Identification of novel unique ma over bar nuka honey markers using high-resolution mass spectrometry-based metabolomics

Ma over bar nuka 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 ma over bar nuka honey (3-phenyllactic acid, 2 '-methox-yacetophenone, 2-methoxybenzoic acid, and 4-hydroxyphenyllactic acid). However, spiking other kinds of honey with these compounds and/or the dilution of ma over bar nuka 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 ma over bar nuka 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 ma over bar nuka honey, even at 75% ma over bar nuka honey purity. Thus, the herein-reported methodology can be employed in the prevention and detection of ma over bar nuka honey adulteration even at low levels, and the tentatively identified markers presented in this work proved valuable for ma over bar nuka honey authentication procedures.