Numerous international governmental agencies that steer policy assume that polystyrene persists in the environment for millennia. Here, we show that polystyrene is completely photochemically oxidized to carbon dioxide and partially photochemically oxidized to dissolved organic carbon. Lifetimes of complete and partial photochemical oxidation are estimated to occur on centennial and decadal time scales, respectively. These lifetimes are orders of magnitude faster than biological respiration of polystyrene and thus challenge the prevailing assumption that polystyrene persists in the environment for millennia. Additives disproportionately altered the relative susceptibility to complete and partial photochemical oxidation of polystyrene and accelerated breakdown by shifting light absorbance and reactivity to longer wavelengths. Polystyrene photochemical oxidation increased approximately 25% with a 10 °C increase in temperature, indicating that temperature is unlikely to be a primary driver of photochemical oxidation rates. Collectively, sunlight exposure appears to be a governing control of the environmental persistence of polystyrene, and thus, photochemical loss terms need to be included in mass balance studies on the environmental fate of polystyrene. The experimental framework presented herein should be applied to a diverse array of polymers and formulations to establish how general these results are for other plastics in the environment.

Chemical dispersants are one of many tools used to mitigate the overall environmental impact of oil spills. In principle, dispersants break up floating oil into small droplets that disperse into the water column where they are subject to multiple fate and transport processes. The effectiveness of dispersants typically decreases as oil weathers in the environment. This decrease in effectiveness is often attributed to evaporation and emulsification, with the contribution of photochemical weathering assumed to be negligible. Here, we aim to test this assumption using Macondo well oil released during the Deepwater Horizon spill as a case study. Our results indicate that the effects of photochemical weathering on Deepwater Horizon oil properties and dispersant effectiveness can greatly outweigh the effects of evaporative weathering. The decrease in dispersant effectiveness after light exposure was principally driven by the decreased solubility of photo-oxidized crude oil residues in the solvent system that comprises COREXIT EC9500A. Kinetic modeling combined with geospatial analysis demonstrated that a considerable fraction of aerial applications targeting Deepwater Horizon surface oil had low dispersant effectiveness. Collectively, the results of this study challenge the paradigm that photochemical weathering has a negligible impact on the effectiveness of oil spill response and provide critical insights into the "window of opportunity" to apply chemical dispersants in response to oil spills in sunlit waters.