Alkenes are oxidized rapidly in the atmosphere by addition of OH and subsequently O2 leading to the formation of Î2-hydroxy peroxy radicals. These peroxy radicals react with NO to form Î2-hydroxy nitrates with a branching ratio α. We quantify α for CM2-C8 alkenes at 295 K ± 3 and 993 hPa. The branching ratio can be expressed as α Combining double low line (0.045 ± 0.016) × N − (0.11 ± 0.05) where N is the number of heavy atoms (excluding the peroxy moiety), and listed errors are 2Ï. These branching ratios are larger than previously reported and are similar to those for peroxy radicals formed from H abstraction from alkanes. We find the isomer distributions of Î2-hydroxy nitrates formed under NO-dominated peroxy radical chemistry to be different than the isomer distribution of hydroxy hydroperoxides produced under HO2-dominated peroxy radical chemistry. Assuming unity yield for the hydroperoxides implies that the branching ratio to form Î2-hydroxy nitrates increases with substitution of RO2. Deuterium substitution enhances the branching ratio to form hydroxy nitrates in both propene and isoprene by a factor of ∼ 1.5. The role of alkene chemistry in the Houston region is re-evaluated using the RONO2 branching ratios reported here. Small alkenes are found to play a significant role in present-day oxidant formation more than a decade (2013) after the 2000 Texas Air Quality Study identified these compounds as major contributors to photochemical smog in Houston.

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NOx environments. Production and loss of IN have a significant influence on the NOx cycle and tropospheric O3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/-3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (∼ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.

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.