperature photoionization detector (PID) equipped with 10 eV (nominal) lamp and electroconductivity detector (ECD) is required. This allows the simultaneous analysis of VOCs that are aromatic or unsaturated by photoionization detector and organohalide by an electrolytic conductivity detector. The reference method that was followed is based on EPA Method 502.2 [26]. The determination of the VOCs was carried out using the on-line Purge and Trap technique (P&T) followed by gas chromatographic (GC) measurement, with the OI Analytical Purge and Trap Unit 4560 with the software Win Trap Plus and the Hewlett Packard 5890 Series II Plus Gas Chromatograph. A wide bore capillary column VOCOL (Supelco), 60 m 0.53 mm i.d. 3.0 m i.d. film thickness was used, and the carrier gas was helium. A special splitter on the column guided the sample into the 2 detectors ECD and PID. The column temperature was held for 10 min at 35C and then programmed to 200C at 4C/min, for 10 min (all expected compounds are eluted). The temperature for the PID detector was 220C and for the ECD 250C. 2.4. Quality control and quality assurance The validation of the methods applied was done according the Standardised Method ISO 17025:2000. The quantitation limits, precision (reproducibility and repeatability) and accuracy (average recovery and recovery range) for both the instrumental stage and the complete method for each pesticide studied were validated.

According to this, each time a set of 20 samples was extracted or reagents were changed, a Laboratory Reagent Blank was analyzed, in order to determine interfering peaks and reduce the possibility of contamination. Blank samples and spike samples of three different concentrations (0.01 g/L, 0.05 g/L and 0.1 g/L) were run to check for interference and cross-contamination. The spiking average ranged from 0.008 to 0.023 g/L with a standard deviation that ranged from 0.001 to 0.004 g/L. The repeatability ranged from 0.003 to 0.011, while the reproducibility ranged from 0.002 to 0.006. Finally the uncertainty ranged from 0.004 to 0.013. For each substance studied, the mean recovery value was set to fall in a range of 30%, while the relative standard deviation (RSD) was set to be less than 20%. If any of the samples failed these criteria, the procedure was repeated. The limit of detection (LOD), the limit of quantitation (LOQ) and the recoveries for each substance are provided in Table 2. 3. Results and discussion Table 3 and Fig. 2 show the ranges of the substances examined for the period between February 2000 and May 2005. The numbers given in parenthesis after the name of the chemical compounds refer to the code number of each compound as set by the EU Directive 76/464/EEC on the discharge of dangerous substances. Hexachlorobutadiene was determined in quite high concentrations (10 g/L), higher than the quality objectives set both by EU and also the national legislation (K 8/2001), [27], (0.1 g/L), in Xeros (1138 894 60) river, while toluene, 1,1,1trichloroethane, 1,2-dichloropropane, vinyl chloride and 1,4-dichlorobenzene were the most frequently found among VOCs and SVOCs. Non compliance with quality objectives was observed in Garyllis (1943 675 80) river for hexachlorobutadiene (84), hexachlorobenzene

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Table 2 % Limit of detection and % recovery at the limit of quantitation limit for the substances analysed Code 46 53 54 55 65 77 79 82 83 84 86 96 100 106 110 112 118 119 128 131 Substance DDT 1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene 1,2-dichloropropane Endrin Ethylbenzene Heptachlor Hexachlorobenzene Hexachlorobutadiene Hexachloroethane Naphthalene Parathion Simazine 1,1,2,2-tetrachloroethane Toluene 1,2,4-trichlorobenzene 1,1,1-trichloroethane Vinyl chloride Atrazine LOD (g/L) 0.004 0.008 0.008 0.02 0.0008 0.003 0.008 0.0005 0.003 0.0006 0.0006 0.0006 0.005 0.005 0.002 0.003 0.002 0.003 0.003 0.005 LOQ (g/L) 0.013 0.03 0.03 0.06 0.003 0.010 0.03 0.002 0.010 0.002 0.002 0.002 0.01 0.01 0.007 0.01 0.006 0.01 0.01 0.01 % Recovery at LOQ 97 100 100 100 100 95 100 79 89 100 83 97 94 86 100 100 100 100 100 72

(83), (quality objective: 0.03 g/L) and 1,2,4trichlorobenzene (118), (quality objective: 0.4 g/L). It is important to note that hexachlorobutadiene (HCBD) is one of the most nephrotoxic chlorinated-hydrocarbon in rodents [28]. Additionally, short-term exposure to high concentrations of hexachlorobenzene (HCB) can lead to kidney and liver damage, central nervous system excitation and seizures, circulatory collapse and respiratory depression [29]. Chronic exposure to hexachlorobenzene can cause diseases such as porphyria, hepatotoxicity, immune suppression, neurotoxicity, cardiotoxicity, alterations in calcium metabolism and reproductive effects [2933]. 1,2,4-trichlorobenzene is well known for its effects in estuarine macrobenthic communities [34], in fish [35], in rats [36], and recently in root growth [37]. The results obtained have shown that the most commonly encountered organochlorine

insecticides were hexachlorobenzene and heptachlor. Hexachlorobenzene was mostly found in Garyllis (1943 675 80) river, while heptachlor was mostly found in Kalavassos Dam (1897 510 50). Atrazine and simazine (chlorotriazine herbicides), despite the fact that their use has been banned, were identified in most of the water bodies examined in low concentrations while from the category of organophosphate insecticides only parathion was identified at three of the water bodies. The following substances were never traced in any of the water samples examined: aldrin (1), azinphos-ethyl (5), azinphos-methyl (6), chlorobenzene (20), chloroform (23), 2-chlorotoluene (38), 1,2-dichloroethane (59), dieldrin (71), fenthion (81), and 1,1,2-trichloroethane (120). It is also noted that none of the substances examined were traced in the following water bodies: Stavros tis Psokas Skarphos (1226 858 60) and Mylou Kornos (1873 524 60).

Table 3 Range of concentrations of the substances examined during 20002005 (concentrations are given in g/L) 5 6 7 9 10 11 12 13 14 15 16 17 18 19

Water body

Substance nd nd nd nd nd nd nd nd0.001 nd nd nd nd nd0.099 nd nd nd nd nd0.018 nd0.001 nd0.05 nd nd nd0.043 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 0.001 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd ndtrace nd nd nd0.046 nd nd nd0.013 nd0.03 nd nd nd nd nd nd nd0.073 nd nd nd nd nd nd nd nd nd nd nd

461 nd0.014 nd nd 0.015 nd0.004 nd

nd4

nd

nd

77 83

nd nd

nd nd

nd nd

84

nd

nd

nd nd0.002 nd

nd nd0.004 nd

nd nd0.003 nd

118

nd

nd10 nd

nd

nd nd4.6 nd2.92 nd3.1

1002 nd0.018 nd nd nd nd nd0.078 nd0.015 nd nd ndtrace5 nd0.002 nd0.093 nd0.001 nd0.012 nd

nd

nd

nd

106

nd

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131

nd0.01 nd

nd

nd0.032 nd

ndtrace nd0.02

ndtrace nd0.003

nd0.471 nd0.053 ndtrace

nd0.06 nd0.094 nd

533

nd

nd

nd

54

nd

nd

nd0.04 nd

55

nd

nd0.024 nd

nd0.014

ndtrace nd

nd2.89 nd2.4 nd3.3

231

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Table 3 (Continued) 5 6 7 9 10 11 12 13 14 15 16 17 18 19

Water body

Substance trace trace nd

65

nd

79

nd

82 nd nd nd nd nd nd nd

nd

nd0.025 nd0.051 nd nd

nd0.025 ndtrace nd

ndtrace ndtrace nd

nd0.029 ndtrace nd

nd0.03 nd0.032 nd

nd0.03 nd0.028 nd

nd0.046 ndtrace nd

nd0.034 ndtrace nd

nd0.039 ndtrace nd

ndtrace nd

nd0.057 ndtrace nd nd

nd0.026 ndtrace nd nd nd nd nd

86

nd

nd

nd

nd0.026 nd0.028 nd0.007 nd

nd0.032 ndtrace nd0.495 nd

96

nd

110

nd

ndtrace nd

ndtrace nd

ndtrace nd0.015 ndtrace ndtrace nd

ndtrace nd

112 nd nd

nd

ndtrace ndtrace nd

ndtrace ndtrace nd

119

nd

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128

nd

ndtrace nd0.007 nd0.071 ndtrace nd ndtrace nd0.06 nd0.037 ndtrace nd0.096

nd0.024 nd0.028 nd

ndtrace ndtrace nd0.045 nd0.129 nd

ndtrace ndtrace nd0.123 ndtrace nd0.138

ndtrace ndtrace nd0.032 ndtrace nd0.097

ndtrace ndtrace nd0.083 nd0.056 nd0.134

ndtrace ndtrace ndtrace nd0.032 nd0.068

ndtrace nd0.018 ndtrace nd0.086 nd

ndtrace nd0.021 nd2.9 ndtrace ndtrace nd8.949 nd0.013 nd0.447

nd0.093 nd0.06 nd0.155

ndtrace nd0.008 nd0.045 nd0.038 nd

nd0.022 nd0.068 nd0.229

nd0.06 nd0.045

List I. List I candidates. 3 List II. 4 nd, not detectable concentration. 5 Trace: concentration between the detection and quantitation limit.

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10 9 8 Concentration in g/L 7 6 5 4 3 2 1 0 Vinyl chloride 1,1,1-trichloroethane Toluene 1,1,2,2-tetrachloroethane Hexachloroethane 1,2,4-Trichlorobenzene Hexachlorobutadiene Ethylbenzene 1,2-dichloropropane 1,4-Dichlorobenzene 1,3-Dichlorobenzene 1,2-Dichlorobenzene Atrazine Simazine Parathion Hexachlorobenzene Heptachlor Endrin DDT 1 5 12 9 15 18

233

Water body

Fig. 3. Comparison of substances concentration in different water bodies in Cyprus during the period 20002005. OCPs = DDT + endrin + hexachlorobenzene + heptachlor OPs = Parathion HBCs = Simazine + atrazine VOCs = Hexachlorobutadiene + 1,2,4-trichlorobenzene + 1,2-dichlorobenzene + 1,3-dichlorobenzene + 1,4-dichlorobenzene + 1,2-dichloropropane + ethylbenzene + hexachloroethane + naphthalene + 1,1,2,2tetrachloroethane + toluene + 1,1,1-trichloroethane + vinyl chloride.

Subtances monitored

Fig. 2. Range of substances concentration in g/L found in water bodies in Cyprus during the period 20002005.

The water bodies where most of substances examined were present are Garyllis River (1943 675 80) and Polemidia dam (1943 675 90). Garyllis River flows downstream towards Polemidia dam. A more detailed investigation is needed in order to examine the exact pollution sources in that area. The operation of the monitoring network is continuing and new legislative measures will be enforced if the results show that such additional measures should be taken. Finally it must be pointed out that more detailed studies have to be carried out covering a wider spectrum of substances to get clear baseline data for the entire areas of the water bodies including a bigger number of sampling points. The comparison between substances in the different water bodies is shown in Fig. 3. It is clear that volatile compounds are present in almost all the samples examined and are present in higher concentrations compared to those of pesticides. Organochlorine pesticides were mostly present in Kalavassos Dam (1897 510 50). Dhiarizos River (1124 931 95) and Dhipotamos

Dam (1873 514 95) have the highest concentrations of herbicides investigated. 4. Conclusions Though, it cannot be seen from the datasets presented in this paper since the data refer to the range of the concentrations of the various compounds investigated, during the years a remarkable decrease is observed for all the substances. The results obtained showed that the most commonly encountered organochlorine insecticides were hexachlorobenzene (in Garyllis river, 1943 675 80) and heptachlor (in Kalavassos Dam, 1897 510 50). Atrazine and simazine which are chlorotriazine herbicides were identified in most of the water bodies examined in low concentrations. Parathion was the only organophosphate insecticide which was identified at three of

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the water bodies. In the two following water bodies, Stavros tis Psokas Skarphos (1226 858 60) and Mylou Kornos (1873 524 60) none of the substances examined were traced. On the other hand, the water bodies where most of substances examined were present are Garyllis River (1943 675 80) and Polemidia dam (1943 675 90). Non compliance with quality objectives has been observed in Garyllis (1943 675 80) river for hexachlorobutadiene (84), hexachlorobenzene (83), (quality objective: 0.03 g/L) and 1,2,4-trichlorobenzene (118), (quality objective: 0.4 g/L). A more detailed study needs to be performed in order to detect the sources of pollution of the rivers and their distribution so as to be able to develop alternative ways for their reduction. The sediments must also be examined in order to evaluate the presence and persistence of pesticides. Finally, the possible risks that the use of surface water for drinking purposes may enclose, as well as the effects on fauna and flora in these ecosystems have to be assessed and evaluated. Acknowledgements This work was carried out in the framework of the reporting obligations of Cyprus in regards to EU Directives 76/464/EEC and 80/68/EEC by the University of Cyprus in collaboration with the General State Laboratory. It was financially supported by the Ministry of Agriculture, Natural Resources and Environment (Environment Service). Experimental analysis was financed by the General State Laboratory of Cyprus. The authors would like to thank Ms P. Efstathiou and Ms P. Piera for their contribution in the analytical work carried out. References
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