Abstract
A highly sensitive ultra-performance liquid chromatographic method with diode-array detection was developed for residue determination of thiophanate methyl (TM), cyromazine (CYR), and their metabolites, carbendazim (MBC) and melamine (MEL). Edible fungi samples were treated using accelerated solvent extraction (ASE) followed by cleanup with solid-phase extraction (SPE). Under optimized conditions, good linearity was achieved with a correlation coefficient (r 2) of ≥0.9998. The limit of quantification was 0.36, 0.24, 0.4, and 0.5 μg kg−1 for MEL, CYR, MBC, and TM, respectively. The intra- and interday precisions (in terms of the relative standard deviation (RSD)) of the four analytes were in the range of 2.3–4.5 and 3.1–6.3 %, respectively. The recoveries for TM, MBC, CYR, and MEL in four edible fungi samples at three spiked levels of 0.6, 6, and 20 μg kg−1 for TM and MBC and 0.4, 4, and 20 μg kg−1 for CYR and MEL were in the range of 82–105 % with RSDs below 5.6 %. The proposed method can be used for the routine determination of CYR and MEL in edible fungi with high sensitivity and accuracy as well as low consumption of reagents.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Explore related subjects
Discover the latest articles and news from researchers in related subjects, suggested using machine learning.References
Anastassiades M, Schwack W (1998) Analysis of carbendazim, benomyl, thiophanate methyl and 2,4-dichlorophenoxyacetic acid in fruits and vegetables after supercritical fluid extraction. J Chromatogr A 825:45
Bai B, Dong MF, Xing ZT, Zhao XY (2011) Determination of 67 different pesticide residues in agaricus bisporus and lentinus edodes fruit bodies by gas chromatography–mass spectrometry. Acta Edulis Fungi 1:63
Chou SS, Hwang DF, Lee HF (2003) High performance liquid chromatographic determination of cyromazine and its derivative melamine in poultry, meats, and eggs. J Food Drug Anal 11:290
Cook AM, Hutter RS (1981) s-Triazines as nitrogen sources for bacteria. J Agric Food Chem 29:1135
GB 2763-2012 Chinese National food safety standard: maximum residue limits for pesticides in food
GB/T 22388-2008 The National Standards of the People’s Republic of China, Determination of melamine in raw milk and dairy products
Liu ZM, Liu WH, Wu QH, Zang XH, Zhou X, Zeng X, Wang Z (2012) Determination of carbendazim and thiabendazole in apple juice by hollow fibre-based liquid phase microextraction-high performance liquid chromatography with fluorescence detection. J Environ Anal Chem 92:582
MMnick RL, Boorman GA, Haseman JK, Montali RJ, Huff J (1984) Urolithiasis and bladder carcinogenicity of melamine in rodents. Toxicol Appl Pharmacol 72:292
Nakamura M, Furumi Y, Watanabe F, Mizukoshi K, Taniguchi M, Nemoto S (2011) Determination of carbendazim, thiophanate, thiophanate-methyl and benomyl residues in agricultural products by liquid chromatography-tandem mass spectrometry. Food Hyg Saf Sci 52:148
Roses M, Canals I, Allemann H, Siigur K, Bosch E (1996) Retention of ionizable compounds on HPLC. 2. Effect of pH, ionic strength, and mobile phase composition on the retention of weak acids. Anal Chem 68:4094
Sancho JV, Ibáñez M, Grimalt S, Pozo ÓJ, Hernández F (2005) Residue determination of cyromazine and its metabolite melamine in chard samples by ion-pair liquid chromatography coupled to electrospray tandem mass spectrometry. Anal Chim Acta 530:237
Sandahl M, Mathiasson L, Jonsson JA (2000) Determination of thiophanate-methyl and its metabolites at trace level in spiked natural water using the supported liquid membrane extraction and the microporous membrane liquid–liquid extraction techniques combined on-line with high-performance liquid chromatography. J Chromatogr A 893:123
Shang BR, Chen YQ, Wang ZY, Yang WJ, Zhang LY (2011) Development and validation of a gas chromatography–mass spectrometry method for the simultaneous determination of melamine and cyromazine in animal feeds. J Anim Vet Adv 10:73
Singh SB, Foster GD, Khan SU (2007) Determination of thiophanate methyl and carbendazim residues in vegetable samples using microwave-assisted extraction. J Chromatogr A 1148:152
Squadrone S, Ferro GL, Marchis D, Mauro C, Palmegiano P, Amato G, Poma GE, Abete MC (2010) Determination of melamine in feed: validation of a gas chromatography–mass spectrometry method according to 2004/882/CE regulation. Food Control 21:714
Sun HW, Ge XS, Lv YK, Wang AB (2012) Application of accelerated solvent extraction in the analysis of organic contaminants, bioactive and nutritional compounds in food and feed. J Chromatogr A 1237:1
Tang J, Cao HQ, Hua RM, Tang F, Yue YD (2011) A multiresidue screening method for the determination of pesticides in edible fungi. J Anhui Agric University 38:549
Veneziano A, Vacca G, Arana S, De Simone F, Rastrelli L (2004) Determination of carbendazim, thiabendazole and thiophanate-methyl in banana (Musa acuminata) samples imported to Italy. Food Chem 87:383
Vonk JW, Sijpesteijn AK (1971) Methyl benzimidazol-2-ylcarbamate, the fungitoxic principle of thiophanate-methyl. Pestic Sci 2:160
WHO (2010) Media centre. International experts limit melamine levels in food
Yang H, Zhao ZH, Wang RX, Dong MF, Song WG (2011) Safety and risk assessment of pesticide residues in edible fungi. Acta Edulis Fungi 18:105
Yokley RA, Mayer LC, Rezaaiyan R, Manuli ME, Cheung MW (2000) Analytical method for the determination of cyromazine and melamine residues in soil using LC-UV and GC-MSD. J Agric Food Chem 48:3352
Yu H, Tao Y, Chen D, Wang Y, Liu Z, Pan Y, Huang L, Peng D, Dai M, Liu Z, Yuan Z (2010) Development of a high performance liquid chromatography method and a liquid chromatography–tandem mass spectrometry method with pressurized liquid extraction for simultaneous quantification and confirmation of cyromazine, melamine and its metabolites in foods of animal origin. Anal Chim Acta 682:48
Zhang ZY, Gong Y, Shan WL, Jian Q, Shen Y, Liu XJ (2012) Determination of thiophanate-methyl and carbendazim in cucumber and soil by QuEChERS-high performance liquid chromatography-triple quadrupole tandem massspectrometry. Chin J Chromatogr 30:91
Zhu XL, Wang SH, Liu Q, Xu Q, Xu SX, Chen HL (2009) Determination of residues of cyromazine and its metabolite, melamine, in animal-derived food by gas chromatography–mass spectrometry with derivatization. J Agric Food Chem 57:11075
Acknowledgments
This work was supported by the Natural Science Foundation of Hebei Province (B2008000583), the sustentation Plan of Science and Technology of Hebei Province (no. 10967126D), and the National 12th Five-Year Major Science and Technology Projects on Control and Prevention of Water Pollution (no. 2012ZX07203-003).
Conflict of Interest
Xingqiang Wu declares that he has no conflict of interest. Xusheng Ge declares that he has no conflict of interest. Shuxuan Liang declares that she has no conflict of interest. Hanwen Sun declares that he has no conflict of interest. This article does not contain any studies with human or animal subjects.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wu, X., Ge, X., Liang, S. et al. A Highly Sensitive Method for the Determination of Thiophanate Methyl, Cyromazine, and Their Metabolites in Edible Fungi by Ultra-Performance Liquid Chromatography Using Accelerated Solvent Extraction and Cleanup with Solid-Phase Extraction. Food Anal. Methods 7, 774–782 (2014). https://doi.org/10.1007/s12161-013-9680-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-013-9680-y