Key Points Statistical models from forecast schemes can explain up to 48% of annual North Atlantic TC frequency Hindcast period analogous to warmer climate keeps only surface winds and SST gradient in regression The CLLJ is a major modulator of future North Atlantic TC frequency
Abstract Diagnosing carbon dioxide (CO 2 ) and methane (CH 4 ) fluxes at subcontinental scales is complicated by sparse observations, limited knowledge of prior fluxes and their uncertainties, and background and transport errors. Multispecies measurements in flasks sampled during the wintertime ACT‐America campaign were used for background characterization and source apportionment of regional anthropogenic CO 2 and CH 4 fluxes when ecosystem CO 2 exchange is likely to be least active. Continental background trace gas mole fractions for regional enhancements are defined using samples from the upper troposphere and assessed using model products. Trace gas enhancements taken from flask samples in the lower troposphere with background levels subtracted out are then interpreted to inform CO 2 and CH 4 enhancement variability in the eastern United States. Strong correlations between CO 2 and CH 4 enhancements in the Midwestern and Mid‐Atlantic United States indicated colocated anthropogenic sources. Oil and natural gas influence was also broadly observed throughout the entire observational domain. In the Midwestern United States, agricultural influence on CO 2 and CH 4 enhancement variability was evident during above‐average wintertime temperatures. Weaker correlations between CO 2 and anthropogenic tracer enhancements in the Southeastern United States indicated potentially nonnegligible wintertime ecosystem CO 2 exchange, with biogenic tracers indicating more active surface processing than other regions. These whole‐air flask samples illuminated significant regional CO 2 and CH 4 sources or sinks during Atmospheric Carbon and Transport‐America (ACT‐America) and can provide additional information for informing regional inverse modeling efforts.
The Houston‐Galveston‐Brazoria urban area contains industrial petrochemical sources that emit volatile organic compounds and nitrogen oxides, resulting in rapid and efficient ozone production downwind. During September to October 2006, the NOAA WP‐3D aircraft conducted research flights as part of the second Texas Air Quality Study (TexAQS II). We use measurements of NO x , SO 2 , and speciated hydrocarbons from industrial sources in Houston to derive source emission ratios and compare these to emission inventories and the first Texas Air Quality Study (TexAQS) in 2000. Between 2000 and 2006, NO x /CO 2 emission ratios changed by an average of −29% ± 20%, while a significant trend in SO 2 /CO 2 emission ratios was not observed. We find that high hydrocarbon emissions are routine for the isolated petrochemical facilities. Ethene (C 2 H 4 ) and propene (C 3 H 6 ) are the major contributors to ozone formation based on calculations of OH reactivity for organic species including C 2 –C 10 alkanes, C 2 –C 5 alkenes, ethyne, and C 2 –C 5 aldehydes and ketones. Measured ratios of C 2 H 4 /NO x and C 3 H 6 /NO x exceed emission inventory values by factors of 1.4–20 and 1–24, respectively. We examine trends in C 2 H 4 /NO x and C 3 H 6 /NO x ratios between 2000 and 2006 for the isolated petrochemical sources and estimate a change of −30% ± 30%, with significant day‐to‐day and within‐plume variability. Median ambient mixing ratios of ethene and propene in Houston show decreases of −52% and −48%, respectively, between 2000 and 2006. The formaldehyde, acetaldehyde, and peroxyacetyl nitrate products produced by alkene oxidation are observed downwind, and their time evolution is consistent with the rapid photochemistry that also produces ozone.
OH and HO 2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC‐8 aircraft during the Intercontinental Chemical Transport Experiment‐A (INTEX‐A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. The HOx results from INTEX‐A are compared to those from previous campaigns and to results for other related measurements from INTEX‐A. Throughout the troposphere, observed OH was generally 0.95 of modeled OH; below 8 km, observed HO 2 was generally 1.20 of modeled HO 2 . This observed‐to‐modeled comparison is similar to that for TRACE‐P, another midlatitude study for which the median observed‐to‐modeled ratio was 1.08 for OH and 1.34 for HO 2 , and to that for PEM‐TB, a tropical study for which the median observed‐to‐modeled ratio was 1.17 for OH and 0.97 for HO 2 . HO 2 behavior above 8 km was markedly different. The observed‐to‐modeled HO 2 ratio increased from ∼1.2 at 8 km to ∼3 at 11 km with the observed‐to‐modeled ratio correlating with NO. Above 8 km, the observed‐to‐modeled HO 2 and observed NO were both considerably greater than observations from previous campaigns. In addition, the observed‐to‐modeled HO 2 /OH, which is sensitive to cycling reactions between OH and HO 2 , increased from ∼1.5 at 8 km to almost 3.5 at 11 km. These discrepancies suggest a large unknown HO x source and additional reactants that cycle HO x from OH to HO 2 . In the continental planetary boundary layer, the observed‐to‐modeled OH ratio increased from 1 when isoprene was less than 0.1 ppbv to over 4 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HO x sources. Progress in resolving these discrepancies requires a focused research activity devoted to further examination of possible unknown OH sinks and HO x sources.
Large‐scale measurements of ozone (O 3 ) and aerosol distributions were made from the NASA DC‐8 aircraft during the Transport and Chemical Evolution over the Pacific (TRACE‐P) field experiment conducted in February–April 2001. Remote measurements were made with an airborne lidar to provide O 3 and multiple‐wavelength aerosol backscatter profiles from near the surface to above the tropopause along the flight track. In situ measurements of O 3 , aerosols, and a wide range of trace gases were made onboard the DC‐8. Five‐day backward trajectories were used in conjunction with the O 3 and aerosol distributions on each flight to indicate the possible origin of observed air masses, such as from biomass burning regions, continental pollution, desert regions, and oceanic regions. Average latitudinal O 3 and aerosol scattering ratio distributions were derived from all flights west of 150°E, and these distributions showed the average latitude and altitude dependence of different dynamical and chemical processes in determining the atmospheric composition over the western Pacific. TRACE‐P (TP) showed an increase in the average latitudinal distributions of both O 3 and aerosols compared to PEM‐West B (PWB), which was conducted in February–March 1994. O 3 , aerosol, and potential vorticity levels were used to identify nine air mass types and quantify their frequency of occurrence as a function of altitude. This paper discusses the characteristics of the different air mass types encountered during TP and compares them to PWB. These results confirmed that most of the O 3 increase in TP was due to photochemistry. The average latitudinal eastward O 3 flux in the western Pacific during TP was found to peak near 32°N with a total average O 3 flux between 14 and 46°N of 5.2 Tg/day. The eastward total CO flux was calculated to be 2.2 Tg‐C/day with ∼6% estimated from Asia. The Asian flux of CO 2 and CH 4 was estimated at 4.9 and 0.06 Tg‐C/day.
Abstract. Comprehensive aircraft measurements of volatile organic compounds (VOCs) covering the South Coast Air Basin (SoCAB) and San Joaquin Valley (SJV) of California were obtained in the summer of 2019. Combined with the CO, CH4, and NOx data, the total calculated gas-phase hydroxyl radical reactivity (cOHRTOTAL) was quantified to be 6.1 and 4.6 s−1 for the SoCAB and SJV, respectively. VOCs accounted for ∼ 60 %–70 % of the cOHRTOTAL in both basins. In particular, oxygenated VOCs (OVOCs) contributed >60 % of the cOHR of total VOCs (cOHRVOC) and the total observed VOC mixing ratio. Primary biogenic VOCs (BVOCs) represented a minor fraction (<2 %) of the total VOC mixing ratio but accounted for 21 % and 6 % of the cOHRVOC in the SoCAB and SJV, respectively. Furthermore, the contribution of BVOCs to the cOHRVOC increased with increasing cOHRVOC in the SoCAB, suggesting that BVOCs were important ozone precursors during high ozone episodes. Spatially, the trace gases were heterogeneously distributed in the SoCAB, with their mixing ratios and cOHR being significantly greater over the inland regions than the coast, while their levels were more evenly distributed in SJV. The results highlight that a better grasp of the emission rates and sources of OVOCs and BVOCs is essential for a predictive understanding of the ozone abundance and distribution in California.
Airborne measurements of a large number of oxygenated organics were carried out in the Pacific troposphere (to 12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measurements included acetaldehyde, propanaldehyde, acetone, methylethyl ketone, methanol, ethanol, PAM and organic nitrates. Independent measurements of formaldehyde, peroxides, and tracers were also available. Highly polluted as well as pristine air masses were sampled. Oxygenated organics were abundant in the clean In troposphere and were greatly enhanced in the outflow regions from Asia. Extremely high concentrations of aldehydes could be measured in the troposphere. It is not possible to explain the large abundances of aldehydes in the background troposphere without invoking significant oceanic sources. A strong correlation between the observed mixing ratios of formaldehyde and acetaldehyde is present. We infer that higher aldehydes (such as acetaldehyde and propanaldehyde) may provide a large source of formaldehyde and sequester Cox throughout the troposphere. The atmospheric behavior of acetone, methylethyl ketone, and methanol is generally indicative of their common terrestrial sources with a Image contribution from biomass/biofuel burning. A vast body of data has been collected and it is being analyzed both statistically and with the help of models to better understand the role that oxygenated organics play in the atmosphere and to unravel their sources and sinks. These results will be presented.
Data obtained during the TRACE‐P experiment is used to evaluate how well the CFORS/STEM‐2K1 regional‐scale chemical transport model is able to represent the aircraft observations. Thirty‐one calculated trace gas and aerosol parameters are presented and compared to the in situ data. The regional model is shown to accurately predict many of the important features observed. The mean values of all the model parameters in the lowest 1 km are predicted within ±30% of the observed values. The correlation coefficients (R) for the meteorological parameters are found to be higher than those for the trace species. For example, for temperature, R > 0.98. Among the trace species, ethane, propane, and ozone show the highest values (0.8 < R < 0.9), followed by CO, SO 2 , and NO y . NO and NO 2 had the lowest values (R < 0.4). Analyses of pollutant transport into the Yellow Sea by frontal events are presented and illustrate the complex nature of outflow. Biomass burning from SE Asia is transported in the warm conveyor belt at altitudes above ∼2 km and at latitudes below 30N. Outflow of pollution emitted along the east coast of China in the postfrontal regions is typically confined to the lower ∼2 km and results in high concentrations with plume‐like features in the Yellow Sea. During these situations the model underpredicts CO and black carbon (among other species). An analysis of ozone production in this region is also presented. In and around the highly industrialized regions of East Asia, where fossil fuel usage dominates, ozone is NMHC‐limited. South of ∼30–35N, ozone production is NO x ‐limited, reflecting the high NMHC/NO x ratios due to the large contributions to the emissions from biomass burning, biogenics sources, and biofuel usage in central China and SE Asia.
