Source identification and budget analysis on elevated levels of formaldehyde within ship plumes: a photochemical/dynamic model analysis

Abstract

Abstract. Elevated levels of formaldehyde (HCHO) along the ship corridors have been observed by satellite sensors, such as ESA/ERS-2 GOME (Global Ozone Monitoring Experiment), and were also predicted by global 3-D chemistry-transport models. In this study, three likely sources of the elevated HCHO levels were investigated to identify the detailed sources and examine the contributions of the sources (budget) of the elevated levels of HCHO in the ship corridors using a newly-developed ship-plume photochemical/dynamic model: (1) primary HCHO emission from ships; (2) secondary HCHO production via the atmospheric oxidation of Non-methane volatile organic compounds (NMVOCs) emitted from ships; and (3) atmospheric oxidation of CH4 within the ship plumes. From multiple ship-plume model simulations, CH4 oxidation by elevated levels of in-plume OH radicals was found to be the main factor responsible for the elevated levels of HCHO in the ship corridors. More than ~91% of the HCHO for the base ship plume case (ITCT 2K2 ship-plume case) is produced by this atmospheric chemical process, except in the areas close to the ship stacks where the main source of the elevated HCHO levels would be primary HCHO from the ships (due to the deactivation of CH4 oxidation from the depletion of in-plume OH radicals). Because of active CH4 oxidation (chemical destruction of CH4) by OH radicals, the instantaneous chemical lifetime of CH4 (τ CH4) decreased to ~0.45 yr inside the ship plume, which is in contrast to τ CH4 of ~1.1 yr in the background (up to ~41% decrease). A variety of likely ship-plume situations at three locations at different latitudes within the global ship corridors was also studied to determine the extent of the enhancements in the HCHOlevels in the marine boundary layer (MBL) influenced by ship emissions. It was found that the ship-plume HCHO levels could be 20.5–434.9 pptv higher than the background HCHO levels depending on the latitudinal locations of the ship plumes (i.e., intensity of solar radiation and temperature), MBL stability and NOx emission rates. On the other hand, NMVOC emissions from ships were not found to be a primary source of photochemical HCHOproduction inside ship plumes due to their rapid and individual dilution. However, the diluted NMVOCs would contribute to the HCHO productions in the background air. The greater impact of ship-plume photochemistry on the atmospheric MBL oxidation cycles, global climate, and marine eco-system in the global ship corridors are also discussed based on the results in this study.