A direct gas chromatography-mass spectrometry (GC-MS) method for the detection of orellanine present in stomach content (Part I)


Intoxication with Cortinarius orellanus Fr. is often lethal or, at the least, disabling for the victim. Orellanine is recognized as the prime toxic substance in this mushroom. Poisoning by other toxic mushrooms can be occasionally mistaken as poisoning by C. orellanus or vice versa. The C. orellanus toxins have a prolonged latent period after ingestion and onset in the appearance of symptoms. These properties of the toxin together with the chemo-, thermo- and photolability have made it difficult to develop a direct analytical method for diagnosing poisoning with orellanine, which in turn is needed to administer the correct medication. The aim of this study was to develop a direct analytical method for the detection of orellanine present in stomach content. Gas chromatography-mass spectrometry with supersonic molecular beams (GC-MS with SMB) was used for the direct detection of orellanine in the stomach fluids of rats after they were fed with food containing C. orellanus. This method can be used as a platform for the future development of analytical procedures for the direct analytical detection of orellanine in humans intoxicated by ingestion of toxic mushrooms. The standard orellanine was isolated from C. orellanus following the procedure described by Prast et al. [1] and was used as an authentic comparison.

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Brondz, I. , Nevo, E. , Wasser, S. and Brondz, A. (2012) A direct gas chromatography-mass spectrometry (GC-MS) method for the detection of orellanine present in stomach content (Part I). Journal of Biophysical Chemistry, 3, 29-34. doi: 10.4236/jbpc.2012.31003.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Prast, H., Werner, E.R., Pfaller, W. and Moser, M. (1988) Toxic properties of the mushroom Cortinarius orellanus. Archives of Toxicology, 62, 81-88. doi:10.1007/BF00316263
[2] Richard, J.-M., Taillandierand, G. and Benoit-Guyod, J.-L. (1985) A quantitative structure-activity relationship study on substituted pyridines as a contribution to the knowledge of the toxic effects of orellanine, a toxin from the mushroom Cortinarius orellanus. Toxicon, 23, 815-824. doi:10.1016/0041-0101(85)90013-3
[3] Heim, R. (1963) Diagnoses latines des especes de champignons ou, nonda associes a la folie du komugl tai et du ndaadl (in French). Revue de Mycologie, 28, 277-283.
[4] Schumacher, T. and H?iland, K. (1983) Review mushroom poisoning caused by species of the genus Cortinarius Fries. Archives of Toxicology, 53, 87-106.
[5] Cantin, D., Richard, J.-M. and Alary, J. (1989) Chromatographic behaviour and determination of orellanine, a toxin from the mushroom Cortinarius orellanus. Journal of Chromatography A, 478, 231-237. doi:10.1016/S0021-9673(01)84389-2
[6] Oubrahim, H., Cantin-Esnault, D. and Richard, J.-M. (1996) Novel methods for identification and quantification of the mushroom nephrotoxin orellanine. Part 1: Development of ESR, electrophoresis and TCL methods. Pharmazie, 51, 231-234.
[7] Rapior, S., Andary, C. and Mousain, D. (1987) Cortinarius section orellani isolation and culture of Cortinarius orellanus. Transactions of the British Mycological Society, 89, 41-44. doi:10.1016/S0007-1536(87)80055-4
[8] Brondz, I., Nevo, E., Wasser, S., H?iland, K., St?rmer, F. and Brondz, A. (2011) Method development for in vivo analyses of toxin orellanine from the toad mushroom Cortinarius orellanus. Separation Science Europe 2011, 10-11 October 2011, the Royal Institution, London, Abstract 9.
[9] Brondz, I. (2011) Historical overview of chromatography and related techniques in analysis of antimalarial drug primaquine. Nova Science Publishers, Inc., New York.
[10] Brondz, I., Fialkov, A.B. and Amirav, A. (2009) Analysis of quinocide in unprocessed primaquine diphosphate and primaquine diphosphate tablets using gas chromatography-mass spectrometry with supersonic molecular beams. Journal of Chromatography A, 1216, 824-829. doi:10.1016/j.chroma.2008.11.043
[11] Fialkov, A.B., Steiner, U., Jones, L. and Amirav, A. (2006) A new type of GC-MS with advanced capabilities. International Journal of Mass Spectrometry, 251, 47-58. doi:10.1016/j.ijms.2005.12.045
[12] Amirav, A., Gordin, A., Poliak, M. and Fialkov, A.B. (2008) Gas chromatography-mass spectrometry with supersonic molecular beams. Journal of Mass Spectrometry, 43, 141-163. doi:10.1002/jms.1380
[13] Fialkov, A.B., Gordin, A. and Amirav, A. (2003) Extending the rage of compounds amenable for gas chromatography mass spectrometry. Journal of Chromatography A, 991, 217-240. doi:10.1016/S0021-9673(03)00247-4
[14] Richard, J.-M. and Ulrich, J. (1989) Mass spectrometry of orellanine, a mushroom toxin, and of related bipyridine-N-oxides. Biomedical and Environmental Mass Spectrometry, 18, 1-4. doi:10.1002/bms.1200180102
[15] Antkowiak, W.Z., Antkowiak, R., Wyrzykiewicz, E. and Czerwiński, G. (1994) Mass spectral fragmentation of orellanine and its tetramethyl ether with regard to their facile thermal and photochemical deoxygenation. Heterocycles, 39, 477-484. doi:10.3987/COM-94-S(B)72
[16] Spiteller, P., Spiteller, M. and Steglich, W. (2003) Occurrence of the fungal toxin orellanine as a diglucoside and investigation of its biosynthesis. Angewandte Chemie International Edition, 42, 2864-2867. doi:10.1002/anie.200351066
[17] Koller, G.E.B., H?iland, K., Janak, K. and St?rmer, F.C. (2002) The presence of orellanine in spores and basidiocarp from Cortinarius orellanus and Cortinarius rubellus. Mycologia, 94, 752-756. doi:10.2307/3761689
[18] Richard, J.-M., Louis, J. and Cantin, D. (1988) Nephrotoxicity of orellanine, a toxin from the mushroom Cortinarius orellanus. Archives of Toxicology, 62, 242-245.
[19] Holmdahl, J., Ahlmén, J., Bergek, S., Lundberg, S. and Persson, S.A. (1987) Isolation and nephrotoxic studies of orellanine from the mushroom Cortinarius speciosissimus. Toxicon, 25, 195-199. doi:10.1016/0041-0101(87)90241-8
[20] Horn, S., Horina, J.H., Krejs, G.J., Holzer, H. and Ratschek, M. (1997) End-stage renal failure from mushroom poisoning with Cortinarius orellanus: Report of four cases and review of the literature. American Journal of Kidney Diseases, 30, 282-286. doi:10.1016/S0272-6386(97)90066-4
[21] Danel, V.C., Saviuc, P.F. and Garon, D. (2001) Main features of Cortinarius spp. poisoning: A literature review. Toxicon, 39, 1053-1060. doi:10.1016/S0041-0101(00)00248-8
[22] Goldfrank, L.R. (2011) Mushrooms. In: Nelson, L.S., Lewin, N.A. and Howland, M.A., et al. Eds., Goldfrank’s Toxicologic Emergencies, McGraw-Hill, New York.
[23] Brent, J. and Palmer, R.B. (2007) Mushrooms. In: Shannon, M.W., Borron, S.W. and Burns, M.J., Eds., Haddad and Winchester’s Clinical Management of Poisoning and Drug Overdose, 4th Edition, Saunders Elsevier, Philadelphia.
[24] Oubrahim, H., Richard, J.-M., Cantin-Esnault, D., SeigleMurandi, F. and Trécourt, F. (1997) Novel methods for identification and quantification of the mushroom nephrotoxin orellanine. Thin-layer chromatography and electrophoresis screening of mushrooms with electron spin resonance determination of the toxin. Journal of Chromatography A, 758, 145-157.
[25] Rohrmoser, M., Kirchmair, M., Feifel, E., Valli, A., Corradini, R., Pohanka, E., Rosenkranz, A. and P?der, R. (1997) Orellanine poisoning: Rapid detection of the fungal toxin in renal biopsy material. Journal of Toxicology—Clinical Toxicology, 35, 63-66. doi:10.3109/15563659709001167
[26] Rapior, S., Delpech, N., Andary, C. and Huchhard, G. (1989) Intoxication by Cortinarius orellanus: Detection and assay of orellanine in biological fluids and renal biopsies. Mycopathologia, 108, 155-161. doi:10.1007/BF00436220
[27] Brondz, I., Ekeberg, D., H?iland, K., Bell, D.S. and Annino, A.R. (2007) The real nature of the indole alkaloids in Cortinarius infractus: Evaluation of artifact formation through solvent extraction method development. Journal of Chromatography A, 1148, 1-7. doi:10.1016/j.chroma.2007.02.074

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