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Air and Groundwater Pollution in an Agricultural Region of the Turkish Mediterranean Coast

September 9, 2008

By Tuncel, Semra G Oztas, Nur Banu; Erduran, M Soner

ABSTRACT Air pollution and groundwater pollution in conjunction with agricultural activity were investigated in Antayla province on the Turkish Mediterranean coast. The air pollution was investigated in terms of gas-phase nitric acid (HNO^sub 3^), sulfur dioxide (SO^sub 2^), ammonia (NH^sub 3^), and particulate matter for a 6- month period in the atmosphere using a “filter pack” system, which was developed and optimized in our laboratory. Ozone was measured by using an automated analyzer. Among all of the gas-phase pollutants, HNO^sub 3^ had the lowest concentration (0.42 [mu]g * m^sup -3^) followed by NH^sub 3^. Agricultural activities seem to be the major source of observed NH^sub 3^ in the air. The current state of water pollution was investigated in terms of organochlorine and organophosphorus pesticides around the greenhouses, in which mainly tomato, pepper, and eggplant are cultivated. Water samples were collected from 40 points, 28 of which were wells and 12 of which were surface water. The pesticide concentrations in water samples were determined by means of solid-phase extraction (SPE) followed by a gas chromatography (GC)-electron capture detector (ECD)/nitrogen phosphorus detector (NPD) system. In general, surface water samples were more polluted by the pesticides than groundwater samples. The most frequently observed pesticides were chlorpyriphos (57%) and aldrin (79%) in groundwater, and chlorpyriphos (75%), aldrin, and endosulfan sulfate (83%) in surface water samples. The highest concentrations were observed for fenamiphos (394.8 ng/L) and aldrin (68.51 ng/L) in groundwater, and dichlorvos (322.2 ng/L) and endosulfan sulfate (89.5 ng/L) in surface water samples. At least one pesticide had a concentration above the health limit in 38% of all the water samples analyzed.

INTRODUCTION

It is increasingly realized that agricultural activities could be important sources of air and water pollution.1 Impacts of agricultural activities are basically due to nitrogencontaining compounds from fertilizers and pesticide applications. The large- scale utilization of mineral nitrogenfertilizer is blamed for nitrate leaching, soil acidification, and gaseous emissions of nitrogen-containing compounds such as ammonia and nitrogen oxides to the air. The principal impact areas for pesticides are bodies of water.

In the last few decades, pesticide use has increased throughout the world for the sake of increasing the agricultural productivity to meet the increasing demand for food production. Although there is a tendency to use less harmful and less persistent chemicals, pollution due to the residues of these chemicals as well as their derivatives and metabolites has been observed in different regions in the world and in different environmental matrices, such as surface waters,2-4 groundwaters,5,6 soil and sediments, 7-9 and air.10-12

There is a growing concern regarding the effect of pesticides on public health, because this large group of chemicals is widely included in the food chain. There is evidence that exposure to pesticides via food and water might pose cancer risk.13,14 In the human body, pesticides may cause neurotoxicity15,16 and reproductive/ developmental abnormalities.17,18

In this paper, air and groundwater pollution related to agricultural activities in the Antalya district of the Turkish Mediterranean coast is investigated. The specific aims of the study include estimation of the contribution of fertilizing activities to air pollution, and analysis of the effects of agricultural activities in terms of pesticides for the surface and groundwaters of the Turkish Mediterranean coast.

EXPERIMENTAL PROCEDURES

Study Area

The sampling station for air pollutants and study area for water pollution in the Antalya region is shown in Figure 1. The city itself has a population of almost 1.5 million. Agriculture and tourism with small- to medium-scale industry are the major means of subsistence in the region. An average of 6 million tourists visit Antalya city and surroundings every year. Antalya is the leading region for tourism in the country.

Agricultural activities are based on fresh vegetables and orchards. Large areas to the west of the city are orchards and vegetable fields; mostly tomatoes, green peppers, and eggplant are cultivated in the greenhouses.19 Approximately 30% of Europe’s fresh vegetable demand is provided from the Antalya region. For many years, fertilizers and different classes of pesticides, including chlorinated and phosphorous pesticides, have been applied in the region. These chemicals contaminated the air, soil, and groundwater for many years. As far as air pollution is concerned, the region is extensively studied in terms of metal pollution in the aerosols,20 but not gas-phase pollutants. This is the first study for determining the gasphase pollutants in conjunction with agriculture. Because industrial activities are limited in the region, we believe agricultural activities play a major role in the atmospheric loading of several criteria pollutants such as sulfur dioxide (SO^sub 2^), oxides of nitrogen (NO^sub x^), ozone (O^sub 3^), particulate matter (PM), sulfate (SO^sub 4^^sup 2-^), nitrate, and ammonium. Among all measured air pollutants, those containing nitrogen are directly related to agricultural activities.

Air Sampling

The monitoring station consists of a caravan, 3 x 2 x 2 m in size, which was placed approximately 30 m away from the sea and far from local point sources. It was equipped with automated analyzers for SO^sub 2^, O^sub 3^, and NO^sub x^ measurements and a refrigerator to store the samples. The filter pack assembly was placed outside at the top of the caravan. It was connected to the gas flow meter and the vacuum pump by means of high-density polyethylene tubes. Sampling of ammonia (NH^sub 3^), nitric acid (HNO^sub 3^), and SO^sub 2^ was done with a previously developed and optimized filter pack system under laboratory conditions by Karakas and Tuncel.21 All parameters except gaseous HNO^sub 3^ were sampled for the months of August, September, and October in 1995 and February, March, and April in 1996. Gaseous HNO^sub 3^ sampling was done for 1 month (between March 17 and April 21, 1997). The sampling period was 24 hr for all samples. Two field blanks were taken with the same filter pack system for approximately 5 min at the end of each month. The filter pack system used in this work for the simultaneous collection of SO^sub 2^, HNO^sub 3^, and NH^sub 3^ was based on the adsorption and absorption of these pollutant gases on the impregnated (chemically treated) and commercially available filter papers. PM was collected on Teflon filters with a pore size of 0.22 [mu]m and 47 mm in diameter; these were placed as the first cartridge of the filter pack assembly. Whatman-41 filters were impregnated for SO^sub 2^ and NH^sub 3^ collection. Commercially available nylon filters collected HNO^sub 3^. Preparation and optimization of the filter pack system is discussed by Karakas and Tuncel.21The sampler drove the air by means of a suction pump with a capacity of 20.30 L [mu] min^sup -1^ through the filter package system, and the flow rate was controlled using a flow meter. By multiplying this flow rate by the duration of sampling, the volume of sampled air was calculated in cubic meters.

Chloride (Cl^sup -^), SO^sub 4^^sup 2-^, and nitrate (NO^sub 3^- ) ions were determined by ion chromatography and ammonium (NH^sub 4^^sup +^) was measured by colorimetry. In addition to gas-phase pollutants, water extracts of collected PM were analyzed for NO^sub 3^-, SO^sub 4^^sup 2-^, and NH^sub 4^^sup +^ using the same techniques.

Water Sampling

The water samples that were subject to pesticide analysis were collected from the Kumluca region, a district on the Mediterranean coast 90 km west of Antalya city. In the region, there is no industrial activity, but two settlement centers exist: Kumluca and Finike. The economy is based on agriculture with citrus gardens and greenhouses being the main investments. The study area covered a 40- by 36-km area and is surrounded by the south edges of the West Taurus mountain chain and the Mediterranean Sea. A photographical image (from Google Earth) of the region is given in Figure 1. In this figure, each sampling point can be found and the high number of greenhouses can be seen near the coast, spreading through the north. The groundwaters were sampled from the wells of the greenhouses. The well waters that were sampled were being used for irrigation purposes only and not for human consumption or drinking. The sampling program was performed between May 4 and 6, 2005 at 40 points, 28 of which were wells and 12 were surface waters. Sampling points were located using a geographical positioning system (GPS). At the groundwater sampling sites, the wells were flushed for 3 min before sample collection. Water samples were collected into 1-L amber glass bottles, which were previously cleaned by washing with detergent and hot water; rinsing with acetone, hexane, and deionized water successively; and dried. The pH, salinity, and conductivity of the water samples were measured at the site and the samples were kept at 4 [degrees]C until analysis. The extraction of pesticides was performed using C18 solid phase extraction (SPE) disks (Supelco, ENVI disks), after the addition of surrogate standards and 5 mL of methanol to keep the SPE disk conditioned during filtration. The extraction disk was conditioned by sequential addition of 10 mL of dichloromethane (DCM), methanol, and deionized water, which were kept in contact with the disk for 90 sec. After filtration of the sample and drying the disk, two portions of 10 mL of DCM eluted the analytes. Water was removed by anhydrous sodium sulfate (rinsed by DCM and hexane, dried at 250 [degrees]C) before a gentle stream of nitrogen evaporated the solution to near dryness. After the addition of internal standards, the volume was brought to 1 mL with acetone.

All of the solvents used were chromatographic grade and purchased from Merck Co. Certified chlorinated pesticide standard solutions and neat organophosphorus pesticide solutions (Dr. Ehrenstorfer brand) were used through the analysis. Working standard solutions were prepared in acetone. Pentachloronitrobenzene (ChemService) and the mixture of 2,4,5,6-tetrachloro-m-xylene and decachlorobiphenyl (ChemService) were used as internal and surrogate standards, respectively, for chlorinated pesticides. For organophosphorus pesticides, triphenyl phosphate (ChemService) and tributyl phosphate (ChemService) were used as internal and surrogate standards, respectively.

The analyses were performed by a HP 6890 series gas chromatograph (GC) coupled with a [mu]-electron capture detector (ECD) and nitrogen phosphorus detector (NPD). All of the gases used were of high purity. The analysis of 17 chlorinated pesticides (aldrin; 4,4′- p,p -dichlorodiphenyldichloroethane (DDD); 4,4′-p,p- dichlorodiphenyldichloroethylene (DDE); 4,4′-p,p- dichlorodiphenyltrichloroethane (DDT); dieldrin; endosulfan-alpha; endosulfan-beta; endosulfan sulfate; endrin; endrin aldehyde; HCH- alpha, beta, gamma and delta isomers; heptachlor; heptachlor endo epoxide; and methoxychlor) was performed with a GC-ECD system using an HP-5 mass spectrometry capillary column (30-m length x 0.25-mm inner diameter x 0.25-[mu]m film thickness). The column temperature increased from 80 to 150 [degrees]C at a rate of 10 [degrees]C/min, was held for 5 min, increased from 150 to 275 [degrees]C at 5 [degrees]C/min, and held for 3 min. Helium was used as a carrier gas with a flow rate of 35 cm/sec at constant flow mode. The split/splitless injector was used in splitless mode and the injector temperature was 250 [degrees]C. Nitrogen was used as make-up gas at a flow rate of 30 mL/min and the detector temperature was 290 [degrees]C.

For the analysis of organophosphorus pesticides (azinphos- methyl, bromophos-ethyl, bromophos-methyl, chlorpyrifos, diazinon, dichlorvos, fenamiphos, fenitrothion, fenthion, malathion, methamidophos, methidathion, parathion-methyl, phosphamidon, and pirimiphosmethyl) a GC-NPD system was used with an HP-1 capillary column (30-m length x 0.25-mm inner diameter x 0.25-[mu]m film thickness). The column temperature was increased from 50 to 100 [degrees]C at a rate of 10 [degrees]C/min, from 100 to 230 [degrees]C at 5 [degrees]C/min, from 230 to 280 [degrees]C at 25 [degrees]C/min, and held for 4 min. Helium gas was used as a carrier with a flow rate of 25 cm/sec at constant flow mode. Again, the split/splitless injector was used in splitless mode and the injector temperature was 250 [degrees]C. The hydrogen and air had a flow rate of 4 and 60 mL/min, respectively. The make-up gas (nitrogen) had a flow rate of 3 mL/min, and the detector temperature was 330 [degrees]C.

RESULTS AND DISCUSSION

Air Pollution

As we have mentioned before, agriculture, tourism, and medium- scale industry (textile and food) are the major sources for atmospheric loadings of the pollutants we studied. All three sources were definitely affecting each one of the pollutants, but agricultural activities were especially important for nitrogen- containing pollutants. Our approach was to examine the behavior of the pollutants rather than quantifying each contributing source. For many years nobody was interested in agriculture as a means of air pollution in the region and only waters were studied.

In Table 1, a summary of the statistics for the air pollutants are given. Parameters presented in the table include the number of samples, arithmetic mean and median values, and standard deviations. All of the measured parameters are listed, although we are aware that some of these pollutants, such as O^sub 3^, are indirectly affected by agriculture. This gives an idea of the atmospheric loadings of all of the measured parameters; however, only those we believe are directly related to agricultural activities will be discussed.

To understand the relative strengths of anthropogenic and sea salt contributions of SO^sub 4^^sup 2-^ in the Mediterranean atmosphere, the non-sea salt SO^sub 4^^sup 2-^ (nss-SO^sub 4^^sup 2- ^) concentrations were calculated using the following equation:

nss-SO^sub 4^^sup 2-^ = t-SO^sub 4^^sup 2-^ – 0.139 [Cl^sup -^], (1)

where t-SO^sub 4^^sup 2-^ is total SO^sub 4^^sup 2-^ and 0.139 is taken as the ratio of SO^sub 4^^sup 2-^ to Cl^sup -^ in seawater.

The highest coefficient of variation (1.61) was observed for Cl^sup -^, probably because of Cl^sup -^ loss as hydrochloric acid from acidic aerosols. Unfortunately, we were not able to confirm this loss because sodium was not measured. Otherwise we could have looked at the correlation between the sodium/Cl^sup -^ ratio and nss- SO^sub 4^^sup 2-^. As it is known, Cl^sup -^ is affected by different sources or meteorological parameters more than the other parameters. Gaseous HNO^sub 3^ and NH^sub 3^ concentrations are relatively lower than other species. Comparable amounts of nss- SO^sub 4^^sup 2-^ and total SO^sub 4^^sup 2-^ suggest that SO^sub 4^^sup 2-^ is mostly of anthropogenic origin. Agricultural activities indirectly affect SO^sub 4^^sup 2-^ concentrations. NH^sub 4^^sup +^ in particulate phase first forms ammonium sulfate and then ammonium nitrate, which means most of the measured SO^sub 4^^sup 2-^ is in the form of ammonium sulfate.22

Seasonal Variations of the Measured Air Pollutants. The seasonal average values of the species measured are given in Figures 2 and 3. As can be seen from Figure 2, SO^sub 4^^sup 2-^ and nss-SO^sub 4^^sup 2-^ have maximum concentrations during summer despite minimum concentrations of SO^sub 2^. Obviously, seasonal variation of SO^sub 2^ is controlled by the gas-to-particle conversion rate and different source strengths during different seasons.

When we consider nitrogen-containing pollutants, one first thinks of NH^sub 3^. The main natural sources of NH^sub 3^ emissions into the atmosphere are soil, oceans, and wild animal excrete. Anthropogenic sources include domestic animal excrete, fertilizers, and biomass burning. NH^sub 4^^sup +^ exists in the air as a result of dissolution of atmospheric NH^sub 3^(g) and scavenging of NH^sub 4^^sup +^ aerosol.23 The equilibrium between particulate-phase NH^sub 4^^sup +^ and SO^sub 4^^sup 2-^ [2NH^sub 4^^sup +^+ SO^sub 4^^sup 2-^ 3 (NH4)2SO4] is very well known. This equilibrium causes inaccuracies in NO^sub 3^- concentrations in the air as excess NH^sub 4^^sup +^ from the above equilibrium forms ammonium nitrate. However, this is not a problem in our case because we simultaneously collected NH^sub 4^^sup +^, HNO^sub 3^ and NO^sub 3^; therefore, we measured total NO^sub 3^.

Seasonal variation of NH^sub 3^ and particulate NH^sub 4^^sup +^ is shown in Figure 3. As seen from Figure 3, seasonal fluctuation of NH^sub 3^ is more pronounced than particulate NH^sub 4^^sup +^. This is most likely due to different gas-to-particle conversion rates during different seasons.

Considerable differences in summer and winter concentrations of NH^sub 3^ gas were observed. This is due to higher source strength (soil fertilizing) and lower tendency to react with HNO^sub 3^(g) at higher temperatures. The observed high concentrations of NH^sub 3^, especially for very hot days such as in August, can be explained by volatilization from fertilizers. The observed differences in concentration for both parameters in summer can again be explained by a high rate of fertilizer and pesticide use in summer. The reported fertilizer consumption in the region is around 290 kg/ha, which is above the country average of 91 kg/ha.24The higher consumption rate of fertilizer than the country average supports the above conclusion.

When considering the surface wind and trajectory data for the sampling site,25 the highest NH^sub 4^^sup +^ concentrations were associated with westerly and northwesterly winds. This is in accordance with the location of vegetable fields and orchards to the west and northwest of the air pollution sampling station. This is an obvious implication of agriculture for the observed NH^sub 3^ concentrations in our study area.

Water Pollution

As stated earlier, water pollution in the region was evaluated in terms of pesticides. The percent recoveries of the studied pesticides and detection limits of the analysis systems are presented in Table 2. The detection limits are the concentrations with a signal-to-noise ratio (S/N) of 3. The surrogate standards were used to monitor the ongoing recovery for each extraction and the percent recoveries were calculated from the extraction of 1 L deionized water spiked with the target pesticides at 0.5 [mu]g/L in organophosphorus, and 0.1 [mu]g/L in chlorinated pesticides. The concentrations presented were the ones obtained after correction with the percent recoveries.

Occurrences of Pesticides in Water Samples. In the discussion of pesticide data one should keep in mind that we present two classes of pesticides (organochlorine and organophosphorus) in two different types of water samples (surface and groundwater). Therefore, before detailed analysis of levels of the pesticides in water samples, we will provide a general view of the distribution of the pollutants between the two different types of water. The percentage of number of samples with a certain pesticide gives a general idea about the pollution. Figure 4 shows the percent occurrences of the two groups of pesticides in two different types of water samples. In all of the samples at least one of the target pesticides was determined. For well water samples, at least one of the organophosphorus pesticides (OPPs) was detected in 75% of the wells and 92% of surface waters. The organochlorine pesticides (OCPs) were detected in 89% of the groundwater and in all of the surface water samples. The observed OPP occurrences reveal current use, and the OCP occurrences indicate past use because they have been banned in the country since the 1980s. However, chlorinated pesticides are very resistant to degradation in the environment, which is why their residues can still be found in soil, water, and sediments. Chlorinated pesticides are still being detected in aquatic environments in studies of different regions of the country.4,8,26

Pesticides were detected more frequently in surface water samples than in well water samples. In the surface water samples, the most frequently detected pesticides were aldrin (83%), endosulfan sulfate (83%), and endosulfan (75%), among OCPs; and chlorpyriphos (75%), parathionmethyl (67%), and diazinon (58%) among OPPs. These frequencies were lowered to 79% for aldrin, 61% for endosulfan, 54% for endosulfan sulfate, 57% for chlorpyriphos, 21% for parathion- methyl, and 18% for diazinon for well water samples.

Dynamics of the Aquifer. The study area consisted of two plains, Finike and Kumluca. There are approximately 300 wells dug in these plains. The well depths range from 10 to 15 m. However, the groundwater depths are between 24 and 180 m. In the Finike plain, the groundwater recharge and discharge rates are 56 x 106 m^sup 3^/ yr, whereas in the Kumluca plain, the rates are 8 x 106 m^sup 3^/ yr. In these plains, only Finike plain has three permanent streams: Karasu, Akcay, and Alakir with discharge rates of 4.5, 1.9, and 2.3 m^sup 3^/sec, respectively.27

Pesticide Concentrations in Water Samples. Before we discuss concentrations of the pesticides we must point out that our sampling period was spring, in which the water level in the reservoirs was the highest. This means that in other seasons the concentrations could be higher than what we have measured.

The distribution of total concentrations of the pesticides among the water samples are given in Figure 5. The European Union directives state that in water intended for human consumption, any pesticide residue must be below 0.1 [mu]g/L and the sum of all pesticides must be below 0.5 [mu]g/L.28 As Figure 5 indicates, in our case 16% of the surface waters and 4% of groundwater exceeded the limit set for the total pesticide concentration. Average total pesticide concentrations were 180 ng/L for well and 321 ng/L for surface waters. For 46% of the samples, the total concentrations of pesticides in well waters were lower than 0.1 [mu]g/L.

The results of the analysis of OCPs and OPPs in well and surface water samples are presented in Tables 3 and 4, respectively. Among all of the sampling points, 32.1% of well water samples contained at least one pesticide with a higher concentration than the limit value set for a single pesticide, which is 0.1 [mu]g/L. Fifty percent of surface water samples contained at least one pesticide with a higher concentration than the limit. For all datasets, the limit value was exceeded in 37.5% of the sampling points.

The data presented in Tables 3 and 4 point out that although the OCPs were observed with a higher frequency than OPPs, their concentrations were much lower. In all of the samples the limit values were exceeded for the OPPs. Therefore our discussions are mainly focused on OPPs.

As seen in Table 3, in well water samples the highest concentrations were observed for fenamiphos, diazinon, and azinphos methyl, which are OPPs. Fenamiphos is used for the control of citrus tree and tomato root nemotodes, and others for tomatoes, peppers, and cucumbers, which are currently cultivated in the region. The highest concentration of fenamiphos (394.8 ng/L) was observed at a well (sampling point 1 in Figure 1) in a citrus tree garden where no other OPPs were observed. This high concentration indicates the current use of this pesticide around the well.

Figure 6 shows the concentration distribution of OPPs among well waters. In sampling points 2, 6, and 12, the cumulative concentrations were close to or higher than the limit value (0.5 [mu]g/L). Azinphos-methyl, phosphamidon, and chlorpyriphos were common pesticides detected in these samples. Use of the same water table could be the reason for the common detections of these pesticides in these wells. In sampling point 13, which is close to sampling point 2, only chlorpyriphos was observed. Although these two wells are closer to each other, the wells might be fed by different water tables.

In samples 7, 11, 15, and 21 at least two OPPs were observed, among which fenamiphos (sample 11), chlorpyriphos and dichlorvos (sample 15), diazinon (sample 7), and azinphos methyl (sample 21) were higher than limit value of 0.1 [mu]g/L for a single pesticide. These samples were collected from tomato and cucumber greenhouses, where these pesticides were currently been used. In samples 3, 4, and 24, although more than one pesticide was observed, none of them exceeded the limit value. These wells are relatively far from greenhouses and orchards.

The distribution of OPPs among surface water samples are given in Figure 7. Generally, pesticide concentrations in surface waters were higher than in groundwaters. Surface runoff is the main mechanism that leads to contamination of surface waters by pesticides and pesticide runoff depends on topography, soil properties, weather conditions, application practices, and chemical properties of the pesticides.2 Studies have shown that up to 5% of applied pesticides are lost via runoff.29 In this study, the surface waters sampled were surrounded by agricultural activities of greenhouses or orchards, in which different types of pesticides are used. Therefore, surface runoff may be the reason for observed surface water pollution in the study area. Moreover, especially for OPPs, the high occurrences and high concentrations in surface waters can be due to improper disposal of empty pesticide containers. Unfortunately, there is no strict regulation for the disposal of empty containers in the area. The containers were disposed in open fields nearby, and even into the surface waters, which poses risks for both environmental and human health.

In sampling points 33 (Akmaz river) and 36 (Alakir river), the total number of OPPs observed and total concentrations were higher than the limit value. These creeks flow through intense agricultural areas. This pollution may be due to the surface runoff they collect on their way to sea. In these samples methidathion, parathion methyl, and diazinon were observed with concentrations exceeding the limit value for any single pesticide. In sample 33, the concentration of endosulfan sulfate (0.09 [mu]g/L) was close to limit value of 0.1 [mu]g/L. This was the highest concentration detected for chlorinated pesticides. The reason for this extreme result may be domestic use of this pesticide around the sampling point.

At sampling points 27 and 35, the number of pesticides observed was smaller; but those detected were higher in concentration than 0.1 [mu]g/L. The maximum concentration for dichlorvos was 322.2 ng/ L. This high concentration was detected in the sample taken from sampling point 27. This sampling point was an open channel used for irrigation and the dichlorvos pollution was due to improper disposal of pesticide containers. In sample 35 (Goksu river), chlorpyriphos, diazinon, and parathion methyl were detected.

CONCLUSIONS

* Behavior of nitrogen-containing pollutants in the air points out agricultural activities as a source.

* The highest gas-phase pollutant concentrations were for O^sub 3^ and SO^sub 2^.

* The groundwaters and surface waters of the region were polluted by OPPs, which are currently being used in the region.

* The surface water concentrations of the pollutants were generally higher than groundwater concentrations.

* There is evidence of past use of chlorinated pesticides, which have been banned in the country since the 1980s. Although lower in concentration, the chlorinated pesticides were more frequently detected than OPPs.

* When single pesticide concentrations are considered, 32.1% of the well samples and 50% of the surface water samples contained OPPs higher than the maximum permissible concentration for human consumption of 0.1 [mu]g/L given by European Union legislation for a single pesticide.

IMPLICATIONS

The agricultural activities on the Turkish Mediterranean coast affect air and groundwater quality in the region. The study area has both touristic and agricultural importance. Currently agriculture- oriented air pollutants (nitrogen compounds) are not at an alarming level, but some of the pesticide concentrations in groundwater are higher than the health limits. This study provides data to develop mitigation options for environmental protection.

REFERENCES

1. Balint, A.; Heltai, G.Y.; Notas, E.; Tarr, Z.S.; Jung, K. Modeling of Environmental Impact of Different Nitrogen Sources in Soil/Atmosphere System; Microchem. J. 2002, 73, 113-124.

2. Konstantinou, I.K.; Hela, D.G.; Albanis, T.A. The Status of Pesticide Pollution in Surface Waters (Rivers and Lakes) of Greece. Part, I: Review on Occurrence and Levels; Environ. Pollut. 2005, 141, 555-570.

3. Tuncer, G.; Karakacs, T.; Balkas, T.I.; Gokcay, C.F.; Aygun, S.; Yurteri, C.; Tuncel, G. Land-Based Sources of Pollution along the Black Sea Coast of Turkey: Concentrations and Annual Loads to the Black Sea; Marine Pollut. Bull. 1998. 36, 409-423. 4. Turgut, C. The Contamination with Organochlorine Pesticides and Heavy Metals in Surface Water in Kucuk Menderes River in Turkey, 2000.2002; Environ. Int. 2003, 29, 29-32.

5. Ekmekci, M. Pesticide and Nutrient Contamination in the Kestel Polje.Kirkgoz Karst Springs, Southern Turkey; Environ. Geol. 2005, 49, 19-29.

6. Senseman, S.; Lavy, T.L.; Daniel, T.C. Monitoring Groundwater for Pesticides at Selected Mixing/Loading Sites in Arkansas; Environ. Sci. Technol. 1997, 31, 283-288.

7. Ayas, Z.; Barlas, N.E.; Kolankaya, D. Determination of Organochlorine Pesticide Residues in Various Environments and Organisms in Goksu Delta, Turkey; Aquatic Toxicol. 1997, 39, 171- 181.

8. Bakan, G.; Ariman, S. Persistent Organochlorine Residues in Sediments along the Coast of Mid-Black Sea Region of Turkey; Marine Pollut. Bull. 2004, 48, 1031-1039.

9. Zhou, J.L.; Maskaoui, K.; Qiu, Y.W.; Hong, H.S.; Wang, Z.D. Polychlorinated Biphenyl Congeners and Organochlorine Insecticides in the Water Column and Sediments of Daya Bay, China; Environ. Pollut. 2001, 113, 373-384.

10. Alegria, H.; Bidleman, T.F.; Figueroa, M.S. Organochlorine Pesticides in the Ambient Air of Chiapas, Mexico; Environ. Pollut. 2006, 140, 483-491.

11. Coupe, R.H.; Manning, M.A.; Foreman, W.T.; Goolsby, D.A.; Majewski, M.S. Occurrence of Pesticides in Rain and Air in Urban and Agricultural Areas of Mississippi, April.September 1995; Sci. Total Environ. 2000, 248, 227-240.

12. Iwata, H.; Tanabe, S.; Ueda, K.U.; Tatsukawa, R. Persistent Organochlorine Residues in Air, Water, Sediments, and Soils from the Lake Baikal Region, Russia; Environ. Sci. Technol. 1995, 29, 792- 801.

13. Hodgson, E.; Levi, P.E. Pesticides: an Important but Underused Model for the Environmental Health Sciences; Environ. Health Perspect. 1996, 104, 97-106.

14. Richter, E.D.; Chlamtac, N. Ames, Pesticides, and Cancer Revisited. Intl. J. Occup. Environ. Health 2002, 8, 63-72.

15. Liou, H.H.; Tsai, M.C.; Chen, C.J.; Jeng, J.S.; Chang, S.C.; Chen, S.Y.; Chen, R.C. Environmental Risk Factors and Parkinson’s Disease: a Case-Control Study in Taiwan; Neurology 1997, 48, 1583- 1588.

16. Kanthasamy, A.G.; Kitazawa, M.; Kanthasamy, A.; Anantharam, V. Dieldrin-Induced Neurotoxicity: Relevance to Parkinson’s Disease Pathogenesis. Neurotoxicology 2005, 26, 701-719.

17. Garry, V.F.; Harkins, M.E.; Erickson, L.L.; Long-Simpson, L.K.; Holland, S.E.; Burroughs, B.L. Birth Defects, Season of Conception, and Sex of Children Born to Pesticide Applicators Living in the Red River Valley of Minnesota, USA; Environ. Health Perspect. 2002, 110, 441- 449.

18. Kelce, W.R.; Stone, C.R.; Laws, S.C.; Gray, L.E.; Kemppainen, J.A.; Wilson, E.M. Persistent DDT Metabolite p, p -DDE is a Potent Androgen Receptor Antagonist; Nature 1995, 375, 581-582.

19. Aktacs-C imen, Z. The Marketing Problems of Undercover Producers in Kumluca District of Antalya; J. Akdeniz Univ. Facul. Econ. Admin. Sci. 2001, 1, 1-14 (in Turkish).

20. Gullu, G.; Dog cents?an, G.; Tuncel, G. Atmospheric Trace Element and Major Ion Concentrations over the Eastern Mediterranean Sea: Identification of Anthropogenic Source Regions; Atmos. Environ. 2005, 39, 6376-6387.

21. Karakacs, D.; Tuncel, S.G. Optimization and Field Application of a Filter Pack System for the Simultaneous Sampling of Atmospheric HNO^sub 3^, NH^sub 3^ and SO^sub 2^; Atmos. Environ. 1997, 31, 1657- 1666.

22. Seinfeld, J.H.; Pardis, S.N. Atmospheric Chemistry and Physics: from Air Pollution to Climate Change; Wiley: New York, 1998.

23. Prospero, J.M.; Barret, K.; Church, T.; Dentener, F.; Duce, R.A.; Galloway, J.N.; Levy, H.; Moody, J.; Quinn, P. Atmospheric Deposition of Nutrients to the North Atlantic Basin; Biogeochem. 1996, 35, 27-73.

24. O zkan, B.; Akcaoz, H.V.; Karadeniz, F. An Economic Analysis of Pesticide and Fertiliser Application in Citrus Production in Turkey; J. Agri. Res. Tanta Univ. Special Issue 2002, 28, 1008- 1019.

25. Erduran, S.M.; M.Sci. Dissertation, Middle East Technical University, September 1997.

26. Barlas, N.E. Determination of Organochlorine Pesticide Residues in Water and Sediment Samples in Inner Anatolia in Turkey; Bull. Environ. Contam. Toxicol. 2002, 69, 236-242.

27. Gunay, G. In Coastal Aquifers Intrusion Technology: Mediterranean Countries; Lopez-Geta, J.A., Gomez, J.D., Orden, J.A., Ramos, G., Rodriguez, L., Eds.; Instituto Geologico y Minero de Espana: Madrid, 2003; 265- 277.

28. Van der Hoff, R.; van Zoonen, P. Trace Analysis by Gas Chromatography; J. Chrom. A 1999, 843, 301-322.

29. Senseman, S.; Lavy, T.L.; Mattice, J.D.; Gbur, E.E.; Skulman, B.W. Trace Level Pesticide Detections in Arkansas Surface Waters; Environ. Sci. Technol. 1997, 31, 395-401.

Semra G. Tuncel, Nur Banu Oztas, and M. Soner Erduran

Department of Chemistry, Middle East Technical University, Ankara, Turkey

About the Authors

Semra G. Tuncel is a full professor at the Department of Chemistry at Middle East Technical University. Nur Banu Oztas is a scientist at the Turkish Atomic Energy Agency, Saraykoy Nuclear Research and Training Center in Ankara, Turkey. M. Soner Erduran is a former graduate student of Prof. Tuncel and is currently a research assistant in the Department of Chemistry and Biochemistry at the University of Maryland in College Park, MD. Please address correspondence to: Semra G. Tuncel, Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey; phone: +90-312-210- 3195; fax: +90-312-2103200; e-mail: semratun@metu.edu.tr.

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