Discovery and measurement of an isotopically distinct source of sulfate in Earth's atmosphere

Sulfate (SO(4)) and its precursors are significant components of the atmosphere, with both natural and anthropogenic sources. Recently, our triple-isotope ((16)O, (17)O, (18)O) measurements of atmospheric sulfate have provided specific insights into the oxidation pathways leading to sulfate, with important implications for models of the sulfur cycle and global climate change. Using similar isotopic measurements of aerosol sulfate in a polluted marine boundary layer (MBL) and primary sulfate (p-SO(4)) sampled directly from a ship stack, we quantify the amount of p-SO(4) found in the atmosphere from ships. We find that ships contribute between 10% and 44% of the non-sea-salt sulfate found in fine [diameter (D) < 1.5 microm) particulate matter in coastal Southern California. These fractions are surprising, given that p-SO(4) constitutes approximately 2-7% of total sulfur emissions from combustion sources [Seinfed JH, Pandis SN (2006) Atmospheric Chemistry and Physics (Wiley-Interscience, New York)]. Our findings also suggest that the interaction of SO(2) from ship emissions with coarse hydrated sea salt particles may lead to the rapid removal of SO(2) in the MBL. When combined with the longer residence time of p-SO(4) emissions in the MBL, these findings suggest that the importance of p-SO(4) emissions in marine environments may be underappreciated in global chemical models. Given the expected increase of international shipping in the years to come, these findings have clear implications for public health, air quality, international maritime law, and atmospheric chemistry.