Continental Emissions Influence the Sources and Formation Mechanisms of Marine Nitrate Aerosols in Spring Over the Bohai Sea and Yellow Sea Inferred From Stable Isotopes

Abstract

AbstractThe influence of continental emissions on the origin and formation mechanisms of atmospheric particulate nitrate (ρ‐NO3−) aerosols in the marine boundary layer remains unclear. Here, synchronous observations of nitrogen isotope ratios (δ15N–NO3−) and oxygen isotope anomaly (Δ17O–NO3−) in ρ‐NO3− were conducted across the Yellow Sea and Bohai Sea in Eastern China. Nitrate concentrations, δ15N–NO3− and Δ17O–NO3− exhibited a pronounced north‐to‐south latitudinal gradient. Combined with backward air mass trajectory analysis, the high nitrate concentration and isotopic characteristics in the northern sea area were found to be affected by the continental outflow near China while the low values in the southern sea area were more related to the oceanic inflow. Stable isotope analysis in R (SIAR) indicated that near the northern sea area, the nitrate radicals (NO3) reacted with hydrocarbons (HC) or dimethyl sulfides (DMS) pathway (NO3 + HC/DMS) played a leading role in nitrate production, whereas the NO2 + OH pathway dominated near the southern sea area. Nitrate in the northern seas originated mainly from nitrogen oxides (NOx = NO + NO2, the gaseous precursor of nitrate) emitted from continental sources, especially coal combustion and biomass burning. While closer to the southern seas, the proportion of NOx generated in the marine environment (from ship and biogenic emissions) increased. Overall, the differential relative contributions of continental and marine atmospheric chemistry and NOx sources lead to the spatial distribution characteristics of atmospheric nitrate concentrations and isotopic values over the Yellow and Bohai Seas.