Investigation of Dicofol and Endosulfan Pesticide Levels In Tahtalı Dam Water or Drinking Water MASTER OF SCIENCE - PDF

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Investigation of Dicofol and Endosulfan Pesticide Levels In Tahtalı Dam Water or Drinking Water By Yeliz SAZOVA A Dissertation Submitted to the Graduate School in Partial Fulfillment of the Requirements

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Investigation of Dicofol and Endosulfan Pesticide Levels In Tahtalı Dam Water or Drinking Water By Yeliz SAZOVA A Dissertation Submitted to the Graduate School in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE Department: Chemistry Major: Chemistry Izmir Institute of Technology Izmir, Turkey October, 2004 We approve the thesis of Yeliz SAZOVA Date of Signature Prof. Dr. Tamerkan ÖZGEN Thesis Adviser Department of Chemistry Prof. Dr. Nafiz DELEN Ege University, Faculty of Agriculture Department of Plant Protection Assoc. Prof. Dr. Ahmet E. EROLU Head of Department of Chemistry Assoc. Prof. Dr. Ahmet E. EROLU Head of Department of Chemistry ii ACKNOWLEDGEMENTS I would like to thank to Prof. Dr. Tamerkan ÖZGEN for his supervision, help, support and encouragement he provided throughout my thesis. I also would like to thank to other members of the thesis committee, Prof. Dr. Nafiz DELEN, Assoc. Prof. Dr. Ahmet E. EROLU, Asst. Prof. Dr. Durmu ÖZDEMR, and Asst. Prof. Dr. Aysun ÇAKAN SOFUOLU for their valuable comments and suggestions. I am very grateful to Asst. Prof. Dr. Ritchie EANES and Rcsh. Asst. Murat Erdoan for their special help and support. Special thanks go to all research assistants for their friendship and their helps during this thesis. Finally, I am thankful to my family for their help, and support. iii ABSTRACT In this study, dicofol (2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol) and endosulfan (6,7,8,10,10 - hexachloro - 1,5,5,1,6,9,9a - hexahydro - 6,9 - methano - 2,4,3 benzadioxathiepin 3-oxide) pesticide concentration levels in Tahtalı Dam Water were investigated. Endosulfan pesticide has two forms which are -Endosulfan and -Endosulfan. Dicofol and Endosulfan are both organochlorine pesticides. Both of these pesticides are widely used for agricultural purposes in Tahtalı Dam Basin. These pesticides could be carried to the Tahtalı Dam Water, and therefore their concentrations should be controlled. Another reason why these pesticides were selected was that their method of determination is not straightforward and a special determination technique has to be used. That is why these pesticides were not studied extensively for zmir area. For the determination of trace amount of above-mentioned pesticides, gas chromatography-mass spectrometry (GC-MS) was generally preferred as reported in most papers [1-3]. The GC-MS instrument in our laboratory has an Ion Trap (IT) mass analyzer. Operating in Selected Ion Storage (SIS) or Tandem mass (MS-MS) modes can increase the sensitivity and selectivity of this instrument. The matrix effect coming from the aqueous solution was eliminated by GC-SIS-MS and GC-MS-MS. Dicofol did not give stable peaks. So, Dicofol did not investigate in this study. The detection limits of the instrument are g/l for -Endosulfan, and g/l for -Endosulfan; therefore a preconcentration process was required because the studied concentrations are in 1-3 g/l levels for surface water and 0.1 g/l levels for drinking water. Solid Phase Extraction (SPE) method was used for sample preconcentration. Gas chromatography (GC) - Mass spectrometry (MS) and Tandem mass spectrometry (MS MS) were employed for the identification and quantification of Dicofol, -Endosulfan, and -Endosulfan pesticides. For SPE procedure ENVI-18 Disk was used, optimizing the extraction volume, ph and the salt concentration. In GC MS MS, the lowest detectable concentrations for the -Endosulfan and -Endosulfan were found as ng/l and ng/l, respectively. Recovery of -Endosulfan for SPE was 112 (±0.002) % in 500 ml water samples spiked with 1 mg/l pesticides. Recovery of the - Endosulfan for SPE was 132 (±0.008) % in 500 ml water samples spiked with 1 mg/l pesticides. iv Water samples, which were collected between 01 August 2002 and 01 January 2003 by ZSU (zmir Büyükehir Belediyesi Su ve Kanalizasyon Genel Müdürlüü), were analyzed using GC-MS system with tandem mass (MS-MS) mode after preconcentration process. Both -Endosulfan and -Endosulfan were not found in detectable amounts in Tahtalı Dam Water although an enrichment technique -SPE- was used. v ÖZ Bu çalımada, Tahtalı Baraj suyunda, dicofol (2,2,2-trikloro-1,1-bis(4- klorofenil) ethanol) ve endosulfan (6,7,8,10,10-hegzakloro-1,5,5,1,6,9,9a-hegzahidro- 6,9-methano-2,4,3-benzadiokzatiepin 3-oksit) pestisitlerinin deriim seviyeleri incelenmitir. Endosulfan, -Endosulfan ve -Endosulfan olmak üzere iki forma sahiptir. Hem Dicofol hem de Endosulfan organoklorlu pestisitlerdir. Bu pestisitlerin her ikisi de Tahtalı Baraj Havzasında yaygın olarak tarımsal amaçlarla kullanılmaktadır ve Tahtalı Baraj suyuna çeitli yollarla taınabilir. Bu yüzden deriimleri kontrol edilmelidir. Bu pestisitlerin seçilmesinin dier bir nedeni de, bunların eser miktarda dorudan tayin yöntemlerinin olmaması ve özel tayin teknikleri gerektirmesidir. Bu nedenle söz konusu pestisitleri saptama çalımaları zmir bölgesinde yaygın olarak yapılmamıtır. Çou makalede de bildirildii gibi, yukarıda bahsedilen pestisitlerin tayininde Gaz Kromatografi - Kütle Spektrometrisi (GC-MS) cihazları genellikle tercih edilmektedir [1-3]. Laboratuvarımızdaki GC-MS cihazı yon Kapanlı (IT) kütle analizörüne sahiptir. Bu cihazın hassasiyeti ve seçicilii, Seçilmi yon Saklama (SIS) ve Tandem-Kütle (MS-MS) modlarında çalıılarak artırılabilir. Yine sulu çözeltilerden gelen matriks etkisi GC-SIS-MS ve GC-MS-MS modlarında çalıılarak giderilebilir. Cihazın saptama sınırı -Endosulfan için g/l ve -Endosulfan için de g/l dir. Yüzey suyunda çalıma seviyesi 1-3 g/l ve içme suyunda 0.1 g/l olduu için hala bir ön deritirme basamaına ihtiyaç duyulmutur. Örneklerin ön deritirilmesi amacıyla Katı Faz Özütleme (SPE) metodu kullanılmıtır. Dicofol, -Endosulfan ve -Endosulfan pestisitlerinin tanımlanması ve miktarlarının belirlenmesi için GC-MS ve MS-MS yöntemleri kullanılmıtır. ENVI-18 Disk kullanılarak yapılan SPE ilemi için hacim, ph ve tuz deriimi optimize edilmitir. GC-MS-MS ile -Endosulfan ve -Endosulfan için en düük saptama sınırı sırasıyla ng/l ve ng/l bulunmutur. 500 ml su örneklerine eklenen 1 mg/l deriimindeki pestisitlerin SPE kullanılarak yapılan -Endosulfana ait geri kazanım sonucu %112 (±0.002) dir. Aynı ekilde SPE kullanılarak yapılan -Endosulfana ait geri kazanım sonucu %132 (±0.008) dir. vi ZSU (zmir Büyükehir Belediyesi Su ve Kanalizasyon Genel Müdürlüü) tarafından 01 Austos 2002 ile 01 Ocak 2003 tarihleri arasında toplanan su örneklerinin ön deritirme ileminden sonra GC-MS sisteminde MS-MS modu ile analizleri yapıldı. Ön deritirme ilemi -SPE- yapılmı olmasına ramen, Tahtalı Baraj suyunda, cihazın saptama sınırında ne -Endosulfan ne de -Endosulfan bulunamamıtır. vii TABLE OF CONTENTS LIST OF FIGURES... xi LIST OF TABLES... xiv Chapter 1 INTRODUCTION Thesis Objective... 3 Chapter 2 PESTICIDES AND PROPERTIES Pesticides Concerns Historical Development of Pesticides Classification of Pesticides According to Chemical Structure According to use Usage Purposes and Areas of Pesticides General Properties of Pesticides Degradation of Pesticides Toxicity of Pesticides Introduction Routes of Pesticides into Water Chapter 3 DICOFOL AND ENDOSULFAN AND THEIR PROPERTIES Dicofol General Properties of Dicofol Physical Properties Uses of Dicofol Toxicological Effects Ecological Effects Environmental Fate Endosulfan General Properties of Endosulfan Physical Properties viii Uses of Endosulfan Toxicological Effects Ecological Effects Environmental Fate Chapter 4 GAS CHROMATOGRAPHY (GC), MASS SPECTROMETRY (MS), AND THEIR COMBINATION Introduction Gas Chromatography Mass Spectrometry Ion Trap Combined Gas Chromatography and Mass Spectrometry Chapter 5 MATERIALS AND METHOD Chemicals and Reagents Calibration Set GC-MS Analysis Sampling Analysis of Water Samples Using Solid Phase Extraction (SPE) Preconcentration Method Chapter 6 RESULTS AND DISCUSSION Comparison of Solvents Comparison of Column Temperature Programs Comparison of Injector Temperature Programs Comparison of GC-MS Modes GC-MS Mode GC-MS (SIS) Mode GC-MS-MS Mode Calibration Results Solid Phase Extraction (SPE) Real Sample Analysis Chapter 7 CONCLUSION ix REFERENCES APPENDIX A - SATURN GC/MS WORKSTATION METHOD LISTING...AA1 A GC Method Report...AA1 A.2. MS Method Report...AA2 APPENDIX B - GC/MS MASS SPECTRA LIBRARY...AB1 APPENDIX C - GENERAL INFORMATION ABOUT TAHTALI DAM...AC1 x LIST OF FIGURES Figure 2.1 Molecular Structure of DDT... 4 Figure 3.1 Molecular Structure of Dicofol Figure 3.2 Molecular Structure of Endosulfan Figure 4.1 Schematic of a Gas Chromatograph Figure 4.2 Components of a Mass Spectrometer Figure 4.3 A Time-of-flight Mass Spectrometer Figure 4.4 A Magnetic Mass Spectrometer Figure 4.5 A Quadrupole Mass Spectrometer Figure 4.6 Ion Trap Mass Spectrometer Figure 4.7 A Schematic Diagram of an Ion Trap Mass Spectrometer Figure 6.1 Figure 6.2 Figure 6.3 GC-MS Chromatogram of 1.0 mg/l Standard Pesticide Mixture Solution GC-MS Chromatogram of 1.0 mg/l Standard Pesticide Mixture Solution GC-MS Chromatogram of 5.0 mg/l Standard Dicofol Solution Figure 6.4 GC-MS Chromatogram of 5.0 mg/l Standard Endosulfan Solution Figure 6.5 Figure 6.6 GC-MS Chromatogram of 5.0 mg/l Standard Pesticide Mixture Solution GC-MS Chromatogram of 10.0 mg/l Standard Pesticide Mixture Solution xi Figure 6.7 Figure 6.8 Figure 6.9 GC-MS Chromatogram of 10.0 mg/l Standard Pesticide Mixture Solution GC-MS Chromatogram of 10.0 mg/l Standard Pesticide Mixture Solution Total Ion GC-MS Chromatogram of 10.0 mg/l Standard Endosulfan Pesticide Solution Figure 6.10 Mass Spectrum of -Endosulfan Figure 6.11 Mass Spectrum of -Endosulfan Figure 6.12 Figure 6.13 Figure 6.14 Figure 6.15 Figure 6.16 Figure 6.17 GC-MS (SIS Mode) Chromatogram of 10.0 mg/l Standard Endosulfan Pesticide Solution GC-MS-MS Chromatogram of 10.0 mg/l Standard Endosulfan Pesticide Solution Chromatogram obtained with GC-MS-MS mode 0.03 mg/l of Endosulfan Pesticides Standard Solution Chromatogram obtained with GC-MS-MS mode 10.0 mg/l of Endosulfan Pesticides Standard Solution Calibration Plot for -Endosulfan for Concentration Range of 0.03 mg/l mg/l Calibration Plot for -Endosulfan for Concentration Range of 0.03 mg/l 10.0 mg/l Figure 6.18 Effect of ph on The Recovery of Endosulfan Pesticide Figure 6.19 Figure 6.20 Effect of Salt Addition on the Recovery of Target Pesticides Effect of Sample Volume on the Recovery of Endosulfan Pesticide xii Figure 6.21 Figure B.1. Figure B.2. Figure B.3. Figure B.4. Figure C.1. Chromatogram A obtained with GC-MS-MS mode 0.05 mg/l of standard pesticide solution, Chromatogram B obtained with GC-MS-MS mode after SPE steps of 500 ml of water sample Mass Spectrum of Endosulfan (from NIST Pesticides Library)...AB1 Mass Spectrum of Endosulfan...AB2 Mass Spectrum of Dicofol (from NIST Pesticides Library)...AB3 Mass Spectrum of Dicofol...AB4 General View of Tahtalı Dam...AC1 xiii LIST OF TABLES Table 2.1 Solubility of Some Pesticides Table 2.2 Relative Persistence of Some Pesticides in Natural Waters Table 2.3 The Half-Life of Some Pesticides in the Environment Table 2.4 Oral Acute Toxicity Classes of Pesticides for Mammals Table 2.5 Toxicity Classes of Pesticides for Fish Table 4.1 Performance Characteristics of Common GC Detectors Table 6.1 Column Temperature Programs Table 6.2 Injector Temperature Programs Table 6.1 MS-MS Parameters Table 6.2 Table 6.3 Table 6.4 Table 6.5 Retention Time Windows (RTWs) and Calibration Data of GC-MS-MS Methods Effect of ph on Recoveries in the Solid Phase Extraction Process Effect of Salt (NaCl) on Recoveries in the Solid Phase Extraction Process Recoveries of Solid Phase Extraction of Pesticides at Different Sample Volumes xiv CHAPTER 1 INTRODUCTION Today, over 500 compounds are registered worldwide as pesticides or metabolites of pesticides [4]. Pesticides can be classified based on functional groups in their molecular structure (e.g. inorganic, organonitrogen, organohalogen, organophosphorus, organosulfur compounds, etc.), or their specific biological activity on target species (e.g. insecticides, fungicides, herbicides, acaricides, etc.) [4,5]. Herbicides are by far the most commonly used pesticides followed by insecticides, fungicides, and others. Pesticide use in agriculture has progressively increased after World War II, leading to increased world food production. Nevertheless, this use and additional environmental pollution due to industrial emission during their production have resulted in the occurrence of residues of these chemicals and their metabolites in food, water, and soil. Legislations were acted out in the USA, European Union (EU) and other countries to regulate pesticides in water, water supply, soil, and food. The development and use of pesticides have played an important role in the increase of agricultural productivity. The majority of such substances are applied directly to soil or sprayed over crop fields and hence are released directly to the environment. Consequently, pesticides can enter as contaminants into natural waters either directly in applications or indirectly from drainage of agricultural lands. The amount and kind of pesticides in water of a given area depends largely on the intensity of production and kind of crops. However, transport of pesticides out of their area of application results in the presence and accumulation of these compounds in many parts of the hydrosphere. For example, atmospheric precipitation is an important route of transport of pesticides, resulting in contamination of environmental waters far away from agricultural areas. Substantial amounts of pesticides have been found in ice and water of polar regions [6,7], lakes [8], seawater [9], rainwater [8,10-12] or potable water [13,14]. Gas chromatography (GC) using the highly sensitive electron-capture detection (ECD) is an analytical technique of great importance especially in the determination of chlorinated hydrocarbon pesticide residues in environmental waters [12,15-17]. This is due not only to the sensitivity and specificity of ECD, but also to the power of GC for separating compounds of similar molecular structure. Consequently, multiresidue analysis is the most common way of determining pesticides. Once the chromatographic separation is reached, information regarding the complexity (number of components), quantity (peak height or area) and identity (retention time) of the components in a mixture is provided. The certainty of identification based solely on retention time value is poor, even for not very complex samples, therefore a supplementary confirmation of the residues is necessary. Only when the identity is firmly established, the quantitative information from the chromatogram can be correctly interpreted without producing false (positive) results. Spectroscopic techniques, conversely to chromatographic techniques, present a rich source of qualitative information from which component identity may be deduced with a reasonable degree of certainty. Thus, spectroscopic and chromatographic techniques provide complementary information about the concentration of the components and their identity in a sample. Nowadays, GC interfaced to mass spectrometry (GC-MS) is the preferred analytical technique for the confirmation of trace compounds [1]. Generally, three modes of GC MS operation are available for pesticide analysis: electron impact (EI), positive chemical ionization (PCI) and negative chemical ionization (NCI). GC-MS in the EI mode is commonly used in the determination of pesticides in water. Positive and negative chemical ionization modes are alternative methods, depending on the compounds they offer better selectivity and/or sensitivity than EI. For increasing the sensitivity, selected ion monitoring (SIM) is commonly used in the determination of pesticides in waters. This mode allows the analysis of trace amounts of pesticides but reduces the qualitative information. The use of tandem mass spectrometry (MS MS) improves the selectivity of the technique with a drastic reduction of the background without losing identification capability. It enables analysis of pesticides at trace levels in the presence of many interfering compounds [18,19]. In spite of high sensitivity and selectivity of the technique a reduced number of reasearchers have applied this technique [20,21]. Evidently, the sensitivity is still not high enough to directly determine the trace amounts of pesticides in drinking and surface water samples at the level required by the European Community (EC). European Union (EU) Waters Directives are 0.1 g/l for each pesticide, 0.5 g/l for total amount in drinking water and 1-3 g/l for surface water [22,23]. 2 Due to these low presence levels, a preconcentration procedure for the analytes must be applied. Preconcentration of contaminants from water samples, and generally sample preparation steps, often require by extraction techniques, based on enrichment on liquid (liquid liquid extraction) or solid (solid liquid extraction) phases [24,25]. Extraction procedures, optimized prior to chromatographic separation, can be coupled on- or off-line to the analysis, which is mainly performed, by liquid chromatographic (LC), gas chromatographic (GC) or gas chromatography - mass spectrometric (GC-MS) methods [24-27] Thesis Objective In this study, investigation of Dicofol and Endosulfan pesticide levels in Tahtalı Dam Water, which is the most important drinking water supply in zmir, were carried out. Study of the variation of Dicofol and Endosulfan amounts in Tahtalı Dam Water for a reasonable period was planned. Mainly twenty pesticides are used for agricultural purposes in Tahtalı Dam Basin. Due to consumption of target pesticides in greater amounts compared to the others, the determination of Dicofol and Endosulfan pesticides and the examination of their levels in the Tahtalı Dam Water was studied. According to European Community (EC) directives the tolerance levels of pesticides in drinking water are 0.1 g/l for one pesticide and 0.5 g/l for total pesticide concentrations. Therefore, sensitive analytical instruments and methods are required for the determination of these amounts. For this purpose, Gas chromatography Mass Spectroscopy (GC-MS) techniques are generally preferred as reported in most papers. The GC-MS instrument in our laboratory has an Ion Trap (IT) mass detector. Working in Selected Ion Storage (SIS) and Tandem (MS-MS) modes could increase the sensitivity and selectivity of this instrument. Nevertheless, a preconcentration process is still required. In this study Solid-Phase Extraction (SPE) methods was used for sample preconcentration process. 3 CHAPTER 2 PESTICIDES AND THEIR PROPERTIES 2.1 Pesticides The name is derived from the Latin words pestis (pestilence, plague) and caedere-to kill. The word pesticide includes all chemicals that are used to kill or control pests. They include herbicides (kills weeds), insecticides (kills insects), fungicides (kills fungi), nematocides (kills nematodes), and rodenticides (kills small mammals). Pesticides are most heavily used in agriculture but they are also heavily used in household as well as silvicultural applications. The first mention of pesticides was made in 1763, when an extracted solution of tobacco was used to control the plant louse. Later, some other uses of pesticides were reported; for example, in 1865, in controlling the Colorado beetle by use of Paris green (copper-aceto-arsenite). However, the discovery of the insecticidal properties of DDT (4,4-dichlorodiphenyl trichloroethane) started the era of pesticide usage on a large scale. DDT (as shown in Figure 2.1.) was first synthesized by Zeidler in 1874, but Müller, who was looking for a mothproofing agent, did not observe its insecticidal properties until Cl H C CCl 3 Cl Figure 2.1 Molecular St
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