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Determination of pesticide residues in fish tissues by modified QuEChERS method and dual-d-SPE clean-up coupled to gas chromatography–mass spectrometry

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Abstract

The aim of this research was to modify the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for the determination of organochlorine and organophosphate pesticides in fatty animal matrices such as fish muscle tissues of carp and sturgeon collected from Carp Valley, Lesser Poland. Pesticides extraction effectiveness was evaluated at 0.030 mg kg−1 spiking level and efficiency of the dispersive-solid-phase extraction (d-SPE) clean-up step was evaluated by comparison testing two different d-SPE clean-up stages, first the addition of the d-SPE sorbent combination (PSA + SAX + NH2), and secondly the addition of C18 after extracts enrichment with the d-SPE sorbent combination (PSA + SAX + NH2), introducing a novel concept of clean-up named dual-d-SPE clean-up. Analysis of pesticide residues was performed by Gas Chromatography Quadrupole Mass Spectrometry (GC/Q-MS) working in selected-ion monitoring (SIM) mode. Linear relation was observed from 0 to 200 ng mL−1 and determination coefficient R 2 > 0.997 in all instances for all target analytes. Better recoveries and cleanliness of extracts in both samples, carp and sturgeon tissues, were obtained after C18 addition during the dual-d-SPE clean-up step. Recoveries were in the range 70–120 %, with relative standard deviation lower than 10 % at 0.030 mg kg−1 spiking level for most pesticides. LODs ranged 0.001–0.003 mg kg−1, while LOQs ranged 0.004–0.009 mg kg−1. The proposed method was successfully applied analyzing pesticide residues in real carp and sturgeon muscle samples; detectable pesticide residues were observed, but in all of the cases contamination level was lower than the default maximum residue levels (MRLs) set by the European Union (EU), Regulation (EC) N 396/2005.

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References

  • Agilent (2014a) Agilent sampliQ products for sample preparation. Agilent Technologies http://www.chem.agilent.com/Library/brochures/5989-9334EN.pdf Accessed March 2014

  • Agilent (2014b) Agilent bond elut silica-based SPE selection guide. Agilent Technologies https://www.chromspec.com/pdf/e/ag78.pdf Accessed March 2014

  • Anastassiades M, Lehotay S, 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. JAOAC Int 86(22):412–431

    CAS  Google Scholar 

  • Berendsen BJA, Stolker LAM, Nielen MWF (2013) Selectivity in the sample preparation for the analysis of drug residues in products of animal origin using LC-MS. Trends Anal Chem 43:229–239

    Article  CAS  Google Scholar 

  • Blasco C, Masia A, Gabriel-Morillas F, Pico Y (2011) Comparison of the effectiveness of recent extraction procedures for antibiotic residues in bovine muscle tissues. JAOAC Int 94(3):991

    CAS  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 Act 743:51–60

    Article  CAS  Google Scholar 

  • Chafer-Pericas C, Balaguer A, Maquieira A, Puchades R (2013) Dispersive solid-phase extraction and immunoassay with internal reference calibration using fatty acid-coated inorganic fluorescent nanoparticles. Anal Biochem 432:31–37

    Article  CAS  Google Scholar 

  • Chai LK, Elie F (2013) A rapid multi-residue method for pesticide residues determination in white and black pepper (Piper nigrum L.). Food Control 32:322–326

    Article  CAS  Google Scholar 

  • Cieslik E, Sadowska-Rociek A, Molina-Ruiz JM, Surma-Zadora M (2011) Evaluation of QuEChERS method for the determination of organochlorine pesticide residues in selected groups of fruits. Food Chem 125:773–778

    Article  CAS  Google Scholar 

  • Covaci A, Voorspoels S, Ramos L, Neels H, Blust R (2007) Recent developments in the analysis of brominated flame retardants and brominated natural compounds. J Chromatogr A 1153:145–71

    Article  CAS  Google Scholar 

  • Cunha SC, Fernandes JO (2011) Multipesticide residue analysis in maize combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by gas chromatography–mass spectrometry. J Chromatogr A 1218:7748–7757

    Article  CAS  Google Scholar 

  • Cunha SC, Lehotay S, Mastovska K, Fernandes JO, Oliveira MBPP (2007) Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives. J Sep Sci 30:620–632

    Article  CAS  Google Scholar 

  • Dagnac T, Garcia-Chao M, Pulleiro P, Garcia-Jares C, Llompart M (2009) Dispersive solid-phase extraction followed by liquid chromatography-tandem mass spectrometry for the multi-residue analysis of pesticides in raw bovine milk. J Chromatogr A 1216:3702–3709

    Article  CAS  Google Scholar 

  • Deme P, Azmeera T, Prabhavathi Devi BLA, Jonnalagadda PR, Prasad RBN, Vijaya Sarathi UVR (2014) An improved dispersive solid-phase extraction clean-up method for the gas chromatography-negative chemical ionisation tandem mass spectrometric determination of multiclass pesticide residues in edible oils. Food Chem 142:144–151

    Article  CAS  Google Scholar 

  • dos Reis Souza MR, Moreira CO, de Lima TG, Aquino A, Dorea HS (2013) Validation of a matrix solid phase dispersion (MSPD) technique for determination of pesticides in lyophilized eggs of the chicken Gallus gallus domesticus. Microchem J 10:395–401

    Article  Google Scholar 

  • Fontana AR, Lana NB, Martinez LD, Altamirano JC (2010) Ultrasound-assisted leaching-dispersive solid-phase extraction followed by liquid-liquid microextraction for the determination of polybrominated diphenyl ethers in sediment samples by gas chromatography-tandem mass spectrometry. Talanta 82:359–66

    Article  CAS  Google Scholar 

  • Fontana AR, Carmago A, Martinez LD, Altamirano JC (2011) Dispersive solid-phase extraction as a simplified clean-up technique for biological sample extracts. Determination of polybrominated diphenyl ethers by gas chromatography-tandem mass spectrometry. J Chromatogr A 1218:2490–2496

    Article  CAS  Google Scholar 

  • Gilbert-Lopez B, Garcia-Reyes JF, Lozano A, Fernandez-Alba AR, Molina-Diaz A (2010) Large-scale pesticide testing in olives by liquid chromatography-electrospray tandem mass spectrometry using two sample preparation methods based on matrix solid-phase dispersion and QuEChERS. J Chromatogr A 1217:6022–6035

    Article  CAS  Google Scholar 

  • Greco L, Serrano R, Blanes MA, Serrano E, Capri E (2010) Bioaccumulation markers and biochemical responses in European sea bass (Dicentrarchus labrax) raised under different environmental conditions. Ecotox Environ Saf 73:38–45

    Article  CAS  Google Scholar 

  • Hercegova A, Domotorova M, Matisova E (2007) Sample preparation methods in the analysis of pesticide residues in baby food with subsequent chromatographic determination. J Chromatogr A 1153:54–73

    Article  CAS  Google Scholar 

  • Hou X, Han M, Dai XH, Yang XF, Yi S (2013) A multiresidue method for the determination of 124 pesticides in rice by modified QuEChERS extraction and gas chromatography-tandem mass spectrometry. Food Chem 138:1198–1205

    Article  CAS  Google Scholar 

  • Kalachova K, Pulkrabova J, Cajka T, Drabova L, Stupak M, Hajslova J (2013) Gas chromatography-triple quadrupole tandem mass spectrometry: a powerful tool for the (ultra)trace analysis of multiclass environmental contaminants in fish and fish feed. Anal Bioanal Chem 405:7803–7815

    Article  CAS  Google Scholar 

  • Kinsella B, Lehotay SJ, Mastovska K, Lightfield AR, Furey A, Danaher M (2009a) New method for the analysis of flukicide and other anthelmintic residues in bovine milk and liver using liquid chromatography-tandem mass spectrometry. Anal Chim Act 637:196–207

    Article  CAS  Google Scholar 

  • Kinsella B, O´Mahony J, Malone E, Moloney M, Cantwell H, Furey A, Danaher M (2009b) Current trends in sample preparation for growth promoter and veterinary drug residue analysis. J Chromatogr A 1216:7977–8015

    Article  CAS  Google Scholar 

  • Lazartigues A, Fratta C, Baodut R, Wiest L, Feidt C, Thomas M, Cren-Olive C (2011a) Multiresidue method for the determination of 13 pesticides in three environmental matrices: water, sediments and fish muscle. Talanta 85:1500–1507

    Article  CAS  Google Scholar 

  • Lazartigues A, Wiest L, Baudot R, Thomas M, Feidt C, Cren-Olive C (2011b) Multiresidue method to quantify pesticides in fish muscle by QuEChERS-based extraction and LC-MS/MS. Anal Bioanal Chem 400:2185–2193

    Article  CAS  Google Scholar 

  • Lehotay S, Mastovska K, Yun SJ (2005) Evaluation of two fast and easy methods for pesticide residue analysis in fatty food matrices. JAOAC Int 88(2):630–638

    CAS  Google Scholar 

  • Liu G, Rong L, Guo B, Zhang M, Li S, Wu Q, Chen J, Chen B, Yao S (2011) Development of an improved method to extract pesticide residues in foods using acetonitrile with magnesium sulphate and chloroform. J Chromatogr A 1218:1429–1436

    Article  CAS  Google Scholar 

  • Nacher-Mestre J, Serrano R, Hernández F, Benedito-Palos L, Perez-Sanchez (2010) Gas chromatography–mass spectrometric determination of polybrominated diphenyl ethers in complex fatty matrices from aquaculture activities. Anal Chim Act 664:190–198

    Article  CAS  Google Scholar 

  • Nardelli V, dell’Oro D, Palermo C, Centonze D (2010) Multi-residue method for the determination of organochlorine pesticides in fish feed based on a cleanup approach followed by gas chromatography-triple quadrupole tándem mass spectrometry. J Chromatogr A 1217:4996–5003

    Article  CAS  Google Scholar 

  • Nerin C, Salafranca J, Aznar M, Batlle R (2009) Critical review on recent developments in solventless techniques for extraction of analytes. Anal Bioanal Chem 393:809–33

    Article  CAS  Google Scholar 

  • Payanan T, Leepipatpiboon N, Varanusupakul P (2013) Low-temperature cleanup with solid-phase extraction for the determination of polycyclic aromatic hydrocarbons in edible oils by reversed phase liquid chromatography with fluorescence detection. Food Chem 141:2720–2726

    Article  CAS  Google Scholar 

  • PN-EN ISO 734–1:2008, Oilseed crush—determination of oil content—Part 1: method of extraction with hexane

  • PN-EN ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories

  • Rajski L, Lozano A, Ucles A, Ferrer C, Fernandez-Alba AR (2013) Determination of pesticide residues in high oil vegetal commoditiesby using various multi-residue methods and clean-ups followed by liquid chromatography tandem mass spectrometry. J Chromatogr A 1304:109–120

    Article  CAS  Google Scholar 

  • Regulation EC/396/2005 (2008) Official Journal of the European Union, Regulation EC/396/2005

  • Ru-zhen Y, Jin-hua W, Ming-lin W, Rong Z, Xiao-yu L, Wie-hua L (2011) Dispersive solid-phase extraction cleanup combined with accelerated solvent extraction for the determination of carbamate pesticide residues in Radix Glycyrrhizae samples by UPLC-MS-MS. J Chromatogr Sci 49

  • Sadowska-Rociek A, Surma M, Cieslik E (2013) Comparison of different modifications on QuEChERS sample preparation method for PAHs determination in black, green, red and white tea. Environ Sci Poll Res 21(2):1326–1338

    Article  Google Scholar 

  • Sanchez-Avila J, Fernandez-Sanjuan M, Vicente J, Lacorte S (2011) Development of multi-residue method for the determination of organic micropollutants in water, sediment and mussels using gas chromatography-tandem mass spectrometry. J Chromatogr A 1218:6799–6811

    Article  CAS  Google Scholar 

  • Sanco, Document N. SANCO/12495/2011. Method validation and quality control procedures for pesticide residues analysis in food and feed

  • Sapozhnikova Y, Lehotay SJ (2013) Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants in fish using fast, low-pressure gas chromatography-tandem mass spectrometry. Anal Chim Act 758:80–92

    Article  CAS  Google Scholar 

  • Souza-Caldas S, Bolzan CM, Jaime de Menezes E, Venquiaruti-Escarron AL, de Martinez Gaspar Martins C, Bianchini A, Primel EG (2013) A vortex-assisted MSPD method for the extraction of pesticide residues from fish liver and crab hepatopancreas with determination by GC-MS. Talanta 112:63–68

    Article  Google Scholar 

  • Stockholm Convention, 2009. http://chm.pops.int/Convention/ThePOPs/ListingofPOPs/tabid/2509/Default.aspx Accessed March 2014

  • 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 A 879:3423–3428

    CAS  Google Scholar 

  • Sun X, Zhu F, Xi J, Lu T, Liu H, Tong Y, Ouyang G (2011) Hollow fiber liquid-phase microextraction as clean-up step for the determination of organophosphorus pesticides residues in fish tissue by gas chromatography coupled with mass spectrometry. Mar Poll Bull 63:102–107

    Article  CAS  Google Scholar 

  • Walorczyk S (2008) Development of a multiresidue 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

    Article  CAS  Google Scholar 

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Acknowledgment

The authors would like to thank TALENTIA Fellowship Program by the Ministry of Economy, Innovation, Science and Employment in Andalusia, Spain, for their financial support. The authors would also like to thank Marek Kozicki, Head of Labotest (www.labotest.com.pl, Torun, Poland), for the cooperation.

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Authors and Affiliations

  1. Malopolska Centre of Food Monitoring, Faculty of Food Technology, University of Agriculture in Krakow, 122 Balicka St, 30-149, Krakow, Poland

    Juan Manuel Molina-Ruiz, Ewa Cieslik & Izabela Walkowska

  2. Department of Animal Products Technology, Faculty of Food Technology, University of Agriculture in Krakow, 122 Balicka St, 30-149, Krakow, Poland

    Iwona Cieslik

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  1. Juan Manuel Molina-Ruiz
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Correspondence to Juan Manuel Molina-Ruiz.

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Molina-Ruiz, J.M., Cieslik, E., Cieslik, I. et al. Determination of pesticide residues in fish tissues by modified QuEChERS method and dual-d-SPE clean-up coupled to gas chromatography–mass spectrometry. Environ Sci Pollut Res 22, 369–378 (2015). https://doi.org/10.1007/s11356-014-3361-2

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