Due to the high bond dissociation energy (BDE) of C-F bonds (116 kcal/mol), perfluorooctanoic acid (PFOA) is a highly recalcitrant pollutant. Herein, we demonstrate a novel method to decompose PFOA in the presence of sunlight and ferric iron (Fe(III)). Under such conditions, 97.8 +/- 1.7% of 50 mu M PFOA decomposed within 28 days into shorter-chain intermediates and fluoride (F-), with an overall defluorination extent of 12.7 +/- 0.5%. No PFOA was removed under visible light, indicating that UV radiation is required for PFOA decomposition. Spectroscopic analysis indicates that the decomposition reaction is likely initiated by electron-transfer from PFOA to Fe(III), forming Fe(II) and an unstable organic carboxyl radical. An alternative mechanism for the formation of this organic radical involves hydroxyl radicals, detected by electron paramagnetic resonance (EPR). The observation that PFOA can be degraded by Fe(III) under solar irradiation provides mechanistic insight into a possibly overlooked natural attenuation process. Because Fe(III) is abundant in natural waters and sunlight is essentially free, this work represents a potentially important step toward the development of simple and inexpensive remediation strategies for PFOA-contaminated water. (C) 2013 Elsevier B.V. All rights reserved.