Differences in New Zealand Hop Cultivars Based on Their Unique Volatile Compounds: An Integrated Fingerprinting and Chemometrics Approach

Hop aroma characteristics originate from hop essential oils, which have complex chemical profiles that remain poorly understood, particularly for New Zealand hops. The aim of this study was to determine volatile compounds that distinguish New Zealand hop cultivars. Untargeted fingerprinting methods based on headspace gas chromatography mass spectrometry (GC-MS) were used to analyse nine hop cultivars. A total of 61 volatile compounds were identified as compounds that differentiated the commercial hop varieties using advanced chemometrics and feature selection techniques. Similarities in volatile composition were found between Wakatu, Wai-iti (TM) and Kohatu (R), which are rich in alcohols. Another grouping was found between Waimea (TM) and Nelson Sauvin (TM), where ketones and esters were commonly found. Rakau (TM) was distinct from the other eight cultivars, distinguished by 2-methylbutyl 3-methylbutanoate and methanethiol hexanoate. Riwaka (TM) contained the greatest number of discriminating volatile compounds when compared to other cultivars, which was dominated by terpenoids, such as geranyl 2-methylbutanoate, perillene and D-limonene. The chemical fingerprinting approach successfully identified volatile compounds that had not been previously found in New Zealand hop cultivars and that discriminated the commercial cultivars. The data obtained in the present study further extend the knowledge of New Zealand hops and will help facilitate targeted breeding.