Abstract
Phthalic acid esters (PAEs) have become an important food safety concern due to their lipophilic properties and propensity to accumulate in adipose tissue in edible fish. In this study, a simple, sensitive, and accurate analytical method was successfully established for simultaneous determination of 19 PAEs in fish samples using gas chromatography coupled with tandem mass spectrometry (GC–MS/MS). A simplified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) procedure was applied for sample preparation, and the Plackett-Burman factorial design was utilized for optimizing extraction parameters. The calibration curves were linear in the range 0.01–0.5 mg/kg for all of the analyzed PAEs, and the limits of quantification (LOQs) were 0.05–20 μg/kg which are much lower than those in previous reports. The average spiked recoveries ranged from 71.2 to 116.3%, with relative standard deviations (RSDs) of 3.9 to 16.2% (n = 6). Finally, the method was applied to analyze 60 real fish samples taken from Shanghai Municipality, China, and the diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), and bis(2-ethoxyethyl)phthalate (DEHP) were found in almost all fish samples tested in this study. The present study demonstrated that the established method was suitable for market surveillance of 19 PAE residues in fish samples.
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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
Bradley EL, Burden RA, Leon I, Mortimer DN, Speck DR, Castle L (2013) Determination of phthalate diesters in foods. Food Addit Contam Part A Chem Anal Control Expo Risk Assess 30:722–734. https://doi.org/10.1080/19440049.2013.781683
Carbone S, Ponzo OJ, Gobetto N, Samaniego YA, Reynoso R, Scacchi P, Moguilevsky JA, Cutrera R (2013) Antiandrogenic effect of perinatal exposure to the endocrine disruptor di-(2-ethylhexyl) phthalate increases anxiety-like behavior in male rats during sexual maturation. Horm Behav 63:692–699. https://doi.org/10.1016/j.yhbeh.2013.01.006
Carrillo JD, Martinez MP, Tena MT (2008) Determination of phthalates in wine by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry. Use of deuterated phthalates as internal standards. J Chromatogr A 1181:125–130. https://doi.org/10.1016/j.chroma.2007.12.053
Chatterjee NS, Utture S, Banerjee K, Ahammed Shabeer TP, Kamble N, Mathew S, Ashok Kumar K (2016) Multiresidue analysis of multiclass pesticides and polyaromatic hydrocarbons in fatty fish by gas chromatography tandem mass spectrometry and evaluation of matrix effect. Food Chem 196:1–8. https://doi.org/10.1016/j.foodchem.2015.09.014
Cheung KC, Zheng JS, Leung HM, Wong MH (2008) Exposure to polybrominated diphenyl ethers associated with consumption of marine and freshwater fish in Hong Kong. Chemosphere 70:1707–1720. https://doi.org/10.1016/j.chemosphere.2007.07.043
Colacino JA, Harris TR, Schecter A (2010) Dietary intake is associated with phthalate body burden in a nationally representative sample. Environ Health Perspect 118:998–1003. https://doi.org/10.1289/ehp.0901712
Czech T, Bonilla NB, Gambus F, González RR, Marínsáez J, Vidal JL, Frenich AG (2016) Fast analysis of 4-tertoctylphenol, pentachlorophenol and 4-nonylphenol in river sediments by QuEChERS extraction procedure combined with GC-QqQ-MS/MS. Sci Total Environ 557–558:681–687
Du L, Ma L, Qiao Y, Lu Y, Xiao D (2016) Determination of phthalate esters in teas and tea infusions by gas chromatography-mass spectrometry. Food Chem 197(Pt B):1200–1206. https://doi.org/10.1016/j.foodchem.2015.11.082
Fan Y, Liu S, Xie Q (2014) Rapid determination of phthalate esters in alcoholic beverages by conventional ionic liquid dispersive liquid-liquid microextraction coupled with high performance liquid chromatography. Talanta 119:291–298. https://doi.org/10.1016/j.talanta.2013.11.023
Garrido Frenich A, de las Nieves Barco Bonilla M, Lopez Martinez JC, Martinez Vidal JL, Romero-Gonzalez R (2009) Determination of di-(2-ethylhexyl)phthalate in environmental samples by liquid chromatography coupled with mass spectrometry. J Sep Sci 32:1383–1389. https://doi.org/10.1002/jssc.200900020
Gu YY, Yu XJ, Peng JF, Chen SB, Zhong YY, Yin DQ, Hu XL (2014) Simultaneous solid phase extraction coupled with liquid chromatography tandem mass spectrometry and gas chromatography tandem mass spectrometry for the highly sensitive determination of 15 endocrine disrupting chemicals in seafood. J Chromatogr B Anal Technol Biomed Life Sci 965:164–172. https://doi.org/10.1016/j.jchromb.2014.06.024
Guo Y, Kannan K (2012) Challenges encountered in the analysis of phthalate esters in foodstuffs and other biological matrices. Anal Bioanal Chem 404:2539–2554. https://doi.org/10.1007/s00216-012-5999-2
Liu P, Chen H, Gao G, Hao Z, Wang C, Ma G, Chai Y, Zhang L, Liu X (2016) Occurrence and residue pattern of phthalate esters in fresh tea leaves and during tea manufacturing and brewing. J Agric Food Chem 64:8909–8917. https://doi.org/10.1021/acs.jafc.6b03864
Liu W, Chen J, Hu J, Ling X, Tao S (2008) Multi-residues of organic pollutants in surface sediments from littoral areas of the Yellow Sea, China. Mar Pollut Bull 56:1091–1103. https://doi.org/10.1016/j.marpolbul.2008.03.021
Liu Y, Wang S, Wang L (2013) Development of rapid determination of 18 phthalate esters in edible vegetable oils by gas chromatography tandem mass spectrometry. J Agric Food Chem 61:1160–1164. https://doi.org/10.1021/jf3053884
Luo L, Yang Y, Wang Q, Li H-p, Z-f L, Z-p Q, Z-g Y (2017) Determination of 4-n-octylphenol, 4-n-nonylphenol and bisphenol A in fish samples from lake and rivers within Hunan Province, China. Microchem J 132:100–106. https://doi.org/10.1016/j.microc.2017.01.012
Ma L, Wang L, Tang J, Yang Z (2016) Optimization of arsenic extraction in rice samples by Plackett–Burman design and response surface methodology. Food Chem 204:283–288. https://doi.org/10.1016/j.foodchem.2016.02.126
Mackintosh CE, Maldonado JA, Ikonomou MG (2006) Sorption of phthalate esters and PCBs in a marine ecosystem. Environ Sci Technol 40:3481–3488
Mills LJ, Chichester C (2005) Review of evidence: are endocrine-disrupting chemicals in the aquatic environment impacting fish populations? Sci Total Environ 343:1–34. https://doi.org/10.1016/j.scitotenv.2004.12.070
Molina-Ruiz JM, Cieslik E, Walkowska I (2014) Optimization of the QuEChERS method for determination of pesticide residues in chicken liver samples by gas chromatography-mass spectrometry. Food Anal Methods 8:898–906. https://doi.org/10.1007/s12161-014-9966-8
Morado Pineiro A, Moreda-Pineiro J, Alonso-Rodriguez E, Lopez-Mahia P, Muniategui-Lorenzo S, Prada-Rodriguez D (2013) Arsenic species determination in human scalp hair by pressurized hot water extraction and high performance liquid chromatography-inductively coupled plasma-mass spectrometry. Talanta 105:422–428. https://doi.org/10.1016/j.talanta.2012.10.070
Moreira MA, Andre LC, Cardeal Zde L (2015) Analysis of plasticiser migration to meat roasted in plastic bags by SPME-GC/MS. Food Chem 178:195–200. https://doi.org/10.1016/j.foodchem.2015.01.078
Mortazavi S, Bakhtiari AR, Sari AE, Bahramifar N, Rahbarizadeh F (2013) Occurrence of endocrine disruption chemicals (bisphenol A, 4-nonylphenol, and Octylphenol) in muscle and liver of, Cyprinus Carpino common, from Anzali wetland, Iran. Bull Environ Contam Toxicol 90:578–584
Munaretto JS, Ferronato G, Ribeiro LC, Martins ML, Adaime MB, Zanella R (2013) Development of a multiresidue method for the determination of endocrine disrupters in fish fillet using gas chromatography-triple quadrupole tandem mass spectrometry. Talanta 116:827–834. https://doi.org/10.1016/j.talanta.2013.07.047
Niu L, Xu Y, Xu C, Yun L, Liu W (2014) Status of phthalate esters contamination in agricultural soils across China and associated health risks. Environ Pollut 195:16–23. https://doi.org/10.1016/j.envpol.2014.08.014
Niu Y, Zhang J, Wu Y, Shao B (2011) Simultaneous determination of bisphenol A and alkylphenol in plant oil by gel permeation chromatography and isotopic dilution liquid chromatography-tandem mass spectrometry. J Chromatogr A 1218:5248–5253
Ros O, Vallejo A, Olivares M, Etxebarria N, Prieto A (2016) Determination of endocrine disrupting compounds in fish liver, brain, and muscle using focused ultrasound solid-liquid extraction and dispersive solid phase extraction as clean-up strategy. Anal Bioanal Chem 408:5689–5700. https://doi.org/10.1007/s00216-016-9697-3
Rozati R, Reddy PP, Reddanna P (2002) Role of environmental estrogens in the deterioration of male factor fertility. Fertil Steril 78:1187–1194
Soto AM, Sonnenschein C (2010) Environmental causes of cancer: endocrine disruptors as carcinogens. Nat Rev Endocrinol 6:363–370. https://doi.org/10.1038/nrendo.2010.87
Sun H, Yang Y, Li H, Zhang J, Sun N (2012) Development of multiresidue analysis for twenty phthalate esters in edible vegetable oils by microwave-assisted extraction-gel permeation chromatography-solid phase extraction-gas chromatography-tandem mass spectrometry. J Agric Food Chem 60:5532–5539. https://doi.org/10.1021/jf3009603
Sun J, Huang J, Zhang A, Liu W, Cheng W (2013) Occurrence of phthalate esters in sediments in Qiantang River, China and inference with urbanization and river flow regime. J Hazard Mater 248-249:142–149. https://doi.org/10.1016/j.jhazmat.2012.12.057
Sun J, Pan L, Zhan Y, Lu H, Tsang DCW, Liu W, Wang X, Li X, Zhu L (2016) Contamination of phthalate esters, organochlorine pesticides and polybrominated diphenyl ethers in agricultural soils from the Yangtze River Delta of China. Sci Total Environ 544:670–676. https://doi.org/10.1016/j.scitotenv.2015.12.012
Xu D, Deng X, Fang E, Zheng X, Zhou Y, Lin L, Chen L, Wu M, Huang Z (2014) Determination of 23 phthalic acid esters in food by liquid chromatography tandem mass spectrometry. J Chromatogr A 1324:49–56
Xu G, Li F, Wang Q (2008) Occurrence and degradation characteristics of dibutyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) in typical agricultural soils of China. Sci Total Environ 393:333–340. https://doi.org/10.1016/j.scitotenv.2008.01.001
Yan H, Cheng X, Liu B (2011) Simultaneous determination of six phthalate esters in bottled milks using ultrasound-assisted dispersive liquid-liquid microextraction coupled with gas chromatography. J Chromatogr B Anal Technol Biomed Life Sci 879:2507–2512. https://doi.org/10.1016/j.jchromb.2011.07.001
Yang J, Li Y, Wang Y, Ruan J, Zhang J, Sun C (2015) Recent advances in analysis of phthalate esters in foods. Trends Anal Chem 72:10–26. https://doi.org/10.1016/j.trac.2015.03.018
Zhang H, Chen X, Jiang X (2011) Determination of phthalate esters in water samples by ionic liquid cold-induced aggregation dispersive liquid–liquid microextraction coupled with high-performance liquid chromatography. Anal Chim Acta 689:137–142. https://doi.org/10.1016/j.aca.2011.01.024
Zhou RZ, Jiang J, Mao T, Zhao YS, Lu Y (2016) Multiresidue analysis of environmental pollutants in edible vegetable oils by gas chromatography-tandem mass spectrometry. Food Chem 207:43–50. https://doi.org/10.1016/j.foodchem.2016.03.071
Zhu H, Cui S, Wang W, Miao J, Feng J, Chen J (2014) Determination of phthalate esters in wine using dispersive liquid–liquid microextraction and gas chromatography. Anal Lett 47:1874–1887. https://doi.org/10.1080/00032719.2014.891126
Acknowledgments
This study was supported by the National Key Research and Development Program of China (2017YFC1600705), National Natural Science Foundation of China (31701519), and the Central Public-interest Scientific Institution Basal Research Fund (1610072017004).
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Yanyang Xu, Rui Weng, Yushun Lu, Xinlu Wang, Dan Zhang, Yun Li, Jing Qiu, and Yongzhong Qian declare that they have no conflict of interest.
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Xu, Y., Weng, R., Lu, Y. et al. Evaluation of Phthalic Acid Esters in Fish Samples Using Gas Chromatography Tandem Mass Spectrometry with Simplified QuEChERS Technique. Food Anal. Methods 11, 3293–3303 (2018). https://doi.org/10.1007/s12161-018-1313-z
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DOI: https://doi.org/10.1007/s12161-018-1313-z