ALBERT

Description: 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 (NOx), 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 NOx, 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 NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

Description: Alkyl nitrates (RONO2) were measured concurrently at a mountain site (TMS) and an urban site (TW) at the foot of the same mountain in Hong Kong from September to November 2010, when high O3 mixing ratios were frequently observed. The abundance and temporal patterns of five C1–C4 RONO2 and their parent hydrocarbons (RH), the RONO2/RH ratios and photochemical age of air masses at TMS differed from those at TW, reflecting different contributions of direct emissions and secondary formation of RONO2 at the two sites. Relative to 2-BuONO2/n-butane, the measured ratios of C1–C2 RONO2/RH at the two sites exhibited significant positive deviations from pure photochemical (PP) curves and background initial ratio (BIR) curves obtained from laboratory kinetic data, suggesting that background mixing ratios had a significant influence on the RONO2 and RH distributions. In contrast to the C1–C2 RONO2/RH ratios, the evolution for the measured ratios of C3 RONO2/RH to 2-BuONO2/n-butane agreed well with the ratio distributions in the PP and BIR curves at the two sites. Furthermore, the ratios of 1-/2-PrONO2 and yields of 1- and 2-PrONO2 suggested that the C3 RONO2 were mainly from secondary formation at TMS, whereas secondary formation and other additional sources had a significant influence on C3 RONO2 mixing ratios at TW. The source apportionment results confirmed that secondary formation was the dominant contributor to all the RONO2 at TMS, while most of the RONO2 at TW were from secondary formation and biomass burning. The findings of the source apportionments and photochemical evolution of RONO2 are helpful to evaluate photochemical processing in Hong Kong using RONO2 as an indicator.

Description: Many taxis and public buses are powered by liquefied petroleum gas (LPG) in Hong Kong. With more vehicles using LPG, they have become the major contributor to ambient volatile organic compounds (VOCs) in Hong Kong. An intervention program aimed to reduce the emissions of VOCs and nitrogen oxides (NOx) from LPG-fueled vehicles was implemented by the Hong Kong Government in September 2013. Long-term real-time measurements indicated that the program was remarkably effective in reducing LPG-related VOCs, NOx and nitric oxide (NO) in the atmosphere. Receptor modeling results further revealed that propane, propene, i-butane, n-butane and NO in LPG-fueled vehicle exhaust emissions decreased by 37.3 ± 0.4, 50.2 ± 0.3, 32.9 ± 0.4, 41.1 ± 0.4 and 75.9 ± 0.3 %, respectively, during the implementation of the program. In contrast, despite the reduction of VOCs and NOx, the O3 production following the program increased by 0.25 ± 0.04 ppbv h−1 (4.8 %). Moreover, the production rate of HOx decreased due to the reduction of VOCs, whereas NO reduction resulted in a more significant decrease of the HOx in destruction compared to the decrease in production, and an increase of hydroxyl (OH) and hydroperoxyl (HO2). Analysis of O3-VOCs-NOx sensitivity in ambient air indicated VOC-limited regimes in the O3 formation before and during the program. Moreover, a maximum reduction percentage of NOx (i.e., 29.4 %) and the lowest reduction ratio of VOCs / NOx (i.e., ~ 3 : 1) in LPG-fueled vehicle emissions were determined to give a zero O3 increment. The findings are of great help to future formulation and implementation of control strategies on vehicle emissions in Hong Kong.

Description: A model intercomparison activity was inspired by the large suite of observations of atmospheric composition made during the International Polar Year (2008) in the Arctic. Nine global and two regional chemical transport models participated in this intercomparison and performed simulations for 2008 using a common emissions inventory to assess the differences in model chemistry and transport schemes. This paper summarizes the models and compares their simulations of ozone and its precursors and presents an evaluation of the simulations using a variety of surface, balloon, aircraft and satellite observations. Each type of measurement has some limitations in spatial or temporal coverage or in composition, but together they assist in quantifying the limitations of the models in the Arctic and surrounding regions. Despite using the same emissions, large differences are seen among the models. The cloud fields and photolysis rates are shown to vary greatly among the models, indicating one source of the differences in the simulated chemical species. The largest differences among models, and between models and observations, are in NOy partitioning (PAN vs. HNO3) and in oxygenated volatile organic compounds (VOCs) such as acetaldehyde and acetone. Comparisons to surface site measurements of ethane and propane indicate that the emissions of these species are significantly underestimated. Satellite observations of NO2 from the OMI (Ozone Monitoring Instrument) have been used to evaluate the models over source regions, indicating anthropogenic emissions are underestimated in East Asia, but fire emissions are generally overestimated. The emission factors for wildfires in Canada are evaluated using the correlations of VOCs to CO in the model output in comparison to enhancement factors derived from aircraft observations, showing reasonable agreement for methanol and acetaldehyde but underestimate ethanol, propane and acetone, while overestimating ethane emission factors.

Description: In a joint NRL/Manila Observatory mission, as part of the Seven SouthEast Asian Studies program (7-SEAS), a 2-week, late September 2011 research cruise in the northern Palawan archipelago was undertaken to observe the nature of southwest monsoonal aerosol particles in the South China Sea/East Sea (SCS/ES) and Sulu Sea region. Previous analyses suggested this region as a receptor for biomass burning from Borneo and Sumatra for boundary layer air entering the monsoonal trough. Anthropogenic pollution and biofuel emissions are also ubiquitous, as is heavy shipping traffic. Here, we provide an overview of the regional environment during the cruise, a time series of key aerosol and meteorological parameters, and their interrelationships. Overall, this cruise provides a narrative of the processes that control regional aerosol loadings and their possible feedbacks with clouds and precipitation. While 2011 was a moderate El Niño–Southern Oscillation (ENSO) La Niña year, higher burning activity and lower precipitation was more typical of neutral conditions. The large-scale aerosol environment was modulated by the Madden–Julian Oscillation (MJO) and its associated tropical cyclone (TC) activity in a manner consistent with the conceptual analysis performed by Reid et al. (2012). Advancement of the MJO from phase 3 to 6 with accompanying cyclogenesis during the cruise period strengthened flow patterns in the SCS/ES that modulated aerosol life cycle. TC inflow arms of significant convection sometimes span from Sumatra to Luzon, resulting in very low particle concentrations (minimum condensation nuclei CN 〈 150 cm−3, non-sea-salt PM2.5 〈 1 μg m−3). However, elevated carbon monoxide levels were occasionally observed suggesting passage of polluted air masses whose aerosol particles had been rained out. Conversely, two drier periods occurred with higher aerosol particle concentrations originating from Borneo and Southern Sumatra (CN 〉 3000 cm−3 and non-sea-salt PM2.5 10–25 μg m−3). These cases corresponded with two different mechanisms of convection suppression: lower free-tropospheric dry-air intrusion from the Indian Ocean, and large-scale TC-induced subsidence. Veering vertical wind shear also resulted in aerosol transport into this region being mainly in the marine boundary layer (MBL), although lower free troposphere transport was possible on the western sides of Sumatra and Borneo. At the hourly time scale, particle concentrations were observed to be modulated by integer factors through convection and associated cold pools. Geostationary satellite observations suggest that convection often takes the form of squall lines, which are bowed up to 500 km across the monsoonal flow and 50 km wide. These squall lines, initiated by cold pools from large thunderstorms and likely sustained by a veering vertical wind shear and aforementioned mid-troposphere dry layers, propagated over 1500 km across the entirety of the SCS/ES, effectively cutting large swaths of MBL aerosol particles out of the region. Our conclusion is that while large-scale flow patterns are very important in modulating convection, and hence in allowing long-range transport of smoke and pollution, more short-lived phenomena can modulate cloud condensation nuclei (CCN) concentrations in the region, resulting in pockets of clean and polluted MBL air. This will no doubt complicate large scale comparisons of aerosol–cloud interaction.

Description: Organosulfur compounds (OSC) are naturally emitted via various processes involving phytoplankton and algae in marine regions, from animal metabolism and from biomass decomposition inland. These compounds are malodorant and reactive. Their oxidation to methanesulfonic and sulfuric acids leads to the formation and growth of atmospheric particles, which are known to have negative effects on visibility, climate and human health. In order to predict particle formation events, accurate measurements of the OSC precursors are essential. Here, two different approaches, proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) and canister sampling coupled with GC-FID are compared for both laboratory standards [dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS) and methanethiol (MTO)] and for a complex sample. Results show that both techniques produce accurate quantification of DMS. While PTR-ToF-MS provides real-time measurements of all four OSCs individually, significant fragmentation of DMDS and DMTS occurs, which can complicate their identification in complex mixtures. Canister sampling coupled with GC-FID provides excellent sensitivity for DMS, DMDS and DMTS. However, MTO was observed to react on metal surfaces to produce DMDS and, in the presence of hydrogen sulfide, even DMTS. Avoiding metal in sampling systems seems to be necessary for measuring all but dimethyl sulfide in air.