Pestisit kalıntı analizlerinde örnek işleme, ekstraksiyon, cleanup ve kromatografik işlemlerin ölçüm belirsizliği değerlendirmeleri

Analiz metodunun ölçüm belirsizlikleri, güvenilebilir sonuçlar elde etmek için gereklidir. Her bir belirsizlik kaynağının saptanması o laboratuvarın sonuçlarının doğruluğunu gösterir. Çoğu analiz metodunun en önemli belirsizlik kaynakları örnek işleme, ekstraksiyon ve cleanup (temizleme, arıtma) işlemidir. Örnek işleme belirsizliğinin hesaplaması, analize alınan porsiyonun tüm laboratuvar örneğini temsil edilebilirliğini de gösterir. Örnekleme sabitesi eşitliğinden (Ks=m x $CV_{sp}^ 2$), belirsizlik ($CV_{sp}$) ve porsiyon miktarı (m) bulunabilir. Belirsizlik bileşeni olan diğer analiz basamakların belirsizliklerinde “bireyselden tüme” ve “tümsel” yaklaşımları uygulanır. Yeni bir metot ise belirsizliğe katkısı olan bileşenler saptandığından, birinci yaklaşım, metodun önemli belirsizlik kaynakları biliniyorsa ikinci yaklaşım uygundur. Her iki yaklaşımda birleştirilmiş standart belirsizlikler (uc) arasında önemli bir fark yoktur. Bu makalede, güncel literatürler ve önceki çalışmalarımızın ışığı doğrultusunda, her iki yaklaşım ile belirsizlik saptama prosedürleri açıklanmıştır.

Anahtar Kelimeler:

kalibrasyon, kromatografi, zararlı öldürücü kalıntıları

Uncertaintiy assessment of sample processing, extraction, cleanup and chromatographic procedures in pesticide residue analysis

The estimation of the uncertainty associated to analytical methods is necessary in order to obtain reliable results. Estimation of each uncertainty sources allows to laboratories to establish the accuracy of results. The main uncertainty sources of the most analytical methods are sample processing, extraction and cleanup. Estimation of sample processing also shows that analytical portion represents the whole laboratory sample. The uncertainty of sample processing ($CV_{sp}$) and the amount of the analytical portion (m) can be calculated by the sampling constant equation (Ks=m x $CV_{sp}$ 2). The “bottom up” and “top-down” strategies is applied for the assessment of uncertainty components of other analytical steps, such as extraction, cleanup. If the analytical method is new, the estimation of contribution of components is imortant, “bottom up” is applied. But if the most important uncertainty sources of method is known, “top-down” strategies is more practical. Actually there is no significant differences between combined standard uncertainty (uc) values calculated with both strategies. In this article, with the basis of update references and our previous study, estimation of uncertainy prosedures are explained.

Keywords:

calibration, chromatography, pesticide residues,

PDF

___

Ambrus, A., Solymosne, E.A., Korsos, I. 1996. Estimation of sample preparation of the analysis of pesticide residues. J Environ Sci Health B, 31, 443-450.
Ambrus, A., 2004. Reliability of measurements of pesticide residues in food. Accred Qual Asur, 9, 288-304
Anonymous, 1995. Guide to the Expression of Uncertainty in Measurement, ISO, Geneva, 1995, ISBN92-67-10188-9.
Anonymous, 2000. EURACHEM/CITAC Guide Quantifying Uncertainty in Analytical Measurements, 2nd edn. http://www.measurementuncertainty.org
Anonymous, 2002a. 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.
Anonymous, 2002b. CITAC /EURACHEM Guide (2002). Guide to Quality in Analytical Chemistry. An aid to Accreditation. Edition 2002. http://www.eurachem. org/guides/CITAC%20EURACHEM%20GUIDE.pdf.
Anonymous, 2005. EN ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories, CEN Management Centre, Brussels, 2005.
Anonymous 2007. European Ccommission DG SANCO, Method validation and quality control procedures for pesticide residue analysisin food and feed, No SANCO/2007/3131/31 October 2007.
Aysal, P., Ambrus, A., Lehotay, S.J., Cannavan, A. 2007. Validation of an efficient method for the determination of pesticide residues in fruits and vegetables using ethyl acetate for extraction. J Environmental Science and Health Part B, 42, 481-490.
El-Bidaoui, M., Jarju, O.P., Maestroni, M., Phakaeiw, Y., Ambrus, A. 2000. Testing the effect of sample processing and storage on stability of residues In: Fajgelj A, Ambrus A (eds) Principles of method validation. Royal Society of Chem., Cambridge, 75-88.
Führ, F. 1991. Radiotracers in pesticide studies; Advantages and limitations. Cience e Cultura, 43,(3), 211-216.
Fussell, R.J., Addie, K.J., Reynolds, S.L., Wilson, M.F. 2002. Assessment of the stability of pesticides during cryogenic sample processing, 1.Apples. J.Agric.Food.Chem, 50, 3, 441-448.
Fussell, R.J., 2004. Pesticide residues ‘Lost and Found’-an update on sample processing techniques for fruit and vegetables. 5th European Pesticide Residues Workshop, Pesticides in Food and Drink. Book of Abstracts, 42, June 13-16, 2004; Stockholm, Sweden.
Fussell, R.J., Hetmanski, M.T., Macarthur R, Findlay D, Smith F, Ambrus A, Brodesser PJ (2007) Measurement uncertainty associated with sample processing of oranges and tomatoes for pesticide residue analysis. J. Agric. Food. Chem, 55, 1062-1070.
Hajšlová, J., Holadová, K., Kocourek, V., Poustka, J., Godula, M., Cuhra, P., Kempný, M., 1998. Matrix-induced effects: a critical point in the gas chromatographic analysis of pesticide residues. Journal of Chromatography A, 800, 283-295.
Hibbert, D. B. 2007. Systematic errors in analytical measurement results. J. Chromatogr. A, 1158, 25-32.
Hill, A., and Reynolds, S.L. 1999. Guidelines for in-house validation of analytical methods for pesticide residues in food and animal feeds. Analyst, 124, 953-958.
Hill, A., Haris, C., Warburton, A. 2000. Effects of sample processing on pesticide residues in fruit and vegetables.In:Fajgelj A, Ambrus A(eds) Principles of method validation. Royal Society of Chemistry, Cambridge, 41-48
Maestroni, B., Ghods, A., El-Bidaoui, M., Rathor, N., Jarju, O.P., Ton, T., Ambrus, A. 2000. Testing the efficiency and uncertainty of sample processing using 14C-labelled Chlorpyrifos. Part II. In Principles of method validation; Fajgelji. A.. Ambrus. A.; Eds. Royal Society of Chemistry, Cambridge, 59-74.
Maestroni, B, 2002. Preparation of Samples and Estimation of Uncertainty of Sample Processing. In Lectures/Uncertainty of sample processing. Training Workshop on Introduction to QC/QA measures in Pesticide Analytical Laboratories. TRC for Food and Pesticide Control. Seibersdorf. Vienna. Austria. June 17 - July 26.
Ömeroğlu, P.Y., Boyacıoğlu, D., Ambrus, A., and Karaali, A. 2005. Uncertainty sources in pesticide residue analysis. 4th MGPR International Symposium of Pesticides in Food and the Environment in Mediterranean Countries, September 21-24 2005, Kuşadası, Aydın, Turkey, Book of Abstracts, 43.
Powley, C.R. 2004. Extraction efficiency considerations for present and future agrochemical residue methods. 5th European Pesticide Residues Workshop (EPRW), Pesticides in Food and Drink. June 13-16 2004; Stockholm, Sweden, Book of Abstracts: 43.
Priel, M 2009 From GUM to alternative methods for measurement uncertainty evaluation, Accred Qual Assur, 14:235–241.
Shegunova, P., Bercaru, O., Olsen, B.S. 2008. Estimation of measurement uncertanty in organic analysis: two practical approaches. Accred Qual Asur 13, (1), 11-18.
Štĕpán, R., Hajšlová, J., Kocourek, V., Tichá, J. 2004. Uncertainties of gas chromatographic measurement of troublesome pesticide residues in apples employing conventional and mass spectrometric detectors. Analytica Chimica Acta, 520, 245-255.
Suszter, G., Ambrus, A., Turcu, M.S., Klaus, P.M., 2006. Estimation of efficiency of processing soil samples for pesticide residues analysis. J Environmental Science and Health Part B, 41, 531-552.
Tiryaki, O., Baysoyu, D. 2006. Estimation of sample processing uncertainty for chlorpyrifos residue in cucumber. Accred and Qual Assurance, 10, (10), 550-553.
Tiryaki, O., Baysoyu, D., Seçer, 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.of Environ. Contam. Toxicol., 80, 1, 38-43.
Tiryaki, O., Baysoyu, D.Estimation of efficiencies and uncertainties of the extraction and cleanup steps of the pesticide residue determination in cucumber using 14C-carbaryl. Accreditation and Quality Assurance(2008) Vol:13 (2):91-99 (2008).
Tiryaki, O., Seçer, E., Aydın, G., Baysoyu, D. 2009. Uncertainty measurement of sample processing of tomato by using 14Cchlorpyrifos for pesticide residue analysis Fresenıus Envıronmental Bulletın, FEB Vol.18; No. 6 (April 2009) Accepted.
Tiryaki, O. Bitki koruma ürünlerinin kalıntı analizlerinde temel laboratuvar işlemlerinin ölçüm belirsizlikleri. Anadolu Tarım Bilim. Derg., 2009, 24(2): 124-132. [Anadolu J. Agric. Sci., 2009, 24(2): 124-132].
Vanatta, L.E., and Coleman, D.E., 2007. Calibration, uncertainty, and recovery in the chromatographic sciences. J. Chromatogr. A, 1146, 139-147.
Visi, E. 2002. Quality Assurance/Quality Control in pesticide residue laboratories. Possibilities of controlling the various analytical steps. FAO/IAEA Training and Reference Centre for Food and Pesticide Control Training workshop on Introduction to QC/QA measures in Pesticide Residue Analytical Lab. IAEA’s Laboratories Seibersdorf; AUSTRIA 17 June- 26 July 2002.