Nektarin ve Şeftali Örneklerinde Bazı Pestisit Kalıntılarının Belirlenmesi İçin Etkin Bir Yöntemin Doğrulanması

Metot doğrulama, yöntemin belirli bir amaca uygunluğunu doğrulayan bir iç kalite kontrol prosedürüdür. Gerçek örneklerin analizinden önce tüm analiz metotları doğrulanmalıdır. Metot doğrulamasını gerçekleştirmek için LOQ, doğrusal aralık, kesinlik, doğruluk ve geri kazanım gibi kriterler dikkate alınmalıdır. Bu çalışma nektarin ve şeftalide boscalid, chlorpyrifos ve tebuconazole analizi için QuEChERS analiz prosedürünü doğrulamak amacıyla yapılmıştır. Nektarin ve şeftali örnekleri 3 farklı seviyede 3 pestisitle spike edilmiştir. Ekstraksiyon ve clean-up basamakları için QuEChERS yöntemi uygulanmuştır. Kromatografik ayrıştırma LC-MS/MS ile yapılmıştır. Matris etkisini elimine etmek için matrisli kalibrasyon (MC) kullanılmıştır. QuEChERS metodu-LC-MS/MS analiz sistemi, pestisitlerin LOQ'larının MRL'nin altında olduğunu göstermiştir. Chlorpyrifos, tebuconazole ve boscalid pestisitlerinin nektarin örneklerinden geri alımları, sırasıyla %108.1, %109.9, ve %124.5 olarak bulunmuştur. Bu değerler şeftali örnekleri için sırasıyla, %108.4, %109.9 ve %122.3 şeklinde olmuştur. Yöntemin tüm geri alımı nektarin için %113.6, şeftali %113.5 olmuştur. Bu değerler SANTE geri kazanım limitleri (%60–140) ile uyumludur. MC eğrileri 3 pestisit için de doğrusal (R2 ≤0.999) olarak bulunmuştur. Geri alım, kesinlik, doğruluk ve doğrusallık gibi bazı diğer yöntem doğrulama kriterleri gerekli aralıklarda bulunmuştur. Nektarin ve şeftali örneklerinde, chlorpyrifos, tebuconazole and boscalid kalıntılarının analizleri için QuEChERS yöntemi uygun bulunmuştur.

Anahtar Kelimeler:

Şeftali, Nektarin, Pestisit Kalıntısı, Metot Doğrulama, QuEChERS

Verification of An Efficient Method for the Determination of Some Pesticide Residues in Nectarine and Peach

Method verification is an internal quality control procedure verifying the suitability of the method for specific purposes. All methods should be verified prior to analyses of real samples. LOQ, range of linearity, precision, accuracy and recovery criteria have to be taken into consideration while performing the method verification. This study was conducted to verify QuEChERS procedure for the analysis of boscalid, chlorpyrifos and tebuconazole in nectarine and peach. Samples spiked at 3 levels of 3 different pesticides. LC-MS/MS was used for chromatographic separation. Matrix calibration (MC) was used to compensate the matrix effect. QuEChERS method revealed that all pesticide LOQs were less than MRL. Recovered boscalid, chlorpyrifos and tebuconazole from matrices were recorded as 123.73% (RSD= 8.89%; n=52), 108.37% (RSD= 14.95%; n=52) and 110.34% (RSD= 15.22%; n=52), respectively. Overall recovery of the QuEChERS-AOAC 2007.01 method was 113.96 %, with RSD value of 14.52 % (n=156; SD=16.55). All recovery ranges were noted as 66.42-139.68%. These values were fit the SANTE recovery ranges (60–140%). MC curves 3 pesticides were linear (R2 ≤0.999). Some other verification criteria, such as accuracy, linearity, precision and recovery were within the specified limits. According to the results of this study, the QuEChERS method is suitable for the analyses of chlorpyrifos, tebuconazole and boscalid in case of nectarine and peachs.

Keywords:

: Peach, Nectarine, Pesticide Residues, Method Verification, QuEChERS,

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Anastassiades, M., Lehotay, S.J., Stajnbaher, D., Schenck, F.J., 2003. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solid-phase extraction for the determination of pesticide residues in produce. J. AOAC Int. 86: 412–431.
Anonymous, 1999. Guidelines for Single-laboratory Validation of Analytical Methods for Trace-level Concentrations of Organic Chemicals AOAC/FAO/IAEA/IUPAC Expert Consultation Meeting, Miskolc, Hungary, 8-11 November, 1999. http://www.iaea.org/trc/ pest-qa_val_ guide.pdf
Brankovic, M., Andelkovic, D., Kocic, H., Kocic, G., 2019. Assessment of GC–MS Response of Selected Pesticides in Apple Matrices Related to Matrix Concentration. J. Environ. Sci. Health B 54: 376–386.
CAC, 2003. Representative Commodities/Samples for Validation of Analytical Procedures for Pesticide Residues. In Codex Alimentarius Commission Guidelines on Good Laboratory Practice in Pesticide Residue Analysis. CAC/GL 40-1993.
Çatak, H., Tiryaki, O., 2020. Insecticide residue analyses in cucumbers sampled from Çanakkale open markets. Turkish Journal Of Entomology. 44(4): 449-460.
Dashtbozorgi, Z., Ramezanib, K. M., Waqif-Husaina, S., 2013. Optimization and validation of a new pesticide residue method for cucumber and tomato using acetonitrile-based extraction-dispersive liquid–liquid microextraction followed by liquid chromatography-tandem mass spectrometry. The Royal Society of Chemistry. 5:1192-1198.
EC, 2002. Commission Directive 2002/63/EC of 11 July 2002 Establishing Community Methods of Sampling for the Official Control of Pesticide Residues in and on Products of Plant and Animal Origin and Repealing. Directive 79/700/EEC. Offi. Journal of European Commission 2002, L 187/30, 1–14.
EURACHEM, 2014. The fitness for purpose of analytical methods -a laboratory guide to method validation and related topics. Second Edition. URL: http://www.eurachem.org
EURACHEM/CITAC, 2000. Guide quantifying uncertainty in analytical measurements, 2nd edn. 2000, LGC United Kingdom, EMPA Switzerland, 1-126 http://www.citac.cc/QUAM2000-1.pdf.
Galietta, G., Egaña, E., Gemelli, F., Maeso, D., Casco, N., Conde, P., & Nuñez, S. (2011). Pesticide dissipation curves in peach, pear and tomato crops in Uruguay. Journal of Environmental Science and Health, Part B., 46, 35-40. https://doi.org/10.1080 /03601234.2010.515504
Green, M.A., 1996. A Practical guide to analytical method validation. Anal Chem. 68:305A–309A.
Kanrar, B., Mandal, S., Bhattacharyya, A., 2010. Validation and uncertainty analysis of a multiresidue method for 42 pesticides in made tea, tea infusion and spent leaves using ethyl acetate extraction and liquid chromatography–tandem mass spectrometry. Journal of Chromatography A. 1217: 1926–1933.
Krynitsky, A.J., Lehotay, S.J., 2002. Overview of analytical Technologies available to regulatory laboratories for the determination of pesticide residues. In Handbook of Residue Analytical Methods for Agrochemicals; Lee, P.W., Ed.; Wiley & Sons: Chichester, England 753–786.
Lehotay, S.J., Kok, A.D., Hiemstra, M., Bodegraven, P.V., 2005. Validation of a fast and easy method for the determination of residues from 229 pesticides in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection. J. AOAC Int. 88 (2): 595–614.
Lehotay, S. J., 2007. Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. J. AOAC Int. 90: 485–520.
Luke, M.A., Froberg, J.E., Masumoto, H.T., 1975. Extraction and cleanup of organochlorine, organophosphate, organonitrogen, and hydrocarbon pesticides in produce for determination by gas-liquid chromatography. J. Assoc. Off. Anal. Chem. 58(5): 1020–1026.
Magnusson, B., Örnemark, U. (eds.), 2014. Eurachem Guide: The Fitness for Purpose of Analytical Methods – A Laboratory Guide to Method Validation and Related Topics, (2nd ed. 2014). ISBN 978-91-87461-59-0. Available from www.eurachem.org.
Mastovska, K., Dorweiler, K., Lehotay, S., Wegscheid, J., Szpylka, K., 2010. Pesticide multiresidue analysis in cereal grains using modified QuEChERS method combined with automated direct sample introduction GC-TOFMS and UPLC-MS/MS techniques. J Agric Food Chem. 58: 10,5959-72.
Mills, P.A., Onley, J.H., Guither, R.A., 1963. Rapid method for chlorinated pesticide residues in nonfatty foods. J. Assoc. Off. Anal. Chem. 46: 186–191.
Omeroglu, P.Y., Boyacioglu, D., Ambrus, A., Karaali, A., Saner, S., 2012. An Overview on steps of pesticide residue analysis and contribution of the individual steps to the measurement uncertainty. Food Analytical Methods. 5: 1469-1480.
Pay, P., Anastassiades, M., Mack, D., Sigalova, I., Tasdelen, B., Oliva, J., 2007. A. Barba, Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection. Anal. Bioanal. Chem. 389: 1697–1714.
Polat, B., Tiryaki, O., 2019. Determination of some pesticide residues in conventional-grown and IPM-grown tomato by using QuEChERS method. Journal Of Envıronmental Scıence and Health Part B-Pestıcıdes Food Contamınants and Agrıcultural Wastes. 54(2): 112-117.
Polat, B., Tiryaki, O., 2020. Assessing washing methods for reduction of pesticide residues in Capia pepper with LC-MS/MS. Journal Of Envıronmental Scıence and Health Part B-Pestıcıdes Food Contamınants and Agrıcultural Wastes. 55(1): 1-10.
SANCO, 2004. Quality Control Procedured for Pesticide Residues Analysis. Document No SANCO/10476/2003; 5/February/2004. http://www.crl-pesticides. eu/ library/docs/ allcrl/ AqcGuidance_ Sanco_2003_10476.pdf. SANTE, 2019. URL: https://ec.europa.eu/food/sites/food/files/plant/docs/pesticides_mrl_guidelines_wrkdoc_ 2019- 12682. Pdf.
Specht, W., Tilkes, M., 1995. Gas-chromatographic determination of pesticide residues after clean-up by gel-permeation chromatography. Fresenius’ Journal of Analytical Chemistry. 301: 300–307.
Tiryaki, O., Baysoyu, D., Secer E., Aydın, G., 2008. Testing the Stability of Pesticides during Sample Processing for the Chlorpyrifos and Malathion Residue Analysis in Cucumber Including Matrix Effects. Bull. Environ. Contam. Toxicol. 80: 38–43 . Tiryaki, O., 2016. Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties. Journal Of Envıronmental Scıence and Health Part B-Pestıcıdes Food Contamınants and Agrıcultural Wastes. 51(10): 722-729.
TSI, 2021. Turkish Statistical Institute. URL: https:// biruni. tuik. gov. tr/ medas/? kn= 92& locale= tr