Determination of naphthalene-derived compounds in apples by ultra-high performance liquid chromatography-tandem mass spectrometry

• A RP-Amide column is proposed for the simultaneous analysis of NAD and NAA and NOA isomers by UHPLC–MS/MS.
• Naphthalene-derived compound fragmentation pathways are established.
• The accurate mass measurement is proposed to confirm the presence of naphthylacetic acid in samples.
• NAA and NAD dissipation curves show important decay within few weeks of application.

Naphthylacetic acid, naphthyloxy acetic acid and naphthylacetamide belong to a group of synthetic substances known as “auxin-like” compounds which are used as growth regulators in vegetables and fruits due to their structure similarities with the indoleacetic acid, the most important plant auxin. This paper reports a selective, sensitive and fast ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC–MS/MS) method for the determination of naphthylacetamide (NAD) and the isomers (α and β) of naphthylacetic acid (NAA) and naphthyloxy acetic (NOA) acid in apple samples. A baseline separation between the respective isomers was achieved using an RP-Amide column with gradient elution. The UHPLC-MS/MS method developed, using electrospray and selected reaction monitoring (SRM) acquisition mode led to a reliable determination of these family of compounds in apple samples at low quantitation levels, down to 1.0 μg kg−1 and 0.25 μg kg−1 respectively. For confirmation of NAA accurate mass measurement is proposed giving at these conditions quantitation limits of 10 μg kg−1 for this compound. The UHPLC-MS/MS method developed was used for the analysis of apple samples harvested in three different apple fields from Lleida (Spain) during the blooming period. NAD and NAA were found in samples collected during 4–5 weeks after application at concentrations between the quantification limits and 43 μg kg−1 and 24 μg kg−1, respectively.

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