The modern apple production involves the use of large amounts of pesticides that can be found in processed products such as apple juice. Harmful effects of pesticide residues on humans, especially children, are well known, hence the content of pesticide residues in fruit, vegetables and their juices should be controlled. This study presents an application of a new, relatively simple and reliable analytical method for qualitative and quantitative determination of three organophosphorus and one organonitrogen pesticide residues in apple juices. The analysis utilizes reversed-phase high-performance liquid chromatography (RP-HPLC) followed by UV diode array detection. Prior to HPLC analysis, a solid-phase extraction (SPE) was used for analytes concentration and sample clean-up. Specificity, selectivity, linearity, precision, accuracy and limit of quantification (LOQ) were examined to assess the validity of the developed method. The method had satisfactory values of multiple correlation coefficients for calibration curves (R2 ≥ 0.95
). The precision was evaluated for the retention times and peak areas, and the estimated values for relative standard deviations (RSD) were 0.05 % - 0.18 % and 0.09 % - 0.62 %, respectively, which indicated an excellent precision of the proposed method. Under the established conditions, the recovery of analytes was 93.80 % - 119.41 %, with relative standard deviations below 0.56 %. This method was successfully applied for determination of some organophosphorus and organonitrogen pesticide residues in apple juices which were taken from Macedonian markets. The achieved values for LOQs were low enough compared to the MRLs of the investigated pesticides in apple according to the Regulation (EC) No 396/2005. Detectable residues of the examined pesticides were not found in the analyzed samples.
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AKAZOME Y: Characteristics and physiological functions of polyphenols from apples. Biofactors, 22(1-4) 311-314, 2004.
ALBERO B, SANCHEZ-BRUNETE C, TADEO JL: Determination of Organophosphorus Pesticides in Fruit Juices by Matrix Solid-Phase Dispersion and Gas Chromatography. J. Agric. Food Chem., 51(24) 6915-6921, 2003.
ATTALLAH ER, BARAKAT DA, MAATOOK GR, BADAWY HA: Validation of a quick and easy (QuEChERS) method for the determination of pesticides residue in dried herbs. J. Food. Agric. Environ., 10(1) 755-762, 2012.
BARTH SW, FAHNDRICH C, BUB A, DIETRICH H, WATZL B, WILL F, BRIVIBA K, RECHKEMMER G: Cloudy apple juice decreases DNA damage, hyperproliferation and aberrant crypt foci development in the distal colon of DMH-initiated rats. Carcinogenesis, 26(8) 1414-1421, 2005.
BORBA DA CUNHA AC, LOPEZ DE ALDA MJ, BARCELO D, PIZZOLATO TM, DOS SANTOS JH: Multianalyte determination of different classes of pesticides (acidic, triazines, phenyl ureas, anilines, organophosphates, molinate and propanil) by liquid chromatography-electrospray-tandem mass spectrometry. Anal. Bioanal. Chem., 378: 940-954, 2004.
CHROMBOOK: Your guide to a fascinating world of chromatography, Merck, KGaA, Darmstadt, Germany, pp. 240-243, 2011.
CUNHA SC, FERNANDES JO, OLIVEIRA MBPP: Fast analysis of multiple pesticide residues in apple juice using dispersive liquid–liquid microextraction and multidimensional gas chromatography–mass spectrometry, J. Chromatogr. A., 1216(51) 8835–8844, 2009.
DOCUMENT No SANCO/12495/2011.: Method validation and quality control procedures for pesticide residues analysis in food and feed, 2011.
DONG MW: Modern HPLC for Practicing Scientists. John Wiley & Sons, Inc., Hoboken, New Jersey, pp. 15-46, 2006.
EUROPEAN COMMISSION, DIRECTORATE GENERAL HEALTH AND CONSUMER PROTECTION.: Guidance document on pesticide residue analytical methods, SANCO/825/00 rev. 8.1, 2010.
HU X, JIANXIN Y, ZHIGANG Y, LANSUN N, YANFEI L, PENG W, JING L, XIN H, XIAOGANG C, YIBIN Z: Determination of multiclass pesticide residues in apple juice by gas chromatography-mass selective detection after extraction by matrix solid-phase dispersion. J AOAC Int., 87(4) 972-985, 2004.
JEANNOT R, SABIK H, SAUVARD E, GENIN E: Application of liquid chromatography with mass spectrometry combined with photodiode array detection and tandem mass spectrometry for monitoring pesticides in surface waters. J. Chromatogr. A., 879(1) 51-71, 2009.
KOAL T, ASPERGER A, EFER J, ENGEWALD W: Simultaneous determination of a wide spectrum of pesticides in water by means of fast on-line SPE-HPLC-MS-MS a novel approach. Chromatographia, 57(1) 93-101, 2003.
KONG XH: Determination of Organophosphorous Pesticide Residues in Apple Juice Concentrate by Solid Phase Microextraction-Gas Chromatography, Food Science, 30(2) 196-200, 2009.
MARKOWSKI J, BARON A, MIESZCZAKOWSKA M, PŁOCHARSKI W: Chemical composition of French and Polish cloudy apple juices. J. Hortic. Sci. & Biotech., ISAFRUIT Special Issue, 68–74, 2009.
MELO LFC, COLLINS CH, JARDIM ICSF: High-performance liquid chromatographic determination of pesticides in tomatoes using laboratory-made NH 2 and C 18 solid-phase extraction materials. J. Chromatogr. A., 1073(1) 75-81, 2005.
MERCER GE: Determination of 112 halogenated pesticides using gas chromatography/mass spectrometry with selected ion monitoring. J AOAC Int., 88(5) 1452-1462, 2005.
PICO Y, BLASCO C, FONT G: Environmental and food applications of LC–tandem mass spectrometry in pesticide-residue analysis: an overview. Mass Spectrom. Rev., 23: 45–85, 2004.
REGULATION (EC) No 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC Text with EEA relevance.
TEXEIRA MJ, AGUIAR A, AFONSO CMM, ALVES A, BASTOS MMSM: Comparison of 424 pesticides levels in grape skin and in the whole grape by a new liquid 425 chromatographic multiresidue methodology. Anal. Chim. Acta., 513(1) 333-340, 2004.
TOMLIN C: The Pesticide Manual Incorporating the Agrochemicals Handbook. 11th Ed., British Crop Protection Council, Royal Society of Chemistry Cambridge, pp. 51-52, 271-274, 435-436, 630-631, 787-788, 1997.
TOPUZ S, OZHAN G, ALPERTUNGA B: Simultaneous determination of various pesticides in fruit juices by HPLC-DAD. Food Control, 16(1) 87-92, 2005.
TSENG SH, LIN YJ, LEE HF, SU SC, CHOU SS, HWANG DF: A multiresidue method for determination 136 pesticides and metabolites in fruit and vegetables: Application of macroporous diatomaceous earth column. J. Food Drug Anal., 15(3) 316-324, 2007.
VELKOSKA-MARKOVSKA L, PETANOVSKA-ILIEVSKA B, Optimization and development of SPE-HPLC-DAD method for the determination of atrazine, malathion, fenitrothion and parathion pesticide residues in apple juice. Maced. J. Chem. Chem. Eng., 32(2) 299-308, 2013.
ZANELLA R, MUNARETTO JS, MARTINS ML: Determination of pesticide multiresidues in apple, pear, and grape using modified QuEChERS and analysis by LC-QTOF MS. Agilent technologies. Inc., 1-11, 2013.