Şeyda KIVRAK, Tolga GÖKTÜRK

Çevresel Su Örneklerinde GC/MSD ile Pestisit Analizi ve Metot Validasyonu

Bu çalışmada, su numunelerinde 130'dan fazla pestisit kalıntısının ppb (μg/L) düzeyinde belirlenmesinde kullanılabilecek hızlı ve çoklu bir analiz yöntemi önerilmiştir. Bu amaçla, analit konsantrasyonunun zenginleştirilmesi için bir Kuderna-Danish Evaporatif Konsantratör ve SIM (Selective Ion Monitoring) modunda çalışan gaz kromotografisi (GC) ile birleştirilmiş kütle spektrometresinin (MSD) kullanıldığı bir yöntem geliştirildi ve çoklu pestisit analizi için validasyonu yapıldı. Kromatografik analizde, pestisitlerin düşük konsantrasyonlarda dahi yüksek hassasiyetle tespit edilebilmesi gerektiğinden dolayı 30m HP-5 MS UI kapiler GC kolonu kullanıldı. Geliştirilen yöntemle miktar tayin limitleri 1.8 ve 29.2 ng.L-1 olarak belirlendi. Yöntem, bileşiklerin çoğunda sırasıyla 10 ppb ve 50 ppb seviyeleri için 70.1-116.5 % ve 70.7 – 114.0% aralıklarında ortalama geri kazanım sağladı. Pestisitlerin birbirinden çok farklı kimyasal yapıları, analizi yapılan tüm bileşikler için iyi bir geri kazanım sağlamayı zorlaştırmış olmasına rağmen sonuçların hassasiyetinin mükemmel olduğu değerlendirilebilir. Metodun seçiciliği, hesaplama ve tanımlama iyonlarının bağıl oranı yoluyla değerlendirildi ve değerlendirme sonucunda yeterli kabul edildi. Gerçek numunelerdeki analizler, enstrümantal yeterlilik kriterlerini ve sistem uygunluğu değerlendirmesini karşılamıştır. Böylelikle, 130 pestisitin nitel ve nicel tayinleri yapılmıştır.

Anahtar Kelimeler:

Pestisit, Su, Aldrin, Validasyon, GC/MSD

Pesticide Analysis and Method Validation with GC/MSD Instrument in Environmental Water Samples

In this study, a rapid and multiple method has been proposed which can be used in determination of more than 130 pesticide residues at ppb (μg/L) level in water samples. For this purpose, a Kuderna-Danish Evaporative Concentrator, which was used for enrichment of the analyte concentration in the samples and gas chromatography coupled mass spectrometry in the selective ion monitoring (SIM) mode was developed and validated for the multi-class determination of pesticides. In the analysis, a 30m HP-5 MS UI capillary GC columns was used. The high sensitivity of chromatographic analysis was necessary, due to that these pesticides must be determined at low concentrations. The method presented quantification limits between 1.8 and 29.2 ng.L-1. Most of the compounds presented mean recoveries between 70.1-116.5 % and 70.7 – 114.0% at 10 ppb and 50 ppb levels, respectively. Although the difference in chemical natures of the pesticides made difficult to attain good recovery for all of the compounds evaluated, the precision of the results was excellent. The selectivity of the method was evaluated through the relative intensity of quantification and qualification ions and was considered adequate. Analysis in real samples met criteria for instrumental qualification and the system suitability evaluation. Thus, qualitative and quantitative determinations of 130 pesticide were done.

Keywords:

Pesticide, Water, Aldrin, Validation, GC/MSD,

PDF

___

[1] Matthews G. A., “Pesticides: Health, Safety and the Environment” Blackwell Publishing, 248s, Oxford, 2008
[2] Laabs V., Amelung W., Pinto A. A., Wantzen M., da Silva C. J., Zech W., “Pesticides in Surface Water, Sediment, and Rainfall of the Northeastern Pantanal Basin” Brazil. Journal of Environmental Quality, 31, 1636-1648, 2002
[3] Arslan H., “Investigation of the Usability of Andesite and Basalt Tubes for Dichlorvos (DDVP) Removal” Mersin University, Graduate School of Natural and Applied Sciences, MSc Thesis, 76s, Mersin, Turkey, 2000
[4] Schwarzenbach R. P., Egli T., Hofstetter T. B., von Gunten U., Wehrli B., “Global Water Pollution and Human Health” The Annual Review of Environment and Resources, 35, 109-136, 2010
[5] Aktar W., Sengupta D., Chowdhury A., “ Impact of Pesticide Use in Agriculture: Their Benefits and Hazards” Interdiciplinary Toxicology, 2, 1-12, 2009
[6] Matsumara F., “Toxicology of Insecticides 2nd Ed.” Plenum Press, 598s, New York, 1985
[7] Rand G. M., Petroçelli S. R., “Fundamentals of Aquatic Toxicology: Methods and Applications” Hemisphere Publishing Cooperation, 666s, Washington, 1985
[8] Chau A. S. Y., Afghan B. K., “Analysis of Pesticides in Water” CRC Press Inc., 202s, Florida, 1982
[9] Guthrie F. E., Perry J. J., “Introduction to Environmental Technology” Elsevier North Holland, 484s, New York, 1980
[10] Beck H., Dross A., Mathar W., “PCDDs, PCDFs and related compounds in the German food supply” Chemosphere, 25, 1539-1550, 1992
[11] Schaum J., Cleverly D., Lober M., Phillips L., Schweer G., “Updated analysis of U.S. sources of dioxin-like compounds and background exposure levels” Organohalogen Compounds, 20, 237–243, 1994
[12] Egemen Ö., Sunlu U., “Su Kalitesi Ders Kitabı” Ege Üniversitesi Basımevi, 153s, Bornova, 1996
[13] Dakeba R. W., McKenzie A. D., G. M. A. Lacroix, Cleroux C., Bowe S., Graham R. A., Conacher H. B. S., Verdier P., “Survey of arsenic in total diet food composites and estimation of the dietary intake of arsenic by Canadian adults and children” Journal of the AOAC International, 76, 14–25, 1993
[14] Bizuik M., Przyjazny A., Czerwinski J., Wiergovski M., “Occurence and Determination of Pesticides in Natural and Treated Waters” Journal of Chromotography A, 754, 103-123, 1996
[15] Guidance document on residue analytical methods, European Union, SANCO (825), 1999
[16] Aboul-Enein H. Y. “Selectivity versus specificity in chromatographic analytical methods” Accreditation and Quality Assurance, 5, 180-181, 2000
[17] Accreditation for chemical laboratories: Guidance on the interpretation of the EN 45000 series of standards and ISO Guide 25, Eurachem/Welec WGD2. Laboratory of the Government Chemist, Teddington, 1993
[18] Accuracy (trueness and precision) of measurement methods and results Part 1: General principles and definitions, TS 5822-1 ISO 5725-1, Turkish Standards Institution, 2000
[19] EEC Drinking Water Guidelines, 91/692/EEC, COM 789 Final 2016/0394 (COD), 2016
[20] Miller J. C., Miller J. N., “Statistical in Analytical Chemistry (3rd ed.)” Ellis Horwood PTR Prentice Hall, 233s, NewYork, 1993
[21] Portion of commodities to which codex maximum residue limits apply and which is analyzed, Codex Alimentarius Commiteee, Rome, 1993
[22] Maximum residue levels of pesticides in or on food and feed of plant and animal origin, Council Directive (EC/ 396), 2005
[23] Maximum residue level of pesticides in or on food and feed of plant and animal origin, as regards the implementing powers conferred on the commission, Council Directive (EC/299), 2008
[24] OECD 617, Guidance Document on Pesticide Residue Analytical Methods, Environment, Health and Safety Publications, 2007
[25] CITAC/EURACHEM Guide; The Fitness for Purpose of Analytical Methods. A Laboratory Guide to Method Validation and Related Topics, LGC UK: Middlesex, UK, s43, 1998