Application of Liquid Chromatography with Diode-Array Detector for Determination of Acetamiprid and 6-chloronicotinic Acid Residues in Sweet Cherry Samples
Abstract
A rapid and simple method for simultaneous determination of acetamiprid and its metabolite 6-chloronicotinic acid in sweet cherry samples has been developed. This residue analysis method is based on the reversed phase separation on C18 column with gradient elution. Analytes’ determination and quantification were performed by high performance liquid chromatography (HPLC) with diode-array detector and chromatograms were extracted at 230 nm. Extraction efficiency experiments demonstrated the ability of this method to extract neonicotinoids from sweet cherry samples. These insecticides were extracted with a mixture of acetonitril/0.1N ammonium-chloride (8/2, v/v). The average recoveries of acetamiprid and 6-chlornicotinic acid from sweet cherry samples were in the range of 95-101% and 73-83%, respectively, with the associated relative standard deviations (RSDs) <5%. Expanded measurement uncertainties for the analyzed compounds were 2.7 and 3.01%. The limit of quantification (LOQ) was 10 µg/kg and 30 µg/kg for acetamiprid and 6-chloronicotinic acid, respectively. Thus, the developed HPLC/DAD method can be considered a useful tool for sensitive and rapid determination of acetamiprid and 6-chloronicotinic acid. Hence, the method may find further application in the analysis of real sweet cherry samples contaminated with these insecticides at a ppb level.
References
COMMISSION REGULATION (EU) No 978/201 of 3 October 2011 amending Annexes II and III to Regulation (EC) No 396/2005 of the European Parliament and of the Council as regards maximum residue levels for acetamiprid, biphenyl, captan, chlorantraniliprole, cyflufenamid, cymoxanil, dichlorprop-P, difenoconazole, dimethomorph, dithiocarbamates, epoxiconazole, ethephon, flutriafol, fluxapyroxad, isopyrazam, propamocarb, pyraclostrobin, pyrimethanil and spirotetramat in or on certain products.
Coscolla, C., Yusa, V., Beser, M.I. and Pastor, A.: Multi-residue analysis of 30 currently used pesticides in fine airborne particulate matter (PM 2.5) by microwave-assisted extraction and liquid chromatographytandem mass spectrometry. Journal of Chromatography A, 1216: 8817–8827, 2009.
Council Directive 91/414/EEC, of 15 July 1991 concerning the placing of plant protection products on the market (OJ L 230, 19.8.1991, p. 1).
del Mar Gómez-Ramos, M., Pérez-Parada, A., García-Reyes, J.F., Fernández-Alba, A.R. and Agüera, A.: Use of an accurate-mass database for the systematic identification of transformation products of organic contaminants in wastewater effluents. Journal of Chromatography A, 1218: 8002-8012, 2011.
Directorate of General Health and Consumer Protection Document No. SANCO/12495/2011, Method validation and quality control procedures for pesticide residues analysis in food and feed.
Ellison, S.L.R., Rosslein, M. and Williams, A.: Quantifying Uncertainty in Analytical Measurement (Second Edition). EURACHEM/CITAC, 2000.
Ferrer, I., Thurman, E.M. and Fernandez-Alba, A.R.: Quantitation and accurate mass analysis of pesticides in vegetables by LC/TOF-MS. Analytical Chemistry, 77: 2818–2825, 2005.
Fidente, P., Seccia, S., Vanni, F. and Morrica, P.: Analysis of nicotinoid insecticides residues in honey by solid matrix partition clean-up and liquidchromatography–electrospray mass spectrometry. Journal of Chromatography A, 1094: 175–178, 2005.
Gaal, F., Guzsvány, V., Lazić, S. and Vidaković, N.: Determination of acetamiprid and 6-chlornicotinic acid by derivative spectrophotometry and HPLC methods. Proceedings of the 12th Symposium on Analytical and Environmental problems-SZAB, Szeged, Hungary, 2005, pp. 88-92.
Gil García, M.D., Martínez Galera, M., Santiago Valverde, R., Galanti, A. and Girotti, S.: Column switching liquid chromatography and post-column photochemically fluorescence detection to determine imidacloprid and 6-chloronicotinic acid in honeybees. Journal of Chromatography A, 1147: 17–23, 2007.
Guzsvány, V.: Prilog karakterizaciji i određivanju nekih neonikotinoida. Doktorska disertacija. Univerzitet u Novom Sadu. Prirodno-matematički fakultet, Novi Sad, 2006.
Guzsvány, V., Lazić, S. and Gaal, F.: Determination of neonicotinoid insecticides in hony by solid-phase extraction and high-performance liquid chromatography. 6th European pesticide resiude Workshop-EPRW, Corfu, Greece, 2006a, p. 148.
Guzsvány, V., Lazić, S., Vidaković, N. and Papp, Zs.: Derivative spectophotometric determination of acetamiprid in the presence of 6-chlornicotinic acid. Journal of Serbian Chememical Society, 77(0): 1-11, 2012.
Guzsvany, V.J., Rajić, Lj.M., Jović, B., Orčić, D.Z., Csanadi, J.J., Lazić, S.D. and Abramović, B.F.: Spectroscopic monitoring of photocatalytic degradation of the insecticide acetamiprid and its degradation product 6-chloronicotinic acid on TiO2 catalyst. Journal of Environmental sceience and health part A-toxic/hazardous substances &environemntal engeneering, 47(12): 1919-1929, 2012a.
Hernández, F., Sancho, J.V., Ibañez, M. and Grimalt, S.: Investigation of pesticide metabolites in food and water by LC-TOF-MS. TrAc – Trends in Analytical Chemistry, 27: 10, 2008.
ISO/IEC 17025 International Standard (Second Edition), General requirements for the competence of testing and calibration laboratories, 2005.
Jansson, C., Pihlstrom, T., Osterdahl, B.G. and Markides, K.E.: A new multiresidue method for analysis of pesticide residues in fruit and vegetables using liquid chromatography with tandem mass spectrometric detection. Journal of Chromatography A, 1023: 93–104, 2004.
Jeschke, P., Moriya, K., Lantzsch, R., Seifert, H., Lindner, W., Jelich, K., Göhrt, A., Beck, M.E. and Etzel, W.: Pflanzenschutz-Nachrichten Bayer, 54: 147−160, 2001.
Kamel, A.: Refined Methodology for the Determination of Neonicotinoid Pesticides and Their Metabolites in Honey Bees and Bee Products by Liquid Chromatography – Liquid Chromatography – Tandemm Mass Spectrometry (LC-MS/MS). Journal of Agricultural and Food Chemistry, 58: 5926-5931, 2010.
Kim, M.R., Na, M.A., Jung, W.Y., Kim, C.S., Sun, N.K., Seo, E.C., Lee, E.M., Pak, Y.G., Byun, J.A., Eom, J.H., Jung, R.S. and Lee, J.H.: Monitoring of pesticide residues in special products. Korean Journal of Pesticide Science, 12: 323–334, 2008.
Lazić, S., Mandić, A., Kelemen-Mašić, Đ., Ekres, S. and Inđić, D.: Ostaci insekticida imidakloprida u krompiru i luku. XII Simpozijum o zaštiti bilja i savetovanje o primeni pesticida, Zlatibor, Srbija, 2002, p. 151.
Lazić, S., Mandić, A. and Klokočar-Šmit, Z.: Optimizacija metoda određivanja ostataka insekticida tiametoksama u paprici. XII Simpozijum o zaštiti bilja i savetovanje o primeni pesticida, Zlatibor, Srbija, 2002a, p. 150.
Lazić, S., Mandić, A., Dedić, B. and Djelmiš, A.: Determination of the insecticide imidacloprid residues in onion. 3rd Symposium of Mediterranean Group of Pesticide Research-"Crop Protection", Aix en Provence, France, 2003, p. 45.
Lazić, S., Mandić, A., Inđić, D., Đelmiš, A. and Dedić, B.: Usage of Different SPE Columns for the Imidacloprid Residues Determination in Tobacco Leaves and Onion. International Conference on Sustainable Agriculture and European Integration Processes, Novi Sad, Serbia, 2004, p. 130.
Lee, Y.E., Noh, H.H., Park, Y.S., Kang, K.W., Jo, S.Y., Lee, S.R., Park, I.Y., Kim, T.H., Jin, Y.D. and Kyoung, K.S.: Monitoring of pesticide residues in agricultural products collected from market in Cheongju and Jeonju. Korean Journal of Pesticide Science, 12: 357–362, 2008.
Lee, S.J., Park, S., Choi, J.Y., Shim, J.H., Shin, E.H., Choi, J.H., Kim, S.T., Abd El-Aty, A.M., Jin, J.S., Bae, D.W. and Shin, S.C.: Multiresidue analysis of pesticides with hydrolyzable functionality in cooked vegetables by liquid chromatography tandem mass spectrometry. Biomedical Chromatography, 23: 719–731, 2009.
Lesueur, C., Knittl, P., Gartner, M., Mentler, A. and Fuerhacker, M.: Analysis of 140 pesticides from conventional farming foodstuff samples after extraction with the modified QuECheRS method. Food Control, 19: 906–914, 2008.
Mandić A., Lazić S., Gaal F., Okresz S. and Kelemen-Mašić, Đ.: Determination of the insecticide imidacloprid residues in potato. Proceedings of the 9th Symposium of Analytical and Environmental Problems, Szeged, Hungary, 2002, pp. 5-9.
Mandić, A., Lazić, S., Okresz, S. and Gaal, F.: Determination of the insecticide imidacloprid in potato (Solanum tuberosum L.) and onion (Allium cepa) by high-performance liquid chromatography with diode-array detection. Journal of Analytical Chemistry, 60(12): 1134-1138, 2005.
Marin, A., Martinez Vidal, J.L., Egea Gonzalez, F.J., Garrido Frenich, A., Glass, C.R. and Sykes, M.: Assessment of potential (inhalation and dermal) and actual exposure to acetamiprid by greenhouse applicators using liquid chromatography–tandem mass spectrometry. Journal of Chromatography B, 804: 269–275, 2004.
Martínez-Vidal, J.L., Plaza-Bolaños, P., Romero-González, R. and Garrido-Frenich, A. Determination of pesticide transformation products: A review of extraction and detection methods. Journal of Chromatography A, 1216: 6767-6788, 2009.
Muccio, A.D., Fidente, P., Barbini, D.A., Dommarco, R., Seccia, S. and Morrica, P.: Application of solid-phase extraction and liquid chromatography– mass spectrometry to the determination of neonicotinoid pesticide residues in fruit and vegetables. Journal of Chromatography A, 1108: 1–6, 2006.
Obana, H., Okihashi, M., Akutsu, K., Kitagawa, Y. and Hori, S.: Determination of acetamiprid, imidacloprid, and nitenpyram residues in vegetables and fruits by high-performance liquid chromatography with diodearray detection. Journal of Agricultural and Food Chemistry, 50: 4464–4467, 2002.
Papp, Z.J., Svancara, I., Guzsvany, V.J., Vytras, K., Gaal, F.F., Voltammetric determination of imidacloprid insecticide in selected samples using a carbon paste electrode. Microchimica Acta, 166 (1-2): 169-175, 2009.
Roberts, T. and Huston, D.: Metabolic Pathways of Agrochemicals, Insecticides and fungicides, part two. The royal society of chemistry, Cambridge, UK, 1999.
Seccia, S., Fidente, P., Montesano, D. and Morrica, P.: Determination of neonicotinoid insecticides residues in bovine milk samples by solidphase extraction clean-up and liquid chromatography with diodearray detection. Journal of Chromatography A, 1214: 115–120, 2008.
Serpil, Y.: Validation and Uncertainty Assessment of Rapid Extraction and Clean-up Methods for the Determination of 16 Organochlorine Pestisicide Residues in Vegetables. Analytica Chimica Acta, 571: 298-307, 2006.
Službeni list Republike Srbije, Pravilnik br. 25/2010 i 28/2011, Pravilnik o maksimalno dozvoljenim količinama ostataka sredstava za zaštitu bilja u hrani i hrani za životinje i o hrani i hrani za životinje za koju se utvrđuju maksimalno dozvoljene količine ostataka sredstava za zaštitu bilja.
Tokieda, M., Ozawa, M., Kobayashi, S. and Gomyo, T.: Method for determination of total residues of the insecticide acetamiprid and its metabolites in crops by gas-chromatography, Nippon Noyaku Gakkaishi, 23: 94-94, 1998.
Tokieda, M., Tanaka, T., Ozawa, M. and Gomyo, T.: High-performance liquid-chromatographic determination of acetamiprid and its degradation products in soil, Nippon Noyaku Gakkaishi, 23: 296-299, 1998a.
Tokieda, M., Ozawa, M. and Gomyo, T.: Methods of determination of acetamiprid and its degradation products in soil by gas chromatography", Journal of pesticide science, 24: 181-185, 1999.
Wanatabe, S., Ito, S., Kamata, Y., Omoda, N., Yamazaki, T., Munakata, H., Kaneko, T., Yuasa, Y. Development of competitive enzyme-linked immunosorbent assays (ELISAs) based on monoclonal antibodies for chloronicotinoid insecticides imidacloprid and acetamiprid. Analytica Chimica Acta, 427: 211–219, 2001.
Žabar, R., Dolenc, D., Jerman, T., Franko, M. and Trebše, P.: Photolytic and photocatalytic degradation of 6-chloronicotinic acid. Chemospehere, 85: 861–868, 2011.
Žabar, R., Persistence, degradation and toxicity of transformation products of selected insecticides. Dissertation. University of Nova Gorica, Graduate school, Nova Gorica, Slovenia, 2012.
Zhang, B., Pan, X., Venne, L., Dunnum, S., McMurry, S.T., Cobb, G.P. and Anderson, T.A.: Development of a method for the determination of 9 currently used cotton pesticides by gas chromatography with electron capture detection. Talanta, 75: 1055–1060, 2008.
Authors retain copyright of the published papers and grant to the publisher the non-exclusive right to publish the article, to be cited as its original publisher in case of reuse, and to distribute it in all forms and media.
The published articles will be distributed under the Creative Commons Attribution ShareAlike 4.0 International license (CC BY-SA). It is allowed to copy and redistribute the material in any medium or format, and remix, transform, and build upon it for any purpose, even commercially, as long as appropriate credit is given to the original author(s), a link to the license is provided, it is indicated if changes were made and the new work is distributed under the same license as the original.
Users are required to provide full bibliographic description of the original publication (authors, article title, journal title, volume, issue, pages), as well as its DOI code. In electronic publishing, users are also required to link the content with both the original article published in Pesticidi i fitomedicina (Pesticides and Phytomedicine) and the licence used.
Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgement of its initial publication in this journal.