Abstract
In this work, a rapid, simple, and environmentally friendly method has been proposed for direct supramolecular microextraction of four organophosphate insecticides (ethion, phosalone, diazinon, chlorpyrifos) and an isothiazolidine acaricide (hexythiazox) in agricultural product samples prior to their determination by high-performance liquid chromatography-ultraviolet spectroscopy. These five target pesticides have been selected as models in combination with chemometrical optimization processing due to their high consumption in rice, cucumber, and tomato samples for pest control. Method is based on the extraction of pesticide residues from homogenized food sample in an aqueous media containing some tetrahydrofuran (THF) and decanoic acid (DeA). Effects of the experimental parameters, including THF volume, DeA content, salt concentration (as a measure of salting-out effect), and pH on extraction recoveries (ERs) and enrichment factors (EFs) were investigated and, then, the significant variables were optimized using central composite design (CCD) as chemometrical processing. At optimum conditions, this method has a linear response over the ranges of 0.10 to 1500 μg kg−1 for target analytes. Limits of detection (LOD) of this method were found to be in the range of 0.05 to 0.20 μg kg−1. Also, relative standard deviation (RSD) of the method was in the range of 3.45 to 12.27% and the enrichment factors ranged from 102- to 178-fold. The method was applied successfully for analysis of the pesticides in agricultural product samples.
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References
Abhilash PC, Jamil S, Singh N (2007) Matrix solid-phase dispersion extraction versus solid-phase extraction in the analysis of combined residues of hexachlorocyclohexane isomers in plant matrices. J Chromatogr A 1176:43–47. https://doi.org/10.1016/j.chroma.2007.11.005
Al-Degs YS, Al-Ghouti MA, El-Sheikh AH (2009) Simultaneous determination of pesticides at trace levels in water using multiwalled carbon nanotubes as solid-phase extractant and multivariate calibration. J Hazard Mater 169:128–135. https://doi.org/10.1016/j.jhazmat.2009.03.065
Amiri Pebdani A, Khodadoust S, Toori MA, Zarezade V, Talebianpoor MSh (2016) Application of the optimized modified stir bar with ZnS nanoparticles loaded on activated carbon for preconcentration of carbofuran and propoxur insecticides in water samples and their HPLC determination. RSC Advances 6:36238. https://doi.org/10.1039/C6RA02318E
Asperger A, Efer J, Koal T, Engewald W (2006) Trace determination of priority pesticides in water by means of high-speed on-line solid-phase extraction–liquid chromatography–tandem mass spectrometry using turbulent-flow chromatography columns for enrichment and a short monolithic column for fast liquid chromatographic separation. J Chromatogr A 960:109–119. https://doi.org/10.1016/S0021-9673(01)01392-9
Ballesteros-Gómez A, Sicilia MD, Rubio S (2010) Supramolecular solvents in the extraction of organic compounds. A review. Anal Chim Acta 677(2):108–130. https://doi.org/10.1016/j.aca.2010.07.027
Barriada-Pereira M, Concha-Grana E, González-Castro MJ, Muniategui-Lorenzo S, López-Mahía P, Prada-Rodríguez D (2003) Microwave-assisted extraction versus Soxhlet extraction in the analysis of 21 organochlorine pesticides in plants. J Chromatogr A 1008:115–122. https://doi.org/10.1016/S0021-9673(03)01061-6
Bonansea RI, Amé MV, Wunderlin DA (2013) Determination of priority pesticides in water samples combining SPE and SPME coupled to GC–MS. a case study: Suquía River basin (Argentina). Chemosphere 90:1860–1869. https://doi.org/10.1016/j.chemosphere.2012.10.007
Britoa NM, Navickienea S, Polese L, Jardim EFG, Abakerli RB, Ribeiro ML (2002) Determination of pesticide residues in coconut water by liquid–liquid extraction and gas chromatography with electron-capture plus thermionic specific detection and solid-phase extraction and high-performance liquid chromatography with ultraviolet detection. J Chromatogr A 957:201–209. https://doi.org/10.1016/S0021-9673(02)00351-5
Buxton R (2007) The Quality Engineering Handbook, and The Handbook of Quality Management,. http://www.statease.com/soft_ftp.html
Carabias-Mart’ınez R, Rodr’ıguez-Gonzalo E, Amigo-Morán MJ, Hernández-Méndez J (1992) Sensitive method for the determination of organophosphorus pesticides in fruits and surface waters by high-performance liquid chromatography with ultraviolet detection. J Chromatogr A 607:37–45. https://doi.org/10.1016/0021-9673(92)87052-A
Chai M, Tan G, Lal A (2008) Optimization of headspace solid-phase microextraction for the determination of pesticide residues in vegetables and fruits. Anal Sci 24:273–276. https://doi.org/10.2116/analsci.24.273
Cortes JM, Sanchez R, Diaz-Plaza EM, Villen J, Vazquez A (2006) Large volume GC injection for the analysis of organophosphorus pesticides in vegetables using the through oven transfer adsorption desorption (TOTAD) interface. J Agric Food Chem 54:1997–2002. https://doi.org/10.1021/jf0524675
Denis H, Stephen C (2004) Pesticide residues in food and drinking water: human exposure and risks, ISBN:978-0-470-09160-9,378,http://eu.wiley.com/WileyCDA/WileyTitle/productCd-0470091606.html. https://doi.org/10.1002/0470091614
Dorr G, Noller B, Woods N, Hewitt A, Hanan J, Adkins S, Ricci PF, Kennedy IR, Solomon K, Gee S, Crosnan A, Wang S (Eds) (2007) Rational environmental management of agrochemicals, ACS Symposium Series, Washington DC, USA, 996:53–65. https://doi.org/10.1021/bk-2014-1168
Fattahi N, Samadi S, Assadi Y, Milani Hosseini MR (2007) Solid-phase extraction combined with dispersive liquid–liquid microextraction-ultra preconcentration of chlorophenols in aqueous samples. J Chromatogr A 1169:63–69. https://doi.org/10.1016/j.chroma.2007.09.002
Fonseca SG, G’omez AB, Rubio S, Bendito DP (2008) Coacervative extraction of Ochratoxin A in wines prior to liquid chromatography/fluorescence determination. Anal Chim Acta 617:3–10. https://doi.org/10.1016/j.aca.2007.11.002
Goto T, Yuko I, Hisao O, Isao S, Hiroshi M, Hiroyuki N (2003) Simple and rapid determination of N-methylcarbamate pesticides in citrus fruits by electrospray ionization tandem mass spectrometry. Anal Chim Acta 487:201–209
Hashi S, Lin L, Min, Yuki H, Yuanyuan S, Jin-Ming L (2005) Simultaneous determination of carbamate and organophosphorus pesticides in fruits and vegetables by liquid chromatography–mass spectrometry. J Chromatogr A 1097:183–187. https://doi.org/10.1016/j.chroma.2005.10.022
José López-Jiménez F, Rubio S, Pérez-Bendito D (2010) Supramolecular solvent-based microextraction of ochratoxin A in raw wheat prior to liquid chromatography-fluorescence determination. J Chromatogr A 1217:2376–2382. https://doi.org/10.4322/sc.2017.008
Khodadoust S, Ghaedi M, Hadjmohammadi MR (2013) Dispersive nano solid material-ultrasound assisted microextraction as a novel method for extraction and determination of bendiocarb and promecarb: response surface methodology. Talanta 116:637–646. https://doi.org/10.1016/j.talanta.2013.07.013
Khodadoust S, Nasiriani T, Zeraatpisheh F (2018) Preparation of a magnetic molecularly imprinted polymer for the selective adsorption of chlordiazepoxide and its determination by central composite design optimized HPLC. New J Chem 42:14444. https://doi.org/10.1039/C8NJ02643B
Lambropoulou DA, Albanis TA (2007) Liquid-phase micro-extraction techniques in pesticide residue analysis. J Biochem Biophys Methods 70:195–228. https://doi.org/10.1016/j.jbbm.2006.10.004
Liu W, Hu Y, Zhao J, Xu Y, Guan Y (2005) Determination of organophosphorus pesticides in cucumber and potato by stir bar sorptive extraction. J Chromatogr A 1095:1–7. https://doi.org/10.1016/j.chroma.2005.07.107
Liu L, Yuki H, Qin Y, Zhou H, Lin J (2006) Rapid analysis of multiresidual pesticides in agricultural products by gas chromatography- mass spectrometry. Chin J Anal Chem:34783–34786. https://doi.org/10.1016/S1872-2040(06)60040-6
Lucı’a P, Ferna’ndez-Alba AR, Vero’nica C, Horacio H (2011) Analytical methods for pesticide residues in rice. Trends Anal Chem 30:270–291. https://doi.org/10.1016/j.trac.2010.12.001
Mallet VN, Duguay M, Bernier M, Trottier N (1990) Evaluation of high performance liquid chromatography-UV for the multi-residue analysis of organophosphorous pesticides in environmental water. Int J Environ Anal Chem 39:271–279. https://doi.org/10.1080/03067319008032070
María Dolores PB, Soledad Rubio B, María Loreto LR, Amalia García P (2009) Determination of bisphenol A in canned fatty foods by coacervative microextraction, liquid chromatography and fluorimetry. Food Addit Contam Part A 26:265–274. https://doi.org/10.1080/02652030802368740
Montgomery DC (2001) Design and analysis of experiments, 5th edn. John Wiley & Sons Ltd., New York,648 pages. https://doi.org/10.1002/qre.458
Norman KNT, Panton SHW (2001) Supercritical fluid extraction and quantitative determination of organophosphorus pesticide residues in wheat and maize using gas chromatography with flame photometric and mass spectrometric detection. J Chromatogr A 907:247–255. https://doi.org/10.1016/9673S0021-(00)01081-5
Padrón Sanz C, Halko R, Sosa Ferrera Z, Santana Rodrıguez JJ (2004) Micellar extraction of organophosphorus pesticides and their determination by liquid chromatography. Anal Chim Acta 524:265–270. https://doi.org/10.1016/j.aca.2004.06.024
Pirsaheb M, Fattahi N, Shamsipur M (2013) Determination of organophosphorous pesticides in summer crops using ultrasound-assisted solvent extraction followed by dispersive liquid–liquid microextraction based on the solidification of floating organic drop. Food Control 34:378–385. https://doi.org/10.1016/j.foodcont.2013.05.013
Prieto AG, Lunar L, Rubio S, Pérez-Bendito D (2008) Decanoic acid reverse micelle-based coacervates for the microextraction of bisphenol A from canned vegetables and fruits. Anal Chim Acta 617:51–58. https://doi.org/10.1016/j.aca.2008.01.061
Rezaee M, Assadi Y, Milani Hosseini MR, Aghaee E, Ahmadi F, Berijani S (2006) Determination of organic compounds in water using dispersive liquid-liquid microextraction. J Chromatogr A 1116:1–9. https://doi.org/10.1016/j.chroma.2006.03.007
Rezaeia F, Yaminia Y, Moradi M, Daraeica B (2013) Supramolecular solvent-based hollow fiber liquid phase microextraction of benzodiazepines. Anal Chim Acta 804:135–142. https://doi.org/10.1016/j.aca.2013.10.026
Ridgway K, Lalljie SPD, Smith RM (2007) Sample preparation techniques for the determination of trace residues and contaminants in foods. J Chromatogr A 1153:36–53. https://doi.org/10.1016/j.chroma.2007.01.134
Ritter L, Goushleff NCI, Arbuckle T, Cole D, Donald M, Raizenne (2006) Addressing the linkage between exposure to pesticides and human health effects—research trends and priorities for research. J Toxicol Environ Health B Crit Rev 9:441–456. https://doi.org/10.1080/10937400600755895
Ruiz FJ, Rubio S, Perez-Bendito D (2006) Tetrabutylammonium-induced coacervation in vesicular solutions of alkyl carboxylic acids for the extraction of organic compound s. Anal Chem 78:7229–7239. https://doi.org/10.1021/ac060427+
Ruiz FJ, Rubio S, Pérez-Bendito D (2007) Water-induced coacervation of alkyl carboxylic acid reverse micelles: phenomenon description and potential for the extraction of organic compounds. Anal Chem 79:7473–7484. https://doi.org/10.1021/ac0708644
Sabik H, Jeannot R (1998) Determination of organonitrogen pesticides in large volumes of surface water by liquid–liquid and solid-phase extraction using gas chromatography with nitrogen–phosphorus detection and liquid chromatography with atmospheric pressure chemical ionization mass spectrometry. J Chromatogr A 818:197–207. https://doi.org/10.1016/S0021-9673(98)00555-X
Sampedro MC, Martin O, Lopez de Armentia C, Goicolea MA, Rodrıguez E, Gómez de Balugera Z (2000) Solid-phase microextraction for the determination of systemic and non-volatile pesticides in river water using gas chromatography with nitrogen–phosphorous and electron-capture detection. J Chromatogr A 893:347–358. https://doi.org/10.1016/S0021-9673(00)00746-9
Sanghi R, Tewari V (2001) Monitoring of pesticide residues in summer fruits and vegetables from Kanpur, India. Bull Environ Contam Toxicol 67:587–593. https://doi.org/10.1007/s001280164
Talebianpoor MSh, Khodadoust S, Mousavi A, Mahmoudi R, Nikbakht J, Mohammadi J (2017) Preconcentration of carbamate insecticides in water samples by using modified stir bar with ZnS nanoparticles loaded on activated carbon and their HPLC determination: Response surface methodology. Microchem J 130:64–70. https://doi.org/10.1016/j.microc.2016.08.002
Tsoutsi C, Konstantinou I, Hela D, Albanis T (2006) Screening method for organophosphorus insecticides and their metabolites in olive oil samples based on headspace solid-phase microextraction coupled with gas chromatography. Anal Chim Acta 573:216–222. https://doi.org/10.1016/j.aca.2006.04.075
Wang D, You J, Lydy MJ (2010) Sediment matrix effects in analysis of pyrethroid insecticides using gas chromatography-mass spectrometry. Arch Environ Contam Toxicol 59:382–392. https://doi.org/10.1007/s00244-010-9506-5
Yu X, Yang H (2017) Pyrethroid residue determination in organic and conventional vegetables using liquid-solid extraction coupled with magnetic solid phase extraction based on polystyrene-coated magnetic nanoparticles. Food Chem 217:303–310. https://doi.org/10.1016/j.foodchem.2016.08.115
Yu X, Ang HC, Yang H , Zheng C, Zhang Y (2017) Low temperature cleanup combined with magnetic nanoparticle extraction to determine pyrethroids residue in vegetables oils. Food Control 74:112–120. https://doi.org/10.1016/j.foodcont.2016.11.036
Yu X, Li Y, Ng M, Yang H, Wang Sh (2018) Comparative study of pyrethroids residue in fruit peels and fleshes using polystyrene-coated magnetic nanoparticles based clean-up techniques. Food Control 85:300–307. https://doi.org/10.1016/j.foodcont.2017.10.016
Acknowledgements
The authors thank the Genetic and Agricultural Biotechnology Institute of Tabarestan, Sari University of Agricultural, Iran for the support provided.
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This work was supported by the Genetic and Agricultural Biotechnology Institute of Tabarestan Foundation (Gabit-T-005).
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Setare Gorji declares that she has no conflict of interest. Pourya Biparva declares that he has no conflict of interest. Morteza Bahram declares that he has no conflict of interest. Ghorbanali Nematzadeh declares that he has no conflict of interest.
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Highlights
• A rapid, simple and environmental friendly method for preconcentration and separation of trace pesticide residues has been proposed.
• Method is based on the extraction of pesticide residues from homogenized food samples by direct supramolecular solvent.
• Several effective parameters on extraction of pesticides were studied and optimized using a chemometrical optimization processing.
• RMSSs-HPLC/UV method is applied successfully to simultaneous extraction of five pesticides in tomato, rice, and cucumber samples.
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Gorji, S., Biparva, P., Bahram, M. et al. Rapid and Direct Microextraction of Pesticide Residues from Rice and Vegetable Samples by Supramolecular Solvent in Combination with Chemometrical Data Processing. Food Anal. Methods 12, 394–408 (2019). https://doi.org/10.1007/s12161-018-1371-2
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DOI: https://doi.org/10.1007/s12161-018-1371-2