Abstract
This paper reports a simple and rapid method for simultaneous determination of the residues of selected herbicides viz. pendimethalin, oxyfluorfen, imazethapyr and quizalofop-p-ethyl in peanut by liquid chromatography-tandem mass spectrometry (LC-MS/MS). A modified approach of the QuEChERS methodology was used to extract the herbicides from the peanut kernel without any clean-up. The method showed excellent linearity (r2 > 0.99) with no significant matrix effect. Accuracy of the method in terms of average recoveries of all the four herbicides ranged between 69.4 –94.4 % at spiking levels of 0.05, 0.10 and 0.25 mg kg−1 with intra-day and inter-day precision RSD (%) between 2.6–16.6 and 8.0–11.3, respectively. Limit of quantification (LOQs) was 5.0 μg kg−1 for pendimethalin, imazethapyr and quizalofop-p-ethyl and 10.0 μg kg−1 for oxyfluorfen. The expanded uncertainties were <11 % for determination of these herbicides in peanut. The proposed method was successfully applied for analysis of these herbicide residues in peanut samples harvested from the experimental field and the residues were below the detection level.
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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(2):412–431
Anonymous (2006) Regulations amending the food and druf regulation (1454 Imazethapyr) Canada Gazette 140: No. 19, May 13, 2006
Banerjee K, Oulkar DP, Dasgupta S, Patil SB, Patil SH, Savant R (2007) Validation and uncertainty analysis of a multiresidue method for pesticides in grapes using ethyl acetate extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1173:98–109
Bletsou AA, Hanafi AH, Dasenaki ME, Thomaidis NS (2013) Development of specific LC-ESI-MS/MS methods to determine bifenthrin, lufenuron and iprodione residue levels in green beans, peas and chili peppers under Egyptian field condition. Food Anal Methods 6:1099–112
Bonmatin JM, Moineau I, Charvet R, Fleche C, Colin ME, Bengsch ER (2003) A LC/APCI-MS/MS method for analysis of imidacloprid in soils, in plants, and in pollens. Anal Chem 75:2027–2033
Botitsi HV, Garbis SD, Economou A, Tsipi DF (2011) Current mass spectrometry strategies for the analysis of pesticides and their metabolites in food and water matrices. Mass Spectrom Rev 30:907–939
Carneiro RP, Oliveira FAS, Madureira FD, de Silva G, Souza WR, Lopes RP (2013) Development and method validation for determination of 128 pesticides in bananas by modified QuEChERS and UHPLC–MS/MS analysis. Food Control 33:413–423
Cortes JM, Toledano RM, Villen J, Vazquez A (2008) Analysis of pesticides in nuts by online reversed-phase liquid chromatography-gas chromatography using the through-oven transfer adsorption/desorption interface. J Agric Food Chem 56:5544–5549
Cunha SC, Lehotay SJ, Mastovska K, Fernandes JO, Beatriz M, Oliveira PP (2007) Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives. J Sep Science 30:620–632
Engebretson J, Hall G, Hengel M, Shibamoto T (2001) Analysis of pendimethalin residues in fruits, nuts, vegetables, grass and mint by gas chromatography. J Agric Food Chem 49:2198–2206
EU Database on MRLs (MRLs updated on 28/01/2013).http://ec.europa.eu/sanco_pesticides/public/index.cfm
EURACHEM/CITAC guide CG 4, EURACHEM CITAC guide. Quantifying uncertainty in analytical measurement (3rd ed.). Available from <http://www.measurementuncertainty.org/>Accessed June, 2014
European Commission (2011) Document SANCO/12495 Method validation and quality control procedures for pesticide residues analysis in food and feed. European Commission: Brussels, 2011. http://ec.europa.eu/food/plant/protection/resources/qualcontrolen.pdf. (Accessed on June 2014)
European Commission Decision 2002/657/EC. Off J Eur Commun L 221:8–36
European Food Safety Authority (EFSA) (2013) Reasoned opinion on the modification of the existing MRLs for pendimethalin in various crops. EFSA Journal 11(5):3217, http://www.efsa.europa.eu/en/efsajournal/doc/3217.pdf
FAS International maximun residue level database. http://www.mrldatabase.com Accessed 6 Feb 2013
Fenoll J, Hellin P, Flores P, Sotomayor JA, Nicolas MI (2008) Determination of oxadiazon and oxyfluorfen in thyme by gas chromatography with electron-capture detection and gas chromatography/mass spectrometry. Int J Environ Anal Chem 88(9):663–670
Ferreira AMC, Laespada MEF, Pavon JLP, Cordero BM (2014) Development of an environmentally friendly methodological approach to determine chlorinated hydrocarbons and chlorobenzenes in soils. Green Chem Lett Rev 7(1):50–59
Food Safety and Standards Authority of India, Food Safety and Standards (contaminants, toxins and residues) Regulations, 2011.http://www.fssai.gov.in/Portals/0/Pdf/Food %20 safe -ty%20and%20standards%20 (contaminats%20toxins%20and%20residues)%20regulation,%2 02011.pdf
Francisco MLDL, Resurreccion AVA (2008) Functional components in peanuts. Crit Rev Food Sci Nutr 48:715–746
Franco S, Marchi MRR-de (2013) Matrix Effects on water analysis for alkylphenols using solid phase extraction gas chromatography–mass spectrometry. Anal Lett 46(16):2557–2569
Govindaraj G, Jain VK (2012) Constraints and strategies for development of small-scale peanut processing units in Gujarat (India): A Garret ranking approach. Int J Agricult Stat Sci 8(2):705–711
Gratz SR, Ciolino LA, Mohrhaus AS et al (2011) Screening and determination of polycyclic aromatic hydrocarbons in seafoods using QuEChERS based extraction and high performance liquid chromatography with fluorescence detection. J AOAC Int 94:1601–1616
Guan W, Zhang H (2012) Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil. Int J Environ Anal Chem 93(6):679–691
Han L, Guo BY, Feng JH, Lu XM, Lin JM (2008) Study on the enantioselective degradation of imazethapyr in soil by CE. Chromatographia 68:1071–1073
Hernandez F, Pozo OJ, Sancho JV, Bijlsma L, Barreda M, Pitarch E (2006) Multiresidue liquid chromatography tandem mass spectrometry determination of 52 non gas chromatography-amenable pesticides and metabolites in different food commodities. J Chromatogr A 1109:242–252
Hu J, Deng Z, Liu C, Zheng Z (2010) Simultaneous analysis of herbicide metribuzin and quizalofop-p-ethyl residues in potato and soil by GC-ECD. Chromatographia 72(7/8):701–706
Jat RS, Meena HN, Singh AL, Surya JN, Misra JB (2011) Weed management in groundnut (Arachis hypogaea) in India - A review. Agri Reviews 32(3):155–171
Jiang Y, Li Y, Jiang Y, Li J, Pan C (2012) Determination of multiresidues in rapeseed, rapeseed oil, and rapeseed meal by acetonitrile extraction, low-temperature cleanup, and detection by liquid chromatography with tandem mass spectrometry J. Agric Food Chem 60:5089–5098
Johnson YS (2012) Determination of polycyclic aromatic hydrocarbons in edible seafood by QuEChERS-based extraction and gas chromatography-tandem mass spectrometry. J Food Sci 77:131–137
Kaljurand M, Koel M (2011) Recent advancements on greening analytical separation. Cri Rev Anal Chem 41(1):2–20
Kmellar B, Fodor P, Pareja L, Ferrer C, Martinez-Uroz MA, Valverde A, Fernandez-Alba AR (2008) Validation and uncertainty study of a comprehensive list of 160 pesticide residues in multi-class vegetables by liquid chromatography-tandem mass spec trometry. J Chromatogr A 1215:37–50
Koesukwiwat U, Lehotay SJ, Mastovska K, Dorweiler KJ, Leepipatpiboon N (2010) Extension of the QuEChERS method for pesticide residues in cereals to flaxseeds, peanuts, and doughs. J Agric Food Chem 58:5950–5958
Koesukwiwat U, Sanguankaew K, Leepipatpiboon N (2008) Rapid determination of phenoxy acid residues in rice by modified QuEChERS extraction and liquid chromatography-tandem mass spectrometry. Anal Chim Acta 626:10–20
Kolberg DI, Prestes OD, Adaime MB, Zanella R (2011) Development of a fast multiresidue method for the determination of pesticides in dry samples (wheat grains, flour and bran) using QuEChERS based method and GC–MS. Food Chem 125:1436–1442
Konieczka P, Namiesnik J (2010) Estimating uncertainty in analytical procedures based on chromatographic techniques. J Chromatogr A 1217:882–891
Lehotay SJ, Mastovska K, Yun SJ (2005) Evaluation of two fast and easy methods for pesticides residue analysis in fatty food matrixes. J AOAC Int 88:630–638
Li L, Zhang H, Pan C, Zhou Z, Jiang S, Liu F (2007a) Multiresidue analytical method of pesticides in peanut oil using low-temperature cleanup and dispersive solid phase extraction by GC-MS. J Sep Science 30:2097–2104
Li L, Zhou Z, Pan C, Qian C, Jiang S, Liu F (2007b) Determination of organophosphorus pesticides in soybean oil, peanut oil and sesame oil by low-temperature extraction and GC-FPD Chromatographia 66:625–629
Madureira FD, Oliveira FAS, Souza WR, Pontelo AP, Oliveira MLG, Silva G (2012) A multi-residue method for the determination of 90 pesticides in matrices with a high water content by LC-MS/MS without clean-up. Food Addit Contam 29(4):665–678
Maldaner L, Santana CC, Jardim ICSF (2008) HPLC determination of pesticides in soybeans using matrix solid-phase dispersion. J Liq Chromatogr Relat Technol 31(7):972–983
Mantzos N, Karakitsou A, Zioris I, Leneti E, Konstantinou I (2013) QuEChERS and solid phase extraction methods for the determination of energy crop pesticides in soil, plant and runoff water matrices. Int J Environ Anal Chem 93(15):1566–1584
Mastovska K, Dorweiler KJ, Lehotay SJ, Wegwcheid JS, Szpylka KA (2010) Pesticide multiresidue analysis in cereal grains using modified QuEChERS method combined with automated direct sample introduction GC-TOFMS and UPLC-MS/MS techniques. J Agric Food Chem 58:5959–5972
Newsome WH, Doucet J, Davies D, Sun WF (2000) Pesticide residues in the Canadian market basket survey 1992 to 1996. Food Addit Contam 17(10):847–854
Pareja L, Cesio V, Heinzen H, Fernández-Alba AR (2011) Evaluation of various QuEChERS based methods for the analysis of herbicides and other commonly used pesticides in polished rice by LC–MS/MS. Talanta 83:1613–1622
Pinto CG, Martin SH, Pavon JLP, Cordero BM (2011) A simplified quick, easy,cheap, effective, rugged and safe approach for the determination of trihalomethanes and benzene, toluene, ethylbenzene and xylenes in soil matrices by fast gas chromatography with mass spectrometry detection. Anal Chim Acta 689:129–136
Reddy PS (1988) Genetics, breeding and varieties. In: Reddy PS (ed) Groundnut. Indian Council of Agricultural Research Kirshi, Pusa, New Delhi, pp 200–317
Romero-Gonzalez R, Frenich AG, Vidal JLM, Prestes OD, Grio SL (2011) Simultaneous determination of pesticides, biopesticides and mycotoxins in organic products applying a quick, easy, cheap, effective, rugged and safe extraction procedure and ultra-high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A 1218:1477–1485
Sadowska-Rociek A, Surma M, Cieslik E (2014) Comparison of different modifications on QuEChERS sample preparation method for PAHs determination in black, green, red and white tea. Environ Sci Pollut Res 21:1326–1338
Sanchez AG, Martos NR, Ballesteros E (2006) Multiresidue analysis of pesticides in olive oil by gel permeation chromatography followed by gas chromatography–tandem mass-spectrometric determination. Anal Chim Acta 558:53–61
Shah J, Jan MR, Shehzad FU, Ara B (2011) Quantification of pendimethalin in soil and garlic samples by microwave-assisted solvent extraction and HPLC method. Environ Monit Assess 175:103–108
Sireesha A, Rao PC, Rao PV, Swapna G, Ramalakshmi CS (2012) Residues of pendimethalin and oxyfluorfen in radish and their persistence in soil. J Crop Weed 8(2):120–125
Sobhanzadeh E, Bakar NKA, Abas MRB, Nemati KA (2012) Simple and efficient multi-residue method based on QuEChERS for pesticides determination in palm oil by liquid chromatography time-of-flight mass spectrometry. Environ Monit Assess 184:5821–5828
Sondhia S (2008) Terminal residues of imazethapyr in soybean grains, straw and soil. Pesticide Res J 20(1):128–129
Sondhia S (2010) Persistence and bioaccumulation of oxyfluorfen residues in onion. Environ Monit Assess 162:163–168
Steinheimer TR, Scoggin KD (1998) Estimation of imazethapyr in agricultural water by its cross-reactivity with either imazaquin or imazapyr ELISA kits. J Agric Food Chem 46:1883–1886
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
Su R, Xu X, Wang X, Li D, Li X, Zhang H, Yu A (2011) Determination of organophosphorus pesticides in peanut oil by dispersive solid phase extraction gas chromatography–mass spectrometry. J Chromatogr B 879(30):3423–3428
Thompson M, Ellison SLR, Wood R (2002) Harmonized guidelines for single laboratory validation of methods of analysis. IUPAC technical report. Pure Appl Chem 74:835–855
Tobiszewski M, Mechlinska A, Zygmunt B, Namiesnik J (2009) Green analytical chemistry in sample preparation for determination of trace organic pollutants. Trac-Trend Anal Chem 28(8):943–951
Walorczyk S (2008) Development of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography–tandem quadrupole mass spectrometry II Improvement and extension to new analytes. J Chromatogr A 1208:202–214
Wang DN (2006) Methods for determination of agricultural chemical residues in foods in Japan. Standard press of China, Beijing, pp 422–445
Wang J-H, Cai F, Wang Y-L, Wang X-L (2009) Pesticide multiresidue analysis of peanuts using automated gel permeation chromatography clean-up/gas chromatography–mass spectrometry. Food Addit Contam 26(3):333–339
Wilkowska A, Biziuk M (2011) Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chem 125:803–812
Wong J, Hao C, Zhang K, Yang P, Banerjee K, Hayward D, Iftakhar I, Schreiber A, Tech K, Sack C, Smoker M, Chen X, Utture SC, Oulkar DP (2010) Development and interlaboratory validation of a QuEChERS-Based liquid chromatography-tandem mass spectrometry method for multiresidue pesticide analysis. J Agric Food Chem 58:5897–5903
Zeng DY, Shi HY, Li B, Wang M, Song BA (2006) Development of an enzyme-linked immunosorbent assay for quantitative determination of quizalofop-p-ethyl. J Agric Food Chem 54:8682–86
Zhou Y-m, Zhang H-s (2009) Detection of imazethapyr in peanut. Agrochemicals (in Chinese) 12:024
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The authors are thankful to Director, Directorate of Groundnut Research (ICAR), Junagadh and Director, National Research Centre for Grapes (ICAR), Pune, for providing necessary facilities for conducting the study.
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Saha, A., Shabeer T. P., A., Banerjee, K. et al. Simultaneous analysis of herbicides pendimethalin, oxyfluorfen, imazethapyr and quizalofop-p-ethyl by LC–MS/MS and safety evaluation of their harvest time residues in peanut (Arachis hypogaea L.). J Food Sci Technol 52, 4001–4014 (2015). https://doi.org/10.1007/s13197-014-1473-9
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DOI: https://doi.org/10.1007/s13197-014-1473-9