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QuEChERS-Based Methods for the Determination of Pesticide Residues in a Dill Using Gas Chromatography with Electron Capture and Nitrogen Phosphorus Detection

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Abstract

In this study, three QuEChERS-based methods of improving sample extract preparation through reduction of unwanted matrix background for pesticide residue analysis in dill (a chlorophyll-containing matrix) were developed and compared. These methods involved the use of (1) dispersive solid-phase extraction (dispersive-SPE), (2) dispersive-SPE combined with liquid–liquid extraction (LLE), and (3) only LLE. Samples were analyzed by gas chromatography with electron capture and nitrogen phosphorus detection (GC-ECD/NPD). The results indicated that cleanup with primary secondary amine (PSA) and graphitized carbon black (GCB) sorbents followed by final solvent exchange from acetonitrile to petroleum ether was the best alternative of the tested methods, resulting in the cleanest extracts. The matrix effect of dill on the most favorable method herein was not significant, and the calibration performed well, with R 2 ≥ 0.99. The overall recoveries at three spiking levels of 0.01, 0.1, and 1.0 mg kg−1 fell in the range between 73 and 110 % (95 % on average) with relative standard deviation (RSD) values equal to or lower than 12 % (5 % on average). Uncertainty for the studied pesticides ranged from 7 to 14 % (with the overall average uncertainty of 11 %). Analyses of real samples revealed the presence of pesticides unapproved for use on dill, as well as exceedances of the maximum residue levels (MRLs) for some pesticides. The samples with residue violation results were also confirmed by gas chromatography–tandem mass spectrometry (GC-MS/MS). The proposed method of sample preparation and chromatographic analysis is sufficient and can be applied with all certainty to determine pesticide residues in dill and other plants of high pigment content, i.e., chlorophyll.

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References

  • Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (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

    CAS  Google Scholar 

  • Bailer J, Aichinger T, Hackl G, Hueber KD, Dachler M (2001) Essential oil content and composition in commercially available dill cultivars in comparison to caraway. Indus Crop Prods 14:229–239

    Article  CAS  Google Scholar 

  • Beyer A, Biziuk M (2007) Przegląd metod oznaczania pozostałości pestycydów i polichlorowanych bifenyli w próbkach żywności. Ecol Chem Eng 14:35–58 [in Polish]

    Google Scholar 

  • Cajka T, Sandy C, Bachanova V, Drabova L, Kalachova K, Pulkrabova J, Hajslova J (2012) Streamlining sample preparation and gas chromatography–tandem mass spectrometry analysis of multiple pesticide residues in tea. Anal Chim Acta 743:51–60. doi:10.1016/j.aca.2012.06.051

    Article  CAS  Google Scholar 

  • Callan NW, Johnson DL, Westcott MP, Welty LE (2007) Herb and oil composition of dill (Anethum graveolens L.): effects of crop maturity and plant density. Ind Crop Prod 25:282–287. doi:10.1016/j.indcrop.2006.12.007

    Article  CAS  Google Scholar 

  • Daly T, Jiwan MA, O’Brien NM, Aherne SA (2010) Carotenoid content of commonly consumed herbs and assessment of their bioaccessibility using an in vitro digestion model. Plant Food Hum Nutr 65:164–169. doi:10.1007/s11130-010-0167-3

    Article  CAS  Google Scholar 

  • del Castillo ML R, Rodriguez-Valenciano M, De la Peña Moreno F, Blanch GP (2012) Evaluation of pesticide residue contents in fruit juice by solid-phase microextraction and multidimensional gas chromatography coupled with mass spectrometry. Talanta 89:77–83, S0039-9140(11)01044-7

    Article  Google Scholar 

  • Document SANCO/12571/2013. Guidance document on analytical quality control and validation procedures for pesticide residues analysis in food and feed. pp. 42.

  • Label-instructions (2015) Label-instructions for use on plant protection products approved for marketing and application with a permit of the Ministry of Agriculture and Rural Development.https://bip.minrol.gov.pl/Informacje-Branzowe/Produkcja-Roslinna/Ochrona-Roslin/Etykiety-Srodkow-Ochrony-Roslin?%2FInformacje-Branzowe%2FProdukcja-Roslinna%2FOchrona-Roslin%2FEtykiety-Instrukcji-Stosowania-Srodkow-Ochrony-Roslin. Accessed 14 April 2015

  • Eurachem/CITAC guide: Quantifying Uncertainty in Analytical Measurement (2012) Ellison SLR, Williams A. (Eds) Third edition ISBN 978-0-948926-30-3. Available from www.eurachem.org.

  • Fenik J, Tankiewicz M, Biziuk M (2011) Properties and determination of pesticides in fruits and vegetables. Trends Anal Chem; TrAC 30:814–826. doi:10.1016/j.trac.2011.02.008

    Article  CAS  Google Scholar 

  • Fernandes VC, Domingues VF, Mateus N, Delerue-Mato C (2011) Determination of pesticides in fruit and fruit juices by chromatographic methods. An overview. J Chromatogr Sci 49:715–730

    Article  CAS  Google Scholar 

  • Jana S, Shekhawat GS (2010) Anethum graveolens, an Indian traditional medicinal herb and spice. Pharmacogn Rev 4:179–184. doi:10.4103/0973-7847.70915

    Article  CAS  Google Scholar 

  • Jirovetz L, Buchbauer G, Stoyanova AS, Georgiev EV, Damianova ST (2003) Composition, quality control, and antimicrobial activity of the essential oil of long-time stored dill (Anethum graveolens L.) seeds from Bulgaria. J Agric Food Chem 51:3854–3857. doi:10.1021/jf030004y

    Article  CAS  Google Scholar 

  • Juan-Garćıa A, Mãnes J, Font G, Pićo Y (2004) Evaluation of solid-phase extraction and stir-bar sorptive extraction for the determination of fungicide residues at low-microg kg(−1) levels in grapes by liquid chromatography-mass spectrometry. J Chromatogr A 1050:119–127

    Article  Google Scholar 

  • Kwona H, Lehotay SJ, Geis-Asteggiante L (2012) Variability of matrix effects in liquid and gas chromatography–mass spectrometry analysis of pesticide residues after QuEChERS sample preparation of different food crops. J Chromatogr A 1270:235–245. doi:10.1016/j.chroma.2012.10.059

    Article  Google Scholar 

  • Lehotay SJ (2011) QuEChERS sample preparation approach for mass spectrometric analysis of pesticide residues in foods. Methods Mol Biol 747:65–91. doi:10.1007/978-1-61779-136-9_4

    Article  CAS  Google Scholar 

  • Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fu W, Mastovska K, Hoh E, Leepipatpiboon N (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1217:2548–2560. doi:10.1016/j.chroma.2010.01.044

    Article  CAS  Google Scholar 

  • Lisiewska Z, Kmiecik W, Korus A (2006) Content of vitamin C, carotenoids, chlorophylls and polyphenols ingreen parts of dill (Anethum graveolensL.) depending on plant height. J Food Comp Anal 19:134–140. doi:10.1016/j.jfca.2005.04.009

    Article  CAS  Google Scholar 

  • Medina-Pastor P, Valverde A, Pihlström T, Masselter S, Gamon M, Mezcua M, Rodríguez-Torreblanca C, Fernández-Alba AR (2011) Comparative study of the main top-down approaches for the estimation of measurement uncertainty in multiresidue analysis of pesticides in fruits and vegetables. J Agric Food Chem 59:7609–7619. doi:10.1021/jf104060h

    Article  CAS  Google Scholar 

  • Namieśnik J, Górecki T (2001) Preparation of environmental samples for the determination of trace constituents. Pol J Environ Stud 10:77–84

    Google Scholar 

  • Ono Y, Yamagami T, Nishina T, Tobino T (2006) Pesticide multiresidue analysis of 303 compounds usings fluid extraction. Anal Sci 22:1473–1776. doi:10.2116/analsci.22.1473

    Article  CAS  Google Scholar 

  • Özcan M (2004) Mineral contents of some plants used as condiments in Turkey. Food Chem 84:437–440. doi:10.1016/S0308-8146(03)00263-2

    Article  Google Scholar 

  • Pakade YB, Tewary DK (2010) Development and applications of single-drop microextraction for pesticide residue analysis: a review. J Sep Sci 33:3683–3691. doi:10.1002/jssc.201000331

    Article  CAS  Google Scholar 

  • Peerakam N, Wattanathorn J, Punjaisee S, Buamongkol S, Sirisa-ard P, Chansakaow S (2014) Chemical profiling of essential oil composition and biological evaluation of Anethum graveolens L. (seed) grown in Thailand. Journal of Natural Sciences Research ISSN 2224–3186 (Paper) ISSN 2225–0921 (Online) 4 (16).

  • Ramos JJ, González MJ, Ramos L (2009) Comparison of gas chromatography-based approaches after fast miniaturized sample preparation for the monitoring of selected pesticide classes in fruits. J Chromatogr A 1216:7307–7313. doi:10.1016/j.chroma.2009.05.013

    Article  CAS  Google Scholar 

  • Rapid Alert System for Food and Feed (RASFF) (2014) https://webgate.ec.europa.eu/rasff-window/portal/?event=SearchForm&cleanSearch=1#. Accessed 14 Oct 2014

  • Regulation (EC) No 1107/2009 of the European Parliament and of the Council of 21 October 2009 concerning the placing of plant protection products on the market and repealing Council Directives 79/117/EEC and 91/414/EEC Official Journal of the European Union L 309/1 24.11.2009. pp. 50.

  • 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. Off. J. L 70, with later amendments. pp. 16 http://ec.europa.eu/sanco_pesticides/public/?event=product.resultat&language=PL&selectedID=169. Accessed 17 Apr 2015

  • Register (2015) Register of plant protection products approved for marketing and application. https://bip.minrol.gov.pl/Informacje-Branzowe/Produkcja-Roslinna/Ochrona-Roslin/Rejestr-Srodkow-Ochrony-Roslin. Accessed 14 Apr 2015

  • Satpathy G, Tyagi YK, Gupta RK (2011) A novel optimised and validated method for analysis of multi-residues of pesticides in fruits and vegetables by microwave-assisted extraction (MAE)–dispersive solid-phase extraction (d-SPE)–retention time locked (RTL)–gas chromatography–mass spectrometry with deconvolution reporting software (DRS). Food Chem 127:1300–1308. doi:10.1016/j.foodchem.2011.01.087

    Article  CAS  Google Scholar 

  • Singh G, Maurya S, de Lampasona MP, Catalan C (2005) Chemical constituents, antimicrobial investigations, and antioxidative potentials of Anethum graveolens L. essential oil and acetone extract: Part 52. J Food Sci 70:M208–M215. doi:10.1111/j.1365-2621.2005.tb07190.x

    Article  CAS  Google Scholar 

  • Słowik-Borowiec M (2015) Validation of a QuEChERS-based gas chromatographic method for multiresidue pesticide analysis in fresh peppermint including studies of matrix effects. Food Anal Methods 8:1413–1424. doi:10.1007/s12161-014-0027-0

    Article  Google Scholar 

  • Stocka J, Tankiewicz M, Biziuk M, Namieśnik J (2011) Green aspects of techniques for the determination of currently used pesticides in environmental samples. Int J Mol Sci 12:7785–7805. doi:10.3390/ijms12117785

    Article  CAS  Google Scholar 

  • Walorczyk S, Drożdżyński D (2012) Improvement and extension to new analytes of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography–tandem quadrupole mass spectrometry revisited. J Chromatogr A 1251:219–231. doi:10.1016/j.chroma.2012.06.055

    Article  CAS  Google Scholar 

  • Walorczyk S, Drożdżyński D, Kierzek R (2015) Determination of pesticide residues in samples of minor drops by gas chromatography and ultra performance liquid chromatography coupled to tandem mass spectrometry. Talant 132:197–204

    Article  CAS  Google Scholar 

  • Yarita T, Aoyagi Y, Otake T (2012) Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean. J Environ Sci Health B 47:942–948. doi:10.1080/03601234.2012.706559

    Article  CAS  Google Scholar 

  • Yazdanparast R, Bahramikia S (2008) Evaluation of the effect of Anethum graveolens L. crude extracts on serum lipids and lipoproteins profiles in hypercholesterolaemic rats. DARU, J Pharm Sci 16:88–94

    CAS  Google Scholar 

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Acknowledgments

Magdalena Sƚowik-Borowiec is grateful to the Institute of Plant Protection – National Research Institute for her pre-doctoral scholarship.

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Authors and Affiliations

  1. Institute of Plant Protection – National Research Institute, Regional Experimental Station, Gen. Langiewicza 28, 35-101, Rzeszów, Poland

    Magdalena Słowik-Borowiec

  2. Institute of Plant Protection – National Research Institute, WładysławaWęgorka 20, 60-318, Poznań, Poland

    Stanisław Walorczyk

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  1. Magdalena Słowik-Borowiec
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  2. Stanisław Walorczyk
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Correspondence to Magdalena Słowik-Borowiec.

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Funding

This work was supported in part by Ministerstwo Nauki i Szkolnictwa Wyższego (Ministry of Science and Higher Education), project ID: SRZ-08.

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Magdalena Słowik-Borowiec declares that she has no conflict of interest. Stanisław Walorczyk declares that he has no conflict of interest.

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This article does not contain any studies with human participants or animals performed by any of the authors.

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Słowik-Borowiec, M., Walorczyk, S. QuEChERS-Based Methods for the Determination of Pesticide Residues in a Dill Using Gas Chromatography with Electron Capture and Nitrogen Phosphorus Detection. Food Anal. Methods 9, 1562–1572 (2016). https://doi.org/10.1007/s12161-015-0333-1

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