Advertisement

Analytical and Bioanalytical Chemistry

, Volume 411, Issue 11, pp 2447–2460 | Cite as

Multi-residue analysis of plant growth regulators and pesticides in traditional Chinese medicines by high-performance liquid chromatography coupled with tandem mass spectrometry

  • Zuliang Luo
  • Lixia Zhang
  • Yan Mou
  • Shengrong Cui
  • Zhe Gu
  • Jing Yu
  • Xiaojun MaEmail author
Research Paper

Abstract

A multi-residue method was developed for the simultaneous determination of 24 plant growth regulators (PGRs) and 11 representative pesticides that were widely applied in plants used in traditional Chinese medicines (TCMs) by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The method was validated taking into consideration EU guidelines; calibration curves for all of the targeted analytes showed correlation coefficients (γ2) higher than 0.9901. The limits of detection (LOD) ranged from 0.2 to 8 μg/kg. The average recovery for all analytes in spiked samples ranged from 63.18 to 127.23%, with a relative standard deviation of ≤ 15%. The proposed method has been applied to 480 batches of TCM samples, including 34 species of medicinal plants, from the TCM market. The results showed that 14 PGRs and 5 pesticides were detected, including choline chloride, chlormequat, paclobutrazol, uniconazole, phoxim, etc. Among them, there were high detection rates for chlormequat (40%), choline chloride (100%), atonik (73.75%), abscisic acid (80.83%), and indole-3-acetic acid (41.25%). The residual level of paclobutrazol in Ophiopogonis radix exceeded the recommended maximum residue limits (MRLs) according to GB 2763–2016. In addition, 14 agrochemicals used in TCM planting were collected and detected; the result showed various PGRs were detected in samples registered as fertilizer. These results indicate that PGRs and pesticides were widely used in the cultivation of medicinal plants, especially for radix and rhizome herbs. The residue of targeted PGRs and pesticides in TCM samples from this study have a high frequency and high level.

Graphical abstract

Keywords

Multi-residue Plant growth regulators Pesticides TCMs HPLC-MS/MS 

Notes

Funding

This work was supported by the CAMS Innovation Fund for Medical Sciences (CIFMS) (No. 2017-I2M-1-013) and Beijing Natural Science Foundation (No. 5172028).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflicts of interest.

Supplementary material

216_2019_1691_MOESM1_ESM.pdf (655 kb)
ESM 1 (PDF 654 kb)
216_2019_1691_MOESM2_ESM.xlsx (76 kb)
Table S2 (XLSX 76 kb)
216_2019_1691_MOESM3_ESM.xlsx (19 kb)
Table S3 (XLSX 18.7 kb)

References

  1. 1.
    Hwang BH, Lee MR. Solid-phase microextraction for organochlorine pesticide residues analysis in Chinese herbal formulations. J Chromatogr A. 2000;898(2):245–56.CrossRefGoogle Scholar
  2. 2.
    General Office of the State Council. Plan for protection and development of Chinese medicinal materials (2015–2020). 2015. http://www.gov.cn/zhengce/content/2015-04/27/content_9662.htm. Accessed 4 Oct 2018.
  3. 3.
    Lu Q, Wu JH, Yu QW, Feng YQ. Using pollen grains as novel hydrophilic solid-phase extraction sorbents for the simultaneous determination of 16 plant growth regulators. J Chromatogr A. 2014;1367:39–47.CrossRefGoogle Scholar
  4. 4.
    Ilias IF, Maksimovi VM, Giannakoula AE, Maksimovi JJD, Ivanovi BDŽ. The effects of plant growth regulators on growth, yield, and phenolic profile of lentil plants. J Food Compos Anal. 2012;28(1):46–53.CrossRefGoogle Scholar
  5. 5.
    Cao S, Zhou X, Xi C, Tang B, Ding X, Zhang L, et al. Cleaning up vegetable samples using a modified “QuEChERS” procedure for the determination of 17 plant growth regulator residues by ultra high performance liquid chromatography–triple quadrupole linear ion trap mass spectrometry. Food Anal Methods. 2016;9(7):2097–104.CrossRefGoogle Scholar
  6. 6.
    Zhao X, Mu Y, Yang M. A simple multi-residue method for determination of plant growth retardants in Ophiopogon japonicus and soil using ultra-performance liquid chromatography-tandem mass spectrometry. Chemosphere. 2018;8(1):329–36.CrossRefGoogle Scholar
  7. 7.
    Zhai YY, Guo BL, Huang WH. Detection of agent “zhuanggenling” and investigation of utilization of plant growth retardants in traditional Chinese medicine cultivation. J Chin Pharm. 2015;40:414–20.Google Scholar
  8. 8.
    Wei H, Wang Y, Jin HY, Ma SC. Research progress in plant growth regulator and their application, content determination in planting traditional Chinese medicine. Chin Pharm J. 2016;51:81–5.Google Scholar
  9. 9.
    Ministry of Health Labour and Welfare, Japan. Maximum residue limits (MRLs) list of agricultural chemicals in foods. 2006. http://www.m5.ws001.squarestart.ne.jp/foundation/search.html. Accessed 15 Oct 2018.
  10. 10.
    United States Environmental Protection Agency. Index to pesticide chemical names, part 180 tolerance information for pesticide chemicals in food and feed commodities. 2009. https://www.ecfr.gov/cgi-bin/text-idx?c=ecfr&sid=1a0ecaf51aa3dba662c9cbf1b4336eaf&tpl=/ecfrbrowse/Title40/40cfr180_main_02.tpl. Accessed 15 Oct 2018.
  11. 11.
    European Commission. Commission Regulation (EU) No 396/2005 of 23 February 2005 Amending Council Directive 91/414/EEC on maximum residue levels of pesticides in or on food and feed of plant and animal origin. 2005. http://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/public/?event=download.MRL. Accessed 15 Oct 2018.
  12. 12.
    Food and Agriculture Organization/World Health Organization. Food standards programme. Codex Alimentarius Commission. Twenty-seventh Session, Geneva, Switzerland, 28 June 03 July 2004. 2004. http://www.fao.org/fao-who-codexalimentarius/codex-texts/dbs/pestres/pesticides/en/. Accessed 15 Oct 2018.
  13. 13.
    National Health and Family Planning Commission and Ministry of Agriculture of the People's Republic of China, China national food safety standard-maximum residue limits for pesticides in food (GB 2763-2016). 2016. http://www.nhfpc.gov.cn/sps/s7891/201702/ed7b47492d7a42359f839daf3f70eb4b.shtml. Accessed 15 Oct 2018.
  14. 14.
    Chinese Pharmacopeia Commission. Pharmacopoeia of People’s Republic of China. Beijing: Chemical Medical Science Press; 2015.Google Scholar
  15. 15.
    Qian G, Wang L, Wu Y, Qi Z, Qin S, Yang L, et al. A monoclonal antibody-based sensitive enzyme-linked immunosorbent assay (ELISA) for the analysis of the organophosphorous pesticides chlorpyrifos-methyl in real samples. Food Chem. 2009;117(2):364–70.CrossRefGoogle Scholar
  16. 16.
    Jiang XX, Shi HY, Wu N, Wang MH. Development of an enzyme-linked immunosorbent assay for diniconazole in agricultural samples. Food Chem. 2011;125(4):1385–9.CrossRefGoogle Scholar
  17. 17.
    Brinkman JHW, Dijk AGV, Wagenaar R, Quirijns JK. Determination of daminozide residues in apples using gas chromatography with nitrogen-phosphorus detection. J Chromatogr A. 1996;723(2):355–60.CrossRefGoogle Scholar
  18. 18.
    Xu R, Wu J, Liu Y, Zhao R, Chen B, Yang M, et al. Analysis of pesticide residues using the quick easy cheap effective rugged and safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection. Chemosphere. 2011;84(7):908–12.CrossRefGoogle Scholar
  19. 19.
    Das AK, Prasad K. Extraction of plant growth regulators present in Kappaphycus alvarezii sap using imidazolium based ionic liquids: detection and quantification by using HPLC-DAD technique. Anal Methods. 2015;7(21):9064–7.CrossRefGoogle Scholar
  20. 20.
    Müller A, Düchting P, Weiler EW. A multiplex GC-MS/MS technique for the sensitive and quantitative single-run analysis of acidic phytohormones and related compounds, and its application to Arabidopsis thaliana. Planta. 2002;216(1):44–56.CrossRefGoogle Scholar
  21. 21.
    Du G, Song Y, Wang Y. Rapid simultaneous determination of multiple pesticide residues in traditional Chinese medicines using programmed temperature vaporizer injection–fast gas chromatography coupled with mass spectrometry. J Sep Sci. 2015;34(23):3372–82.CrossRefGoogle Scholar
  22. 22.
    Riediker S, Obrist H, Varga N, Stadler RH. Determination of chlormequat and mepiquat in pear, tomato, and wheat flour using on-line solid-phase extraction (Prospekt) coupled with liquid chromatography-electrospray ionization tandem mass spectrometry. J Chromatogr A. 2002;966(1):15–23.CrossRefGoogle Scholar
  23. 23.
    Ma L, Zhang H, Xu W, He X, Yang L, Luo Y, et al. Simultaneous determination of 15 plant growth regulators in bean sprout and tomato with liquid chromatography–triple quadrupole tandem mass spectrometry. Food Anal Methods. 2013;6(3):941–51.CrossRefGoogle Scholar
  24. 24.
    Kim KG, Park DW, Kang GR, Kim TS, Yang Y, Moon SJ, et al. Simultaneous determination of plant growth regulator and pesticides in bean sprouts by liquid chromatography–tandem mass spectrometry. Food Chem. 2016;208(7):239–44.CrossRefGoogle Scholar
  25. 25.
    European Commission. Document no. SANTE/11813/2017, Guidance document on analytica quality control and method validation procedures for pesticides residues analysis in food and feed. 2018. https://ec.europa.eu/food/sites/food/files/plant/docs/pesticides_mrl_guidelines_wrkdoc_2017-11813.pdf. Accessed 24 Mar 2018.
  26. 26.
    Chen L, Song F, Liu Z, Zhong Z, Xing J, Liu S. Multi-residue method for fast determination of pesticide residues in plants used in traditional chinese medicine by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. J Chromatogr A. 2012;1225(1):132–40.CrossRefGoogle Scholar
  27. 27.
    Luo Z, Shi H, Zhang K, Qin X, Guo Y, Ma X. Liquid chromatography with tandem mass spectrometry method for the simultaneous determination of multiple sweet mogrosides in the fruits of Siraitia grosvenorii and its marketed sweeteners. J Sep Sci. 2016;39(21):4124–35.CrossRefGoogle Scholar
  28. 28.
    Xu D, Huang H, Lu M, Zhou S, Zhou Y. Simultaneous determination of 21 plant growth regulators in various fruits using QuEChERS coupled with an HPLC-MS/MS technique. 2015. https://www.agilent.com/cs/library/applications/5991-5506EN.pdf. Accessed 12 Sep 2018.
  29. 29.
    Liu C, Dou X, Zhang L, Li Q, Qin J, Duan Y, et al. Determination of triazine herbicides and their metabolites in multiple medicinal parts of traditional Chinese medicines using streamlined pretreatment and UFLC-ESI-MS/MS. Chemosphere. 2017;190:103–13.CrossRefGoogle Scholar
  30. 30.
    Danezis GP, Anagnostopoulos CJ, Liapis K, Koupparis MA. Multi-residue analysis of pesticides, plant hormones, veterinary drugs and mycotoxins using HILIC chromatography- MS/MS in various food matrices. Anal Chim Acta. 2016;942:121–38.CrossRefGoogle Scholar
  31. 31.
    Wei H, Jin HY, Wang Y, Ma SC. Simultaneous determination of 23 plant growth regulator residues in Chinese materia medica by ultra performance liquid chromatography-tandem mass spectrometry. Chin Tradit Herb Drugs. 2017;48(8):1653–60.Google Scholar
  32. 32.
    Sapozhnikova Y, Lehotay SJ. 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 Acta. 2013;758(1):80–92.CrossRefGoogle Scholar
  33. 33.
    Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ. 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. 2003;86(2):412–31.Google Scholar
  34. 34.
    Koesukwiwat U, Lehotay SJ, Mastovska K, Dorweiler KJ, Leepipatpiboon N. Extension of the QuEChERS method for pesticide residues in cereals to flaxseeds, peanuts, and doughs. J Agric Food Chem. 2010;58(10):5950.CrossRefGoogle Scholar
  35. 35.
    Golge O, Kabak B. Evaluation of QuEChERS sample preparation and liquid chromatography-triple-quadrupole mass spectrometry method for the determination of 109 pesticide residues in tomatoes. Food Chem. 2015;176:319–32.CrossRefGoogle Scholar
  36. 36.
    Choi S, Kim S, Jin YS, Kim MK, Kim JH. Development and verification for analysis of pesticides in eggs and egg products using QuEChERS and LC–MS/MS. Food Chem. 2015;173:1236–42.CrossRefGoogle Scholar
  37. 37.
    Tomasini D, Sampaio MR, Caldas SS, Buffon JG, Duarte FA, Primel EG. Simultaneous determination of pesticides and 5-hydroxymethylfurfural in honey by the modified QuEChERS method and liquid chromatography coupled to tandem mass spectrometry. Talanta. 2012;99(18):380–6.CrossRefGoogle Scholar
  38. 38.
    Orozco FA, Cole DC, Forbes G, Kroschel J, Wanigaratne S, Arica D. Monitoring adherence to the international code of conduct: highly hazardous pesticides in central Andean agriculture and farmers’ rights to health. Int J Occup Environ Health. 2009;15(3):255–68.CrossRefGoogle Scholar
  39. 39.
    Kholodar AV, Sidorova KK, Shumny VK. Effects of synthetic auxin (2,4-D) on the level of indolyl-3-acetic acid in cultivars and supernodulating mutants of pea (Pisum sativum L.). Dokl Biol Sci. 2002;386(1–6):460–1.CrossRefGoogle Scholar
  40. 40.
    Von SKA. Systematic review of carcinogenic outcomes and potential mechanisms from exposure to 2,4-D and MCPA in the environment. J Toxicol. 2013;2013(1):371610.Google Scholar
  41. 41.
    Guha N, Roos AD, Kogevinas M, Loomis D, Rushton L. O04-3 IARC working group meta-analysis of 2,4-d exposure and the risk of NHL. Occup Environ Med. 2016;73(Suppl 1):A8.1–A8.Google Scholar
  42. 42.
    Zhai YY, Guo BL, Cheng M. Review on application of plant growth retardants in medicinal plants cultivation. Chin Pharm J. 2013;38(17):2739–44.Google Scholar
  43. 43.
    Gonçalves ICR, Araújo ASF, Carvalho EMS, Carneiro RFV. Effect of paclobutrazol on microbial biomass, respiration and cellulose decomposition in soil. Eur J Soil Biol. 2009;45(3):235–8.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Zuliang Luo
    • 1
  • Lixia Zhang
    • 1
    • 2
  • Yan Mou
    • 2
  • Shengrong Cui
    • 1
  • Zhe Gu
    • 1
  • Jing Yu
    • 2
  • Xiaojun Ma
    • 1
    Email author
  1. 1.Institute of Medicinal Plant Development, Chinese Academy of Medical SciencesPeking Union Medical CollegeBeijingChina
  2. 2.Yunnan Branch, Institute of Medicinal Plant DevelopmentChinese Academy of Medical SciencesJing HongChina

Personalised recommendations