Identification of novel unique mānuka honey markers using high-resolution mass spectrometry-based metabolomics.

Mānuka honey is a valuable commodity produced by bees foraging the flowers of Leptospermum scoparium , a bush native to New Zealand and Australia. Due to its high value and proven health benefits, authenticity fraud in the sale of this food is a significant risk, as recounted in the literature. Four compulsory natural products must be present at minimum concentrations to authenticate mānuka honey (3-phenyllactic acid, 2′-methoxyacetophenone, 2-methoxybenzoic acid, and 4-hydroxyphenyllactic acid). However, spiking other kinds of honey with these compounds and/or the dilution of mānuka honey with other varieties may result in fraud going undetected. In this work, liquid chromatography coupled with high-resolution mass spectrometry and a metabolomics-based strategy has allowed us to tentatively identify 19 natural products –putative mānuka honey markers–, nine of which are reported for the first time. Chemometric models applied to these markers allowed the detection of both spiking and dilution fraud attempts of mānuka honey, even at 75% mānuka honey purity. Thus, the herein-reported methodology can be employed in the prevention and detection of mānuka honey adulteration even at low levels, and the tentatively identified markers presented in this work proved valuable for mānuka honey authentication procedures. [Display omitted] • Mānuka honey is a valuable commodity for which fraud has been reported. • Fraud via spiking of natural products or via dilution with other honeys is possible. • Employing HRMS, 19 natural products in mānuka honey have been identified. • 12 of them are mānuka exclusive, of which nine had never been reported in mānuka. • Statistical analysis permitted authenticating mānuka honey against fraud attempts. [ABSTRACT FROM AUTHOR]