Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC ⁴ RS) and ground-based (SOAS) observations in the Southeast US

Abstract

Formation of organic nitrates (RONO₂) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NO_x), but the chemistry of RONO₂ formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO₂) in the GEOS-Chem global chemical transport model with ∼25 × 25 km² resolution over North America. We evaluate the model using aircraft (SEAC⁴RS) and ground-based (SOAS) observations of NO_x, BVOCs, and RONO₂ from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO₂ species measured during the campaigns. Gas-phase isoprene nitrates account for 25-50% of observed RONO₂ in surface air, and we find that another 10% is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10% of observed boundary layer RONO₂ were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO₃ accounts for 60% of simulated gas-phase RONO₂ loss in the boundary layer. Other losses are 20% by photolysis to recycle NO_x and 15% by dry deposition. RONO₂ production accounts for 20% of the net regional NO_x sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NO_x emissions. This segregation implies that RONO₂ production will remain a minor sink for NO_x in the Southeast US in the future even as NO_x emissions continue to decline.