A sensitive and high-efficiency method for simultaneous detection of pyraclostrobin, prochloraz, and its metabolite in apple and soil based on QuEChERS pretreatment combined with rapid resolution liquid chromatography tandem mass spectrometry was established and validated. The limits of quantification of three compounds in two matrixes were 0.005 mg kg−1. The average recoveries of pyraclostrobin, prochloraz, and 2,4,6-trichlorophenol in soil matrix were in the ranges of 87–105%, 86–95%, and 90–96%, respectively, with all the relative standard deviations (RSDs) of < 9.6%, while recoveries were 89–93%, 83–97%, and 89–101% in apple with the RSDs of < 6.5% at three spiking levels. For verify the applicability of this method, the real samples from three representative locations were detected. The degradation behaviors and residue distributions of pyraclostrobin and prochloraz and its metabolite in apple ecosystem were investigated. The field experiment data showed that the dissipation of pyraclostrobin and prochloraz in apple and soil followed pseudo-first-order kinetic models. The half-lives of pyraclostrobin in soil and apple were 8.6–19.8 and 7.9–15.1 days, while prochloraz were 8.9–21 and 5.8–12.4 days. The highest terminal residue of total prochloraz and pyraclostrobin in apple, after spraying three to four times with the interval of 28 days, was far below the maximum residue limits recommended by China. This research could provide guidance on a reasonable usage of prochloraz and pyraclostrobin in apple orchard.
Pyraclostrobin Prochloraz Metabolite Apple QuEChERS method RRLC-MS/MS
Limits of detection
Limits of quantification
Maximum residue limits
Rapid resolution liquid chromatography tandem mass spectrometry
Relative standard deviations
Emulsion in water
This is a preview of subscription content, log in to check access.
This study was funded by the National Natural Science Foundation of China (grant no. 21677009) and the Natural Science Foundation of Beijing (grant no. 8162029).
Compliance with Ethical Standards
Conflict of Interest
X.F. declares that she has no conflict of interest. S.Z. declares that he has no conflict of interest. X.C. declares that she has no conflict of interest. J.H. declares that she has no conflict of interest.
This article does not contain any studies with human participants or animals performed by any of the authors.
Informed consent was obtained from all individual participants included in the study.
Aktar MW, Sengupta D, Purkait S, Ganguly M, Paramasivam M (2008) Degradation dynamics and dissipation kinetics of an imidazole fungicide (prochloraz) in aqueous medium of varying pH. Interdiscipl Toxicolog 1(3–4):203Google Scholar
Arts ICW, Hollman PCH, Bueno de Mesquita HB et al (2001) Dietary catechins and epithelial cancer incidence: the Zutphen elderly study. Int J Cancer 92:298–302CrossRefGoogle Scholar
Bajpai VK, Choi SW, Cho MS et al (2009) Isolation and morphological identification of apple anthracnose fungus of Colletotrichum sp. KV-21. Korean J Environ Agric 28:442–446CrossRefGoogle Scholar
Bao Y, Liu Q, Chen J, Lin Y, Wu B, Xie J (2012) Quantification of nerve agent adducts with albumin in rat plasma using liquid chromatography-isotope dilution tandem mass spectrometry. J Chromatogr A 1229:164–171 (in Chinese)CrossRefGoogle Scholar
Bartlett DW, Clough JM, Godwin JR et al (2002) The strobilurin fungicides. Pest Manag Sci 58:649–662CrossRefGoogle Scholar
Cengiz MF, Catal M, Erler F, Bilgin AK (2014) Rapid and sensitive determination of the prochloraz residues in the cultivated mushroom, Agaricus bisporus (Lange) Imbach. Anal Methods UK 6(6):1970–1976CrossRefGoogle Scholar
Davis PA, Polagruto JA, Valacchi G, Phung A, Soucek K, Keen CL et al (2006) Effect of apple extracts on NF-B activation in human umbilical vein endothelial cells. Exp Biol Med 231:594–598CrossRefGoogle Scholar
De PM, Taccheo BM, Damiano V, Fabbro D, Bruno R (1997) Simplified determination of combined residues of prochloraz and its metabolites in vegetable, fruit and wheat samples by gas chromatography. J Chromatogr A 765(1):127Google Scholar
de Oliveira LA, Pacheco HP, Scherer R (2016) Flutriafol and pyraclostrobin residues in Brazilian green coffees. Food Chem 190:60–63CrossRefGoogle Scholar
Feskanich D, Ziegler RG, Michaud DS et al (2000) Prospective study of fruit and vegetable consumption and risk of lung cancer among men and women. J Natl Cancer Inst 92:1812–1823CrossRefGoogle Scholar
Fulcher JM, Wayment DG, White PM Jr et al (2014) Pyraclostrobin wash-off from sugarcane leaves and aerobic dissipation in agricultural soil. J Agric Food Chem 62(10):2141–2146Google Scholar
Fuse JI, Kanamori H, Ideyoshi N (2010) Determination of prochloraz and its metabolites in fruits and vegetables by GC. J Food Hyg Soc Jpn 41:61–651CrossRefGoogle Scholar
Guo X, Wu W, Song N et al (2017) Residue dynamics and risk assessment of pyraclostrobin in rice, plants, hulls, field soil, and paddy water. Hum Ecol Risk Assess 23:67–81CrossRefGoogle Scholar
Hameed BH (2007) Equilibrium and kinetics studies of 2,4,6-trichlorophenol adsorption onto activated clay. Colloids Surf A 307(1–3):45–52CrossRefGoogle Scholar
Hameed BH, Tan IAW, Ahmad AL (2008) Adsorption isotherm, kinetic modeling and mechanism of 2,4, 6-trichlorophenol on coconut husk-based activated carbon. Chem Eng J 144:235–244CrossRefGoogle Scholar
Hanafi A, Garau VL, Caboni P, Sarais G, Cabras P (2010) Minor crops for export: a case study of boscalid, pyraclostrobin, lufenuron and lambda-cyhalothrin residue levels on green beans and spring onions in Egypt. J Environ Sci Health B 45(6):493–500CrossRefGoogle Scholar
Lafuente MT, Tadeo JL (2015) High performance liquid chromatography determination of prochloraz residues in citrus fruit. J Sep Sci 7(5):268–270Google Scholar
Lee DH, Kim D, Jeon Y et al (2007) Molecular and cultural characterization of Colletotrichum spp.causing bitter rot of apples in Korea. Plant Pathol J 23:37–44CrossRefGoogle Scholar
Lehotay SJ, Kyungae S, Hyeyoung K et al (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1217:2548–2560CrossRefGoogle Scholar
Li H, Li J, Hou C et al (2010) A sub-nanomole level electrochemical method for determination of prochloraz and its metabolites based on medical stone doped disposable electrode. Talanta 83:591–595CrossRefGoogle Scholar
Li K, Wu S, Xu S et al (2016) Oiling out and polymorphism control of pyraclostrobin in cooling crystallization. Ind Eng Chem Res 55:11631–11637CrossRefGoogle Scholar
Lu P, Wu C, Shi Q et al (2016) A sensitive and validated method for determination of T-2 and HT-2 toxin residues in shrimp tissues by LC-MS/MS. Food Anal Methods 9:1–15CrossRefGoogle Scholar
Navickiene S, Ribeiro ML (2005) An alternative LC-UV procedure for the determination of prochloraz residues in fruits. J Braz Chem Soc 16(2):157–162CrossRefGoogle Scholar
Niessen WMA, Manini P, Andreoli R (2006) Matrix effects in quantitative pesticide analysis using liquid chromatography-mass spectrometry. Mass Spectrom Rev 25:881–899CrossRefGoogle Scholar
Patyal SK, Sharma ID, Chandel RS et al (2013) Dissipation kinetics of trifloxystrobin and tebuconazole on apple (Malus domestica) and soil: a multi-location study from north western Himalayan region. Chemosphere 92:949–954CrossRefGoogle Scholar
Polese L, Jardim EFG, Navickiene S et al (2006) Prochloraz residue levels in ginger submitted to Sportak 450 CE″ postharvest treatment. Eclética Quím 31(2):59–62CrossRefGoogle Scholar
Shabeer TPA, Girame R, Hingmire S, Banerjee K, Sharma AK, Oulkar D et al (2015) Dissipation pattern, safety evaluation, and generation of processing factor (PF) for pyraclostrobin and metiram residues in grapes during raisin preparation. Environ Monit Assess 187(2):4268CrossRefGoogle Scholar
Vinggaard AM, Nellemann C, Dalgaard M et al (2002) Antiandrogenic effects in vitro and in vivo of the fungicide prochloraz. Toxicol Sci 69:344–353CrossRefGoogle Scholar
Yoon H, Liu RH (2007) Effect of selected phytochemicals and apple extracts on NF-B activation in human breast cancer MCF-7 cells. J Agric Food Chem 55:3167–3173CrossRefGoogle Scholar
Zhang F, Wang L, Li Z, Wu D, Pan H, Pan C (2012) Residue dynamics of pyraclostrobin in peanut and field soil by QuEChERS and LC–MS/MS. Ecotoxicol Environ Saf 78(2):116–122CrossRefGoogle Scholar
Zou Z, He Z, Li H, Han P, Tang J, Xi C, Li Y, Zhang L, Li X (2012) Development and application of a method for the analysis of two trichothecenes: deoxynivalenol and T-2 toxin in meat in China by HPLC-MS/MS. Meat Sci 90:613–617 (in Chinese)CrossRefGoogle Scholar