The behaviour of the antioxidant tert-butylhydroquinone (TBHQ) on the storage stability of biodiesel was investigated. Storage conditions were simulated through static immersion corrosion tests in biodiesel (with and without TBHQ) using copper coupons. Measurements of oxidation stability (Rancimat induction period) and metal release at different stages of corrosion were performed. After 24 h of the static immersion test, the neat and TBHQ-doped biodiesels presented induction times below the EN 14214 limit (6 h). Copper release was more intense in the neat biodiesel which evidenced that TBHQ retarded the corrosion process as a corrosion inhibitor. Ion trap-time-of-flight mass spectrometry (IT-TOF-MS) revealed the presence of considerable amounts of tert-butylquinone (TBQ) in the TBHQ-doped biodiesel exposed to the corrosion process. As TBHQ molecules adsorb at the copper surface to inhibit corrosion, these molecules are catalytically oxidised to TBQ. IT-TOF-MS also indicated the formation of new molecules of high molecular weight only presented in the TBHQ-doped biodiesel deteriorated by the corrosion process. MS(2) spectra gave clear evidence of the formation of new complexes between free radicals of long-chain molecules (fatty acid derivatives) and TBQ radicals during biodiesel deterioration. (C) 2011 Elsevier Ltd. All rights reserved.