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Emission estimates of carbon dioxide (CO2) and methane (CH4) and the meteorological factors affecting them are investigated over Sacramento, California, using an aircraft equipped with a cavity ring-down greenhouse gas sensor as part of the Alpha Jet Atmospheric eXperiment (AJAX) project. To better constrain the emission fluxes, we designed flights in a cylindrical pattern and computed the emission fluxes from two flights using a kriging method and Gauss's divergence theorem. Differences in wind treatment and assumptions about background concentrations affect the emission estimates by a factor of 1.5 to 7. The uncertainty is also impacted by meteorological conditions and distance from the emission sources. The vertical layer averaging affects the flux estimate, but the choice of raw wind or mass-balanced wind is more important than the thickness of the vertical averaging for mass-balanced wind for both urban and local scales. The importance of vertical mass transfer for flux estimates is examined, and the difference in the total emission estimate with and without vertical mass transfer is found to be small, especially at the local scale. The total flux estimates accounting for the entire circumference are larger than those based solely on measurements made in the downwind region. This indicates that a closed-shape flight profile can better contain total emissions relative to a one-sided curtain flight because most cities have more than one point source and wind direction can change with time and altitude. To reduce the uncertainty of the emission estimate, it is important that the sampling strategy account not only for known source locations but also possible unidentified sources around the city. Our results highlight that aircraft-based measurements using a closed-shape flight pattern are an efficient and useful strategy for identifying emission sources and estimating local- and city-scale greenhouse gas emission fluxes.

We present two new products from near-infrared Greenhouse Gases Observing Satellite (GOSAT) observations: Lowermost tropospheric (LMT, from 0 to 2.5km) and upper tropospheric-stratospheric (U, above 2.5km) carbon dioxide partial column mixing ratios. We compare these new products to aircraft profiles and remote surface flask measurements and find that the seasonal and year-to-year variations in the new partial column mixing ratios significantly improve upon the Atmospheric CO2 Observations from Space (ACOS) and GOSAT (ACOS-GOSAT) initial guess and/or a priori, with distinct patterns in the LMT and U seasonal cycles that match validation data. For land monthly averages, we find errors of 1.9, 0.7, and 0.8ppm for retrieved GOSAT LMT, U, and XCO2; for ocean monthly averages, we find errors of 0.7, 0.5, and 0.5ppm for retrieved GOSAT LMT, U, and XCO2. In the southern hemispheric biomass burning season, the new partial columns show similar patterns to MODIS fire maps and MOPITT multispectral CO for both vertical levels, despite a flat ACOS-GOSAT prior, and a CO-CO2 emission factor comparable to published values. The difference of LMT and U, useful for evaluation of model transport error, has also been validated with a monthly average error of 0.8 (1.4)ppm for ocean (land). LMT is more locally influenced than U, meaning that local fluxes can now be better separated from CO2 transported from far away.

We describe a method for removing systematic biases of column-averaged dry air mole fractions of CO2 (XCO2) and CH4 (XCH4) derived from short-wavelength infrared (SWIR) spectra of the Greenhouse gases Observing SATellite (GOSAT). We conduct correlation analyses between the GOSAT biases and simultaneously retrieved auxiliary parameters. We use these correlations to bias correct the GOSAT data, removing these spurious correlations. Data from the Total Carbon Column Observing Network (TCCON) were used as reference values for this regression analysis. To evaluate the effectiveness of this correction method, the tnzuncorrected/corrected GOSAT data were compared to independent XCO2 and XCH4 data derived from aircraft measurements taken for the Comprehensive Observation Network for TRace gases by AIrLiner (CONTRAIL) project, the National Oceanic and Atmospheric Administration (NOAA), the US Department of Energy (DOE), the National Institute for Environmental Studies (NIES), the Japan Meteorological Agency (JMA), the HIAPER Pole-to-Pole observations (HIPPO) program, and the GOSAT validation aircraft observation campaign over Japan. These comparisons demonstrate that the empirically derived bias correction improves the agreement between GOSAT XCO2/XCH4 and the aircraft data. Finally, we present spatial distributions and temporal variations of the derived GOSAT biases.

Deep convection in the Asian summer monsoon is a significant transport process for lifting pollutants from the planetary boundary layer to the tropopause level. This process enables efficient injection into the stratosphere of reactive species such as chlorinated very-short-lived substances (Cl-VSLSs) that deplete ozone. Past studies of convective transport associated with the Asian summer monsoon have focused mostly on the south Asian summer monsoon. Airborne observations reported in this work identify the East Asian summer monsoon convection as an effective transport pathway that carried record-breaking levels of ozone-depleting Cl-VSLSs (mean organic chlorine from these VSLSs ~500 ppt) to the base of the stratosphere. These unique observations show total organic chlorine from VSLSs in the lower stratosphere over the Asian monsoon tropopause to be more than twice that previously reported over the tropical tropopause. Considering the recently observed increase in Cl-VSLS emissions and the ongoing strengthening of the East Asian summer monsoon under global warming, our results highlight that a reevaluation of the contribution of Cl-VSLS injection via the Asian monsoon to the total stratospheric chlorine budget is warranted., Competing Interests: Competing interests statement:The authors declare no competing interest.

California methane (CH 4 ) emissions are quantified for three years from two tower networks and one aircraft campaign. We used backward trajectory simulations and a mesoscale Bayesian inverse model, initialized by three inventories, to achieve the emission quantification. Results show total statewide CH 4 emissions of 2.05 ± 0.26 (at 95% confidence) Tg/yr, which is 1.14 to 1.47 times greater than the anthropogenic emission estimates by California Air Resource Board (CARB). Some of differences could be biogenic emissions, superemitter point sources, and other episodic emissions which may not be completely included in the CARB inventory. San Joaquin Valley (SJV) has the largest CH 4 emissions (0.94 ± 0.18 Tg/yr), followed by the South Coast Air Basin, the Sacramento Valley, and the San Francisco Bay Area at 0.39 ± 0.18, 0.21 ± 0.04, and 0.16 ± 0.05 Tg/yr, respectively. The dairy and oil/gas production sources in the SJV contribute 0.44 ± 0.36 and 0.22 ± 0.23 Tg CH 4 /yr, respectively. This study has important policy implications for regulatory programs, as it provides a thorough multiyear evaluation of the emissions inventory using independent atmospheric measurements and investigates the utility of a complementary multiplatform approach in understanding the spatial and temporal patterns of CH 4 emissions in the state and identifies opportunities for the expansion and applications of the monitoring network.

The Rim Fire was one of the largest wildfires in California history, burning over 250,000 acres during August and September 2013 affecting air quality locally and regionally in the western U.S. Routine surface monitors, remotely sensed data, and aircraft based measurements were used to assess how well the Community Multiscale Air Quality (CMAQ) photochemical grid model applied at 4 and 12 km resolution represented regional plume transport and chemical evolution during this extreme wildland fire episode. Impacts were generally similar at both grid resolutions although notable differences were seen in some secondary pollutants (e.g., formaldehyde and peroxyacyl nitrate) near the Rim fire. The modeling system does well at capturing near-fire to regional scale smoke plume transport compared to remotely sensed aerosol optical depth (AOD) and aircraft transect measurements. Plume rise for the Rim fire was well characterized as the modeled plume top was consistent with remotely sensed data and the altitude of aircraft measurements, which were typically made at the top edge of the plume. Aircraft-based lidar suggests O 3 downwind in the Rim fire plume was vertically stratified and tended to be higher at the plume top, while CMAQ estimated a more uniformly mixed column of O 3 . Predicted wildfire ozone (O 3 ) was overestimated both at the plume top and at nearby rural and urban surface monitors. Photolysis rates were well characterized by the model compared with aircraft measurements meaning aerosol attenuation was reasonably estimated and unlikely contributing to O 3 overestimates at the top of the plume. Organic carbon was underestimated close to the Rim fire compared to aircraft data, but was consistent with nearby surface measurements. Periods of elevated surface PM 2.5 at rural monitors near the Rim fire were not usually coincident with elevated O 3 ., (Published by Elsevier B.V.)

Spaceborne measurements by NASA's Orbiting Carbon Observatory-2 (OCO-2) at the kilometer scale reveal distinct structures of atmospheric carbon dioxide (CO 2 ) caused by known anthropogenic and natural point sources. OCO-2 transects across the Los Angeles megacity (USA) show that anthropogenic CO 2 enhancements peak over the urban core and decrease through suburban areas to rural background values more than ~100 kilometers away, varying seasonally from ~4.4 to 6.1 parts per million. A transect passing directly downwind of the persistent isolated natural CO 2 plume from Yasur volcano (Vanuatu) shows a narrow filament of enhanced CO 2 values (~3.4 parts per million), consistent with a CO 2 point source emitting 41.6 kilotons per day. These examples highlight the potential of the OCO-2 sensor, with its unprecedented resolution and sensitivity, to detect localized natural and anthropogenic CO 2 sources., (Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

The current United States (US) National Ambient Air Quality Standard (NAAQS) for O3 (75 ppb) is expected to be revised to between 60 and 70 ppb. As the NAAQS becomes more stringent, characterizing the extent of O3 and precursors transported into the US is increasingly important. Given the high elevation, complex terrain, and location in the Intermountain West, the State of Nevada is ideally situated to intercept air transported into the US. Until recently, measurements of O3 and associated pollutants were limited to areas in and around the cities of Las Vegas and Reno. In 2011, the Nevada Rural Ozone Initiative began and through this project 13 surface monitoring sites were established. Also in 2011, the NASA Ames Alpha Jet Atmospheric eXperiment (AJAX) began making routine aircraft measurements of O3 and other greenhouse gases in Nevada. The availability of aircraft and surface measurements in a relatively rural, remote setting in the Intermountain West presented a unique opportunity to investigate sources contributing to the O3 observed in Nevada. Our analyses indicate that stratosphere to troposphere transport, long-range transport of Asian pollution, and regional emissions from urban areas and wildfires influence surface observations. The complexity of sources identified here along with the fact that O3 frequently approaches the threshold being considered for a revised NAAQS indicate that interstate and international cooperation will be necessary to achieve compliance with a more stringent regulatory standard. Further, on a seasonal basis we found no significant difference between daily 1-h maximum O3 at surface sites, which ranged in elevation from 888 to 2307 m, and aircraft measurements of O3 <2500 m which suggests that similar processes influence daytime O3 across rural Nevada and indicates that column measurements from Railroad Valley, NV are useful in understanding these processes., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H 2 SO 4 ) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1 H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface.

The solubility of gas-phase acetic acid (CH(3)COOH, HAc) and trifluoroacetic acid (CF(3)COOH, TFA) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (207-245 K) and acid composition (40-75 wt %, H(2)SO(4)). For both HAc and TFA, the effective Henry's law coefficient, H*, is inversely dependent on temperature. Measured values of H* for TFA range from 1.7 × 10(3) M atm(-1) in 75.0 wt % H(2)SO(4) at 242.5 K to 3.6 × 10(8) M atm(-1) in 40.7 wt % H(2)SO(4) at 207.8 K. Measured values of H* for HAc range from 2.2 × 10(5) M atm(-1) in 57.8 wt % H(2)SO(4) at 245.0 K to 3.8 × 10(8) M atm(-1) in 74.4 wt % H(2)SO(4) at 219.6 K. The solubility of HAc increases with increasing H(2)SO(4) concentration and is higher in strong sulfuric acid than in water. In contrast, the solubility of TFA decreases with increasing sulfuric acid concentration. The equilibrium concentration of HAc in UT/LS aerosol particles is estimated from our measurements and is found to be up to several orders of magnitude higher than those determined for common alcohols and small carbonyl compounds. On the basis of our measured solubility, we determine that HAc in the upper troposphere undergoes aerosol partitioning, though the role of H(2)SO(4) aerosol particles as a sink for HAc in the upper troposphere and lower stratosphere will only be discernible under high atmospheric sulfate perturbations.

The solubility of gas-phase ethanol (ethyl alcohol, CH3CH2OH, EtOH) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (209-237 K) and acid composition (39-76 wt % H2SO4). Ethanol is very soluble under these conditions: effective Henry's law coefficients, H, range from 4 x 10(4) M atm(-1) in the 227 K, 39 wt % acid to greater than 10(7) M atm(-1) in the 76 wt % acid. In 76 wt % sulfuric acid, ethanol solubility exceeds that which can be precisely determined using the Knudsen cell technique but falls in the range of 10(7)-10(10) M atm(-1). The equilibrium concentration of ethanol in upper tropospheric/lower stratospheric (UT/LS) sulfate particles is calculated from these measurements and compared to other small oxygenated organic compounds. Even if ethanol is a minor component in the gas phase, it may be a major constituent of the organic fraction in the particle phase. No evidence for the formation of ethyl hydrogen sulfate was found under our experimental conditions. While the protonation of ethanol does augment solubility at higher acidity, the primary reason H increases with acidity is an increase in the solubility of molecular (i.e., neutral) ethanol.