Skip to main content
SpringerLink
Log in

Survey of pyrrolizidine alkaloids in teas and herbal teas on the Swiss market using HPLC-MS/MS

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Pyrrolizidine alkaloids (PAs) are a large class of natural compounds amongst which the esterified 1,2-unsaturated necine base is toxic for humans and livestock. In the present study, a method was developed and validated for the screening and quantification of nine PAs and one PA N-oxide in teas (Camellia sinensis (L.) O. Kuntze) and herbal teas (camomile, fennel, linden, mint, rooibos, verbena). Samples were analysed by HPLC on a RP-column, packed with sub-2 μm core-shell particles, and quantified using tandem mass spectrometry operating in the positive electrospray ionisation mode. These PAs and some of their isomers were detected in a majority of the analysed beverages (50/70 samples). In 24 samples, PA concentrations were above the limit of quantification and the sum of the nine targeted PAs was between 0.021 and 0.954 μg per cup of tea. Thus, in some cases, total concentrations exceed the maximum daily intake recommended by the German Federal Institute for Risk Assessment and the UK’s Committee On Toxicity (i.e. 0.007 μg kg−1 bw).

ᅟ

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Codex Alimentarius Commission (2011) Discussion paper on pyrrolizidine alkaloids. CX/CF 11/5/14

  2. Zhang F, Wang C-H, Xiong A-Z, Wang W, Yang L, Branford-White CJ, Wang Z-T, Bligh SWA (2007) Quantitative analysis of total retronecine esters-type pyrrolizidine alkaloids in plant by high performance liquid chromatography. Anal Chim Acta 605:94–101. doi:10.1016/j.aca.2007.10.021

    Article  CAS  Google Scholar 

  3. Fu PP, Xia Q, Lin G, Chou MW (2004) Pyrrolizidine alkaloids: genotoxicity, metabolism enzymes, metabolic activation, and mechanisms. Drug Metab Rev 36:1–55. doi:10.1081/dmr-120028426

    Article  CAS  Google Scholar 

  4. Bartkowski J-PB, Wiedenfeld H, Roeder E (1997) Quantitative photometric determination of senkirkine in Farfarae Folium. Phytochem Anal 8:1–4. doi:10.1002/(SICI)1099-1565(199701)8:1<1::AID-PCA328>3.0.CO;2-H

    Article  CAS  Google Scholar 

  5. BfR (2013) Pyrrolizidine alkaloids in herbal teas and teas

  6. Wiedenfeld H, Edgar J (2011) Toxicity of pyrrolizidine alkaloids to humans and ruminants. Phytochem Rev 10:137–151. doi:10.1007/s11101-010-9174-0

    Article  CAS  Google Scholar 

  7. Li YH, Kan WLT, Li N, Lin G (2013) Assessment of pyrrolizidine alkaloid-induced toxicity in an in vitro screening model. J Ethnopharmacol 150:560–567. doi:10.1016/j.jep.2013.09.010

    Article  CAS  Google Scholar 

  8. Bach N, Thung SN, Schaffner F (1989) Comfrey herb tea-induced hepatic veno-occlusive disease. Am J Med 87:97–99

    Article  CAS  Google Scholar 

  9. Gyorik S, Stricker H (2009) Severe pulmonary hypertension possibly due to pyrrolizidine alkaloids in polyphytotherapy. Swiss Med Wkly 139:210–211

    CAS  Google Scholar 

  10. Kumana CR, Ng M, Lin HJ, Ko W, Wu PC, Todd D (1985) Herbal tea induced hepatic veno-occlusive disease: quantification of toxic alkaloid exposure in adults. Gut 26:101–104

    Article  CAS  Google Scholar 

  11. McGee J, Patrick RS, Wood CB, Blumgart LH (1976) A case of veno-occlusive disease of the liver in Britain associated with herbal tea consumption. J Clin Pathol 29:788–794

    Article  CAS  Google Scholar 

  12. Ridker PN, McDermont WV (1989) Hepatotoxicity due to comfrey herb tea. Am J Med 87:701

    Article  CAS  Google Scholar 

  13. Roulet M, Laurini R, Rivier L, Calame A (1988) Hepatic veno-occlusive disease in newborn infant of a woman drinking herbal tea. J Pediatr 112:433–436

    Article  CAS  Google Scholar 

  14. Spang R (1989) Toxicity of tea containing pyrrolizidine alkaloids. J Pediatr 115:1025

    Article  CAS  Google Scholar 

  15. Sperl W, Stuppner H, Gassner I, Judmaier W, Dietze O, Vogel W (1995) Reversible hepatic veno-occlusive disease in an infant after consumption of pyrrolizidine-containing herbal tea. Eur J Pediatr 154:112–116

    Article  CAS  Google Scholar 

  16. Conseil de l’Institut suisse des produits thérapeutiques (2006) Ordinance on complementary and herbal medicinal products

  17. Committee on toxicity of chemicals in food consumer products and the environment (2008) Statement on pyrrolizidine alkaloids in food

  18. Boppre M, Colegate SM, Edgar JA, Fischer OW (2008) Hepatotoxic pyrrolizidine alkaloids in pollen and drying-related implications for commercial processing of bee pollen. J Agric Food Chem 56:5662–5672. doi:10.1021/jf800568u

    Article  CAS  Google Scholar 

  19. Coulombe Jr RA (2003) Pyrrolizidine alkaloids in foods. In: Advances in food and nutrition research, 45. Academic, 61–99. doi:http://dx.doi.org/10.1016/S1043-4526(03)45003-1

  20. Deinzer ML, Arbogast BL, Buhler DR, Cheeke PR (1982) Gas chromatographic determination of pyrrolizidine alkaloids in goat’s milk. Anal Chem (Washington, DC, U S) 54:1811–1814. doi:10.1021/ac00248a035

  21. Edgar JA, Roeder E, Molyneux RJ (2002) Honey from plants containing pyrrolizidine alkaloids: a potential threat to health. J Agric Food Chem 50:2719–2730. doi:10.1021/jf0114482

    Article  CAS  Google Scholar 

  22. Kempf M, Reinhard A, Beuerle T (2010) Pyrrolizidine alkaloids (PAs) in honey and pollen-legal regulation of PA levels in food and animal feed required. Mol Nutr Food Res 54:158–168. doi:10.1002/mnfr.200900529

    Article  CAS  Google Scholar 

  23. Bosi CF, Rosa DW, Grougnet R, Lemonakis N, Halabalaki M, Skaltsounis AL, Biavatti MW (2013) Pyrrolizidine alkaloids in medicinal tea of Ageratum conyzoides. Rev Bras Farmacogn 23:425–432. doi:10.1590/S0102-695X2013005000028

    Article  CAS  Google Scholar 

  24. Cao Y, Colegate SM, Edgar JA (2013) Persistence of echimidine, a hepatotoxic pyrrolizidine alkaloid, from honey into mead. J Food Compos Anal 29:106–109. doi:10.1016/j.jfca.2012.11.005

    Article  CAS  Google Scholar 

  25. Cramer L, Schiebel H-M, Ernst L, Beuerle T (2013) Pyrrolizidine alkaloids in the food chain: development, validation, and application of a new HPLC-ESI-MS/MS sum parameter method. J Agric Food Chem. doi:10.1021/jf403647u

    Google Scholar 

  26. Griffin CT, Danaher M, Elliott CT, Kennedy DG, Furey A (2013) Detection of pyrrolizidine alkaloids in commercial honey using liquid chromatography-ion trap mass spectrometry. Food Chem 136:1577–1583. doi:10.1016/j.foodchem.2012.02.112

    Article  CAS  Google Scholar 

  27. Griffin CT, Gosetto F, Danaher M, Sabatini S, Furey A (2014) Investigation of targeted pyrrolizidine alkaloids in traditional Chinese medicines and selected herbal teas sourced in Ireland using LC-ESI-MS/MS. Food Addit Contam Part A 31:940–961. doi:10.1080/19440049.2014.900193

    Article  CAS  Google Scholar 

  28. Koleva II, van Beek TA, Soffers AEMF, Dusemund B, Rietjens IMCM (2012) Alkaloids in the human food chain—natural occurrence and possible adverse effects. Mol Nutr Food Res 56:30–52. doi:10.1002/mnfr.201100165

    Article  CAS  Google Scholar 

  29. Tang J, Cheng M, Hattori M (2012) Pyrrolizidine alkaloid profile in a traditional Chinese herbal medicine Chuan Zi Wan (Ligulariae Radix et Rhizoma) by liquid chromatography/electrospray ionization ion trap mass spectrometry. Anal Methods 4:2797–2808. doi:10.1039/c2ay25300c

    Article  CAS  Google Scholar 

  30. EFSA Panel on Contaminants in the Food Chain (CONTAM) (2011) Scientific opinion on pyrrolizidine alkaloids in food and feed. EFSA J 9:2406

    Google Scholar 

  31. Crews C (2013) Methods for analysis of pyrrolizidine alkaloids. In: Mérillon J-M, Ramawat KG (eds) Natural products. Springer, Berlin, pp 1049–1068. doi:10.1007/978-3-642-22144-6_186

    Chapter  Google Scholar 

  32. Guillarme D, Nguyen DTT, Rudaz S, Veuthey J-L (2008) Method transfer for fast liquid chromatography in pharmaceutical analysis: application to short columns packed with small particle. Part II: Gradient experiments. Eur J Pharm Biopharm 68:430–440. doi:http://dx.doi.org/10.1016/j.ejpb.2007.06.018

  33. Kumar P, Rubies A, Centrich F, Granados M, Cortes-Francisco N, Caixach J, Companyo R (2013) Targeted analysis with benchtop quadrupole-orbitrap hybrid mass spectrometer: application to determination of synthetic hormones in animal urine. Anal Chim Acta 780:65–73. doi:10.1016/j.aca.2013.04.017

    Article  CAS  Google Scholar 

  34. Mroczek T, Ndjoko-Ioset K, Glowniak K, Mietkiewicz-Capala A, Hostettmann K (2006) Investigation of Symphytum cordatum alkaloids by liquid-liquid partitioning, thin-layer chromatography and liquid chromatography-ion-trap mass spectrometry. Anal Chim Acta 566:157–166. doi:10.1016/j.aca.2006.03.016

    Article  CAS  Google Scholar 

  35. Bieri S, Varesio E, Muñoz O, Veuthey J-L, Christen P (2006) Use of porous graphitic carbon column for the separation of natural isomeric tropane alkaloids by capillary LC and mass spectrometry. J Pharm Biomed Anal 40:545–551. doi:http://dx.doi.org/10.1016/j.jpba.2005.07.007

  36. Hubert P, Nguyen-Huu JJ, Boulanger B, Chapuzet E, Chiap P, Cohen N, Compagnon PA, Dewé W, Feinberg M, Lallier M, Laurentie M, Mercier N, Muzard G, Nivet C, Valat L, Rozet E (2007) Harmonization of strategies for the validation of quantitative analytical procedures: a SFSTP proposal—part II. J Pharm Biomed Anal 45:70–81. doi:10.1016/j.jpba.2007.06.013

    Article  CAS  Google Scholar 

  37. EFSA (2005) Opinion of the scientific committee on a request from EFSA related to a harmonised approach for risk assessment of substances which are both genotoxic and carcinogenic. EFSA J 282:1–31

    Google Scholar 

  38. Social science statistics. http://www.socscistatistics.com/Default.aspx

  39. Dubecke A, Beckh G, Lullmann C (2011) Pyrrolizidine alkaloids in honey and bee pollen. Food Addit Contam Part A 28:348–358. doi:10.1080/19440049.2010.541594

    Article  CAS  Google Scholar 

  40. European Herbal Infusions Association (2014) Compendium of Guidelines for Herbal and Fruit Infusions. 5

Download references

Acknowledgments

Dr Pierre-Marie Allard and Dr Florence Mehl (School of Pharmaceutical Sciences, EPGL, Switzerland) are gratefully acknowledged for their assistance with Quadrupole-Orbitrap data acquisition and statistical analysis, respectively.

Author information

Authors and Affiliations

  1. School of Pharmaceutical Sciences, EPGL, University of Geneva, University of Lausanne, Quai Ernest-Ansermet 30, 1211, Geneva 4, Switzerland

    Caroline Mathon & Philippe Christen

  2. Official Food and Veterinary Control Authority of Geneva, Quai Ernest-Ansermet 22, 1211, Geneva 4, Switzerland

    Caroline Mathon, Patrick Edder & Stefan Bieri

Authors
  1. Caroline Mathon
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Patrick Edder
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Stefan Bieri
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Philippe Christen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Stefan Bieri.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 103 kb)

ESM 2

(XLSX 15.3 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mathon, C., Edder, P., Bieri, S. et al. Survey of pyrrolizidine alkaloids in teas and herbal teas on the Swiss market using HPLC-MS/MS. Anal Bioanal Chem 406, 7345–7354 (2014). https://doi.org/10.1007/s00216-014-8142-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-014-8142-8

Keywords

Search

Navigation