Abstract
Morpholine is a precursor of carcinogenic nitrosamines and although the possibility of their formation in the human stomach after ingestion of morpholine-treated apples is reported as highly unlikely morpholine has not been authorised as a food additive in the EU. Methods for its detection are required since it is permitted in other jurisdictions and may be present on food through direct treatment of fruit with waxes containing the compound, through steam treatment during processing or from packaging. Methods using derivatising agents with the inclusion of UV chromophores such as dansyl chloride yield good separation and high sensitivity but with mass spectrometric fragment ions predominantly originated from the derivatising group rather than the morpholine moiety. An amine acetylation derivatisation method is proposed from which fragment ions originating from the morpholine group are detected using widely available GC–MS. With full validation, a forensically robust confirmation of the presence of morpholine via its N-acetyl derivative is possible in support of regulatory analysis.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Akyüz M (2008) Simultaneous determination of aliphatic and aromatic amines in ambient air and airbourne particulate matters by gas chromatography–mass spectrometry. Atmos Environ 42:3809–3819
Akyüz M, Ata S (2006) Simultaneous determination of aliphatic and aromatic amines in water and sediment samples by ion pair extraction and gas chromatography–mass spectrometry. J Chromatogr 1129:88–94
Bosin TR, Faull KF (1988) Measurement of beta-carbolines by high performance liquid chromatography with fluorescence detection. J Chromatogr 428:229–236
ChemIDplus (2011) US National Library of Medicine, ChemIDplus Lite
ChemSpider (2011) RSC, ChemSpider, the free chemical database, Morpholine; synonyms, 1-oxa-4-azacyclohexane, tetrahydro-2H-1,4-oxazine, tetrahydro-1,4-oxazine, tetrahydro-1,4-isoxazine, diethylene oximide, diethyleneimide oxide and diethylene imidoxide
Diamond HA (1990) Reasonable doubt: to define, or not to define. Columbia Law Rev 90:1716–1736
Food Standards Agency (2010) Press Releases, “Update on fruit glazed with wax containing morpholine”, 8 October 2010
Food Standards Agency (2011) Food Law, Practice Guidance (England)
Fournier M, Lesage J, Ostiguy C, Tra HV (2008) Sampling and analytical methodology development for the determination of primary and secondary low molecular weight amines in ambient air. J Environ Monit 10:379–386
Hamano T, Mitsuhashi Y, Matsuki Y (1981) Glass capillary gas chromatography of secondary amines after derivatisation with benzenesulfonyl chloride. Agric Biol Chem 45:2237–2243
Hotchkiss JH, Vecchio AJ (1983) Analysis of direct contact paper and paperboard food packaging for N-nitrosomorpholine and morpholine. J Food Sci 48:240–241
Health and Safety Executive (2007) Workplace exposure limits, EH40/2007
IPCS (1995) Morpholine, Health and Safety Guide, IPCS International Programme on Chemical Safety, Health and Safety Guide No. 92, United Nations Environment Programme, International Labour Organisation, Geneva
Kataoka H, Shindoh S, Makita M (1995) Determination of secondary amines in various foods by gas chromatography with flame ionisation detection. J Chromatogr A 695:142–148
Law Commission (2009) The Admissibility of Expert Evidence in Criminal Proceedings in England and Wales, A New Approach to the Determination of Evidentiary Reliability, The Law Commission, Consultation Paper No 190
Lehotay SJ, Mastovska K, Amirav A et al (2008) Identification and confirmation of chemical residues in food by chromatography–mass spectrometry and other techniques. Trends Anal Chem 27:1070–1090
Lindahl R, Wästerby A, Levin JO (2001) Determination of morpholine in air by derivitisation with 1-naphthylisocyanate and HPLC analysis. Analyst 126:152–154
MacDonald I, Hulme A (2000) Food Standards Regulation, the new law. Jordan Publishing Ltd, Bristo, ISBN 0 85308 649 4
Maizels M, Budde WL (2001) Exact mass measurements for confirmation of pesticides and herbicides determined by liquid chromatography/time-of-flight mass spectrometry. Anal Chem 73:5436–5440
NLM (2011) US National Library of Medicine Hazardous Substances Data Bank
Paik M-J, Choi Y, Kim K-R (2006) Simultaneous profiling analysis of alkylphenols and amines by gas chromatography and gas chromatography–mass spectrometry. Anal Chim Acta 560:218–226
Pfundstein B, Tricker AR, Pressmann R (1991) Determination of primary and secondary amines in foods using gas chromatography and chemiluminescence detection with a modified thermal energy analyser. J Chromatogr 539:141–148
Sen NP, Baddoo PA (1980) An investigation on the possible presence of morpholine and N-nitrosomorpholine in wax-coated apples. J Food Saf 9:183–191
Singer GM, Lijinsky W (1976) Naturally occurring nitrosatable compounds. I, Secondary amines in foodstuffs. J Agric Food Chem 24:550–553
Sulaiman Z (2010a) Food Standards Agency, Imported Food Team, Enforcement & Local Authority Delivery Division, letter to Enforcement Authorities, 16 December 2010, Reference: IFD/E/10/016
Sulaiman Z (2010b) Food Standards Agency, Imported Food Team, Enforcement & Local Authority Delivery Division, letter to Enforcement Authorities, 23 December 2010, Reference: IFD/10/019
The National Institute of Standards and Technology (NIST) (2008) Standard Reference Database 69
Thorburn Burns D, Alliston GV (1971) Some studies on the photolytic decomposition stage in the estimation of N-nitrosamines. J Food Technol 6:433–438
US Food and Drug Administration (2011) Listing of Food Additive Status
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Walker, M.J., Gray, K., Hopley, C. et al. Forensically Robust Detection of the Presence of Morpholine in Apples—Proof of Principle. Food Anal. Methods 5, 874–880 (2012). https://doi.org/10.1007/s12161-011-9324-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-011-9324-z