Molecular recognition of emerald ash borer infestation using leaf spray mass spectrometry

RATIONALE: The introduction of the emerald ash borer (Agrilus planipennis) (EAB) from Asia to Michigan, USA, in the 1990s caused the widespread death of ash trees in two Canadian provinces and 24 US states. The three current methods for the detection of emerald ash borer infestation, visual surveys, tree girdling and artificial traps, can be unreliable, and there is clearly a need for a rapid, dependable technique for the detection of emerald ash borer infestation. METHODS: Leaf spray, an ambient ionization method for mass spectrometry (MS), gives direct chemical information on a leaf sample by applying a high voltage to a naturally or artificially sharply pointed leaf piece causing ions to be generated directly from the leaf tip for MS analysis. RESULTS: Leaflets from 23 healthy and EAB-infested ash trees were analyzed by leaf spray mass spectrometry in an attempt to distinguish healthy and EAB-infested ash trees. In negative ion mode, healthy ash trees showed an increased abundance of ions m/z 455.5, 471.5 and 487.5, and ash trees infested with the EAB displayed an increased abundance of ions m/z 181 and 217. The identities of the chemical discriminators ursolic acid and oleanolic acid in healthy ash trees, and six-carbon sugar alcohols in infested ash trees, were determined by tandem mass spectrometry and confirmed with standards. CONCLUSIONS: This preliminary study suggests that leaf spray mass spectrometry of ash tree leaflets provides a potential tool for the early detection of ash tree infestation by the emerald ash borer. Copyright (C) 2016 John Wiley & Sons, Ltd.