Abstract
In this study, a simple and rapid dispersive liquid-liquid microextraction method was established, and the residuals of four isomers of hexachlorocyclohexane and six kinds of pyrethroid pesticides in milk were simultaneously determined by gas chromatography electron capture detector (GC-ECD). The milk sample was first extracted with acetonitrile and cleaned with primary secondary amine (PSA). Then 0.5 mL of acetonitrile was mixed with 140 μL of cyclohexane and rapidly injected into 3 mL of pure water. After vortexing and centrifugation, the floating phase was removed with a 0.1-mL pipette into the GC-ECD. The type and volume of extraction solvent, volume of disperser solvent, volume of water, vortex time, and amount of salt were optimized. Under optimal extraction conditions, the ten pesticides showed a good linear relationship in a certain concentration range in milk matrix, and the correlation coefficients were greater than 0.99. The limits of detection ranged from 0.07 to 2 μg/kg, and the limits of quantitation ranged from 0.2 to 5 μg/kg. The average recovery rates were between 70.1% and 106.3%, and the relative standard deviations were less than 15.2%. This method can be used for the determination of hexachlorocyclohexane and pyrethroid pesticides in milk and for subsequent research.
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References
Abhilash PC, Singh V, Singh N (2009) Simplified determination of combined residues of lindane and other HCH isomers in vegetables, fruits, wheat, pulses and medicinal plants by matrix solid-phase dispersion (MSPD) followed by GC–ECD. Food Chem 113:267–271. https://doi.org/10.1016/j.foodchem.2008.07.004
Aguinaga N, Campillo N, Viñas P, Hernández-Córdoba M (2007) Determination of 16 polycyclic aromatic hydrocarbons in milk and related products using solid-phase microextraction coupled to gas chromatography-mass spectrometry. Anal Chim Acta 596:285–290. https://doi.org/10.1016/j.aca.2007.06.005
Anand N, Kundu A, Ray S (2018) A validated method for the determination of neonicotinoid, pyrethroid and organochlorine residues in human milk. Chromatographia 81:315–325. https://doi.org/10.1007/s10337-017-3436-6
Asensio-Ramos M, Ravelo-Pérez LM, González-Curbelo MÁ, Hernández-Borges J (2011) Liquid phase microextraction applications in food analysis. J Chromatogr A 1218:7415–7437. https://doi.org/10.1016/j.chroma.2011.05.096
Berger M, Löffler D, Ternes T, Heininger P, Ricking M, Schwarzbauer J (2016) The effect of distribution processes on the isomeric composition of hexachlorocyclohexane in a contaminated riverine system. Int J Environ Sci Technol 13:995–1008. https://doi.org/10.1007/s13762-016-0940-4
Berijani S, Assadi Y, Anbia M, Milani Hosseini MR, Aghaee E (2006) Dispersive liquid-liquid microextraction combined with gas chromatography-flame photometric detection. Very simple, rapid and sensitive method for the determination of organophosphorus pesticides in water. J Chromatogr A 1123:1–9. https://doi.org/10.1016/j.chroma.2006.05.010
Bordet F, Inthavong D, Fremy JM (2002) Interlaboratory study of a multiresidue gas chromatographic method for determination of organochlorine and pyrethroid pesticides and polychlorobiphenyls in milk, fish, eggs, and beef fat. J AOAC Int 85:1398–1409
CAC (Codex Alimentarius Commission) (2018) Codex Online Database Pesticides Residues in Food. Link: http://www.fao.org/fao-who-codexalimentarius/codex-texts/dbs/pestres/commodities-detail/en/?lang=en&c_id=187.
Caldas SS, Costa FP, Primel EG (2010) Validation of method for determination of different classes of pesticides in aqueous sample by dispersive liquid-liquid microextraction with liquid chromatography-tandem mass spectrometric detection. Anal Chim Acta 665:55–62. https://doi.org/10.1016/j.aca.2010.03.004
Campillo N, Peñalver R, Hernández-Córdoba M (2010) Determination of dimethylselenide and dimethyldiselenide in milk and milk by-products by solid-phase microextraction and gas chromatography with atomic emission detection. Talanta 80:1856–1861. https://doi.org/10.1016/j.talanta.2009.10.034
Campillo N, Viñas P, Férezmelgarejo G, Hernández-Córdoba M (2013) Dispersive liquid-liquid microextraction for the determination of macrocyclic lactones in milk by liquid chromatography with diode array detection and atmospheric pressure chemical ionization ion-trap tandem mass spectrometry. J Chromatogr A 1282:20–26. https://doi.org/10.1016/j.chroma.2013.01.086
Cao H, Chen XZ, Zhu Y, Li ZG, Wu XG, Zhu Y (2013) Determination of sulfonamides and quinolones in milk by QuEChERS and ultra performance liquid chromatography-tandem mass spectrometry. Food Sci Technol 38:323–329. https://doi.org/10.13684/j.cnki.spkj.2013.06.025
Cao JP, Xie QL, Zhou JM, Yi ZH (2015) Application progress of dispersive liquid-liquid microextraction in food analysis. J Instrum Anal 34:616–624. https://doi.org/10.3969/j.issn.1004-4957.2015.05.020
Cao JP, Di HW, Zhou JM, Liang YF, Xie QL (2016) A review on dispersive liquid-liquid microextraction method. J Instrum Anal 35:913–921. https://doi.org/10.3969/j.issn.1004-4957.2016.07.025
Chung TL, Liao CJ, Chen MF (2010) Comparison of liquid–liquid extraction and solid-phase extraction for the determination of polycyclic aromatic hydrocarbons in the milk of Taiwan. J Taiwan Inst Chem E 41:178–183. https://doi.org/10.1016/j.jtice.2009.07.003
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. https://doi.org/10.1016/j.chroma.2009.02.048
Di Muccio A, Pelosi P, Barbini DA, Generali T, Ausili A, Vergori F (1997) Selective extraction of pyrethroid pesticide residues from milk by solid-matrix dispersion. J Chromatogr A 765:51–60. https://doi.org/10.1016/S0021-9673(96)01005-9
Farajzadeh MA, Djozan D, Mogaddam MRA, Bamorowat M (2011) Extraction and preconcentration technique for triazole pesticides from cow milk using dispersive liquid-liquid microextraction followed by GC-FID and GC-MS determinations. J Sep Sci 34:1309–1316. https://doi.org/10.1002/jssc.201000928
Farajzadeh MA, Djozan D, Mogaddam MRA, Norouzi J (2012) Determination of phthalate esters in cow milk samples using dispersive liquid-liquid microextraction coupled with gas chromatography followed by flame ionization and mass spectrometric detection. J Sep Sci 35:742–749. https://doi.org/10.1002/jssc.201100853
Farajzadeh MA, Mogaddam MRA, Ghorbanpour H (2014) Development of a new microextraction method based on elevated temperature dispersive liquid–liquid microextraction for determination of triazole pesticides residues in honey by gas chromatography-nitrogen phosphorus detection. J Chromatogr A 1347:8–16. https://doi.org/10.1016/j.chroma.2014.04.067
Farajzadeh MA, Mogaddam MRA (2016) Low-density-solvent-based air-assisted liquid-liquid microextraction followed by gas chromatography with flame ionization detection for the determination of synthetic phenolic antioxidants in milk samples. J Sep Sci 39:1160–1167. https://doi.org/10.1002/jssc.201501210
Gao XS, Zhang Y, Wang SX, Hua R, Zhang XM (2010) Determination of pyrethroid pesticide residues in milk by QuEChERS-gas chromatography. China Dairy Cattle 8:56–60. https://doi.org/10.3969/j.issn.1004-4264.2010.08.020
Gao YL, Xu C, Liu SB, Sun P (2018) Determination of seven pyrethroid pesticides in liquid milk by dispersive liquid–liquid microextraction based on the solidification of a floating organic droplet followed by GC. Chromatographia 81:539–544. https://doi.org/10.1007/s10337-017-3457-1
Jank L, Hoff RB, Tarouco PC, Barreto F, Pizzolato TM (2012) β-Lactam antibiotics residues analysis in bovine milk by LC-ESI-MS/MS: a simple and fast liquid-liquid extraction method. Food Addit Contam Part A 29:497–507. https://doi.org/10.1080/19440049.2011.604044
Karaseva NM, Amelin VG, Tret’yakov AV (2014) QuEChERS coupled to dispersive liquid-liquid microextraction for the determination of aflatoxins B1 and M1 in dairy foods by HPLC. J Anal Chem 69:461–466. https://doi.org/10.1134/S1061934814030071
Khay S, El-Aty AMA, Choi JH, Shin EH, Shin HC, Kim JS, Chang BJ, Lee CH, Shin SC, Jeong JY, Shim JH (2009) Simultaneous determination of pyrethroids from pesticide residues in porcine muscle and pasteurized milk using GC. J Sep Sci 32:244–251. https://doi.org/10.1002/jssc.200800481
Knobel G, Calimag-Williams K, Campiglia AD (2013) Analysis of polycyclic aromatic hydrocarbon metabolites in cow's milk by liquid–liquid extraction and synchronous room-temperature fluorescence spectroscopy. Anal Methods 5:1577–1582. https://doi.org/10.1039/c3ay26114j
Kokosa JM (2013) Advances in solvent-microextraction techniques. Trends Anal Chem 43:2–13. https://doi.org/10.1016/j.trac.2012.09.020
Liang P, Xu J, Li Q (2008) Application of dispersive liquid-liquid microextraction and high-performance liquid chromatography for the determination of three phthalate esters in water samples. Anal Chim Acta 609:53–58. https://doi.org/10.1016/j.aca.2007.12.025
Li XJ, Yu H, Peng RF, Gan PS (2017) Determination of 19 sulfonamides residues in pork samples by combining QuEChERS with dispersive liquid–liquid microextraction followed by UHPLC–MS/MS. J Sep Sci 40:1377–1384. https://doi.org/10.1002/jssc.201601034
Liu D, Min SG, Ping H, Song XZ (2016) The application of directly suspended droplet microextraction for the evaluation of phthalic acid esters in cow's milk by gas chromatography mass spectrometry. J Chromatogr A 1443:66–74. https://doi.org/10.1016/j.chroma.2016.03.062
Liu HL (2014) Research progress of overview on sample pretreatment of pesticides residue in milk. J Food Saf Qual 5:1419–1426 http://www.chinafoodj.com/ch/reader/create_pdf.aspx?file_no=20140217003&flag=1&journal_id=spzljcxb
Liu XJ, Zhao AJ, Zhang AN, Liu HQ, Xiao WJ, Wang CJ, Wang XD (2011) Dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry determination of polychlorinated biphenyls and polybrominated diphenyl ethers in milk. J Sep Sci 34:1084–1090. https://doi.org/10.1002/jssc.201000767
Mahmoudpour M, Mohtadinia J, Ansarin M, Nemati M (2016) Dispersive liquid–liquid microextraction for HPLC-UV determination of PAHs in milk. J AOAC Int 99:527–533. https://doi.org/10.5740/jaoacint.15-0169
Maragou NC, Lampi EN, Thomaidis NS, Koupparis MA (2006) Determination of bisphenol A in milk by solid phase extraction and liquid chromatography-mass spectrometry. J Chromatogr A 1129:165–173. https://doi.org/10.1016/j.chroma.2006.06.103
Miao XX, Liu DB, Wang YR, Yang YY, Yang XY, Gong HR (2015) Modified QuEChERS in combination with dispersive liquid–liquid microextraction based on solidification of the floating organic droplet method for the determination of organophosphorus pesticides in milk samples. J Chromatogr Sci 53:1813–1820. https://doi.org/10.1093/chromsci/bmv089
Morelli-Cardoso MHW, Cardozo RTM, Mello JL, Abrantes S, Menezes KMP (1999) Extraction and clean-up method for the determination of twenty organochlorine pesticide residues in tomatoes by GLC-ECD. J Sep Sci 22:619–622. https://doi.org/10.1002/(SICI)1521-4168(19991101)22:11<619::AID-JHRC619>3.0.CO;2-0
Rezaee M, Yamini Y, Faraji M (2010) Evolution of dispersive liquid–liquid microextraction method. J Chromatogr A 1217:2342–2357. https://doi.org/10.1016/j.chroma.2009.11.088
Rúbies A, Guo LL, Centrich F, Granados M (2016) Analysis of non-steroidal anti-inflammatory drugs in milk using QuEChERS and liquid chromatography coupled to mass spectrometry: triple quadrupole versus Q-Orbitrap mass analyzers. Anal Bioanal Chem 408:5769–5778. https://doi.org/10.1007/s00216-016-9679-5
Salas JH, González MM, Noa M, Pérez NA, Díaz G, Gutiérrez R, Zazueta H, Osuna I (2003) Organophosphorus pesticide residues in Mexican commercial pasteurized milk. J Agric Food Chem 51:4468–4471. https://doi.org/10.1021/jf020942i
Singh S, Nelapati K (2017) Effect of food processing on degradation of hexachlorocyclohexane and its isomers in milk. Vet World 10:270–275. https://doi.org/10.14202/vetworld.2017.270-275
Shamsipur M, Najmeh Y, Ghambarian M (2016) Combination of solid-phase extraction with dispersive liquid–liquid microextraction followed by GC–MS for determination of pesticide residues from water, milk, honey and fruit juice. Food Chem 204:289–297. https://doi.org/10.1016/j.foodchem.2016.02.090
Tuncel SG, Şenlik D (2016) Determination of phthalates in milk by ultrasound-assisted dispersive liquid–liquid microextraction and gas chromatography–mass spectrometry. Anal Lett 49:1334–1343. https://doi.org/10.1080/00032719.2015.1098654
Wang S, Yang S, Liu F, Xue J, You X (2012) Review on the application of liquid phase microextraction in pesticide residue analysis. Chinese J Pestic Sci 14:461–474. https://doi.org/10.3969/j.issn.1008-7303.2012.05.01
Yu X, Ang HC, Yang HS, Zheng C, Zhang YQ (2016) 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
Zgoła-Grześkowiak A, Grześkowiak T (2011) Dispersive liquid-liquid microextraction. Trends Anal Chem 30:1382–1399. https://doi.org/10.1016/j.trac.2011.04.014
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Yuanling Zhao declares no conflict of interest. Xi’ai Hou declares no conflict of interest. Dongmei Qin declares no conflict of interest. Dan Liu declares no conflict of interest.
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Zhao, Y., Hou, X., Qin, D. et al. Dispersive Liquid-Liquid Microextraction Method for the Simultaneous Determination of Four Isomers of Hexachlorocyclohexane and Six Pyrethroid Pesticides in Milk by Gas Chromatography Electron Capture Detector. Food Anal. Methods 13, 370–381 (2020). https://doi.org/10.1007/s12161-019-01662-w
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DOI: https://doi.org/10.1007/s12161-019-01662-w