The photochemical production and evolution of six C2-C5 alkyl nitrates (ethyl-, 1-propyl-, 2-propyl-, 2-butyl-, 2-pentyl-, and 3-pentyl nitrate) was investigated using selected data from 5500 whole air samples collected downwind of Asia during the airborne Transport and Chemical Evolution over the Pacific (TRACE-P) field campaign (February-April 2001). Air mass age was important for selecting appropriate field data to compare with laboratory predictions of C5 alkyl nitrate production rates. In young, highly polluted air masses, the ratio between the production rates of 3-pentyl nitrate and 2-pentyl nitrate from n-pentane was 0.60-0.65. These measured ratios show excellent agreement with results from a field study in Germany (0.63 ± 0.06), and they agree better with predicted ratios from older laboratory kinetic studies (0.63-0.66) than with newer laboratory results (0.73 ± 0.08). TRACE-P samples that did not show influence from marine alkyl nitrate sources were used to investigate photochemical alkyl nitrate evolution. Relative to 2-butyl nitrate/n-butane, the measured ratios of ethyl nitrate/ethane and 2-propyl nitrate/propane showed notable deviations from modeled values based on laboratory kinetic data, suggesting additional Asian sources of their alkyl peroxy radical precursors. By contrast, the measured ratios of 1-propyl-, 2-pentyl-, and 3-pentyl nitrate to their respective parent hydrocarbons were fairly close to modeled values. The 1-propyl nitrate findings contrast with field studies in North America, and suggest that air downwind of Asia was not significantly impacted by additional 1-propyl nitrate precursors. The sensitivity of modeled photochemical processing times to hydroxyl radical concentration, altitude, city ventilation times, and dilution is discussed.

A time-dependent photochemical box model is used to examine the photochemistry of the equatorial and southern subtropical Pacific troposphere with aircraft data obtained during two distinct seasons: the Pacific Exploratory Mission-Tropics A (PEM-Tropics A) field campaign in September and October of 1996 and the Pacific Exploratory Mission-Tropics B (PEM-Tropics B) campaign in March and April of 1999. Model-predicted values were compared to observations for selected species (e.g., NO2, OH, HO2) with generally good agreement. Predicted values of HO2 were larger than those observed in the upper troposphere, in contrast to previous studies which show a general underprediction of HO2 at upper altitudes. Some characteristics of the budgets of HOx, NOx, and peroxides are discussed. The integrated net tendency for O3 is negative over the remote Pacific during both seasons, with gross formation equal to no more than half of the gross destruction. This suggests that a continual supply of O3 into the Pacific region throughout the year must exist in order to maintain O3 levels. Integrated net tendencies for equatorial O3 showed a seasonality, with a net loss of 1.06×1011 molecules cm-2 s-1 during PEM-Tropics B (March) increasing by 50% to 1.60×1011 molecules cm-2 s-1 during PEM-Tropics A (September). The seasonality over the southern subtropical Pacific was somewhat lower, with losses of 1.21×1011 molecules cm-2 s-1 during PEM-Tropics B (March) increasing by 25% to 1.51×1011 molecules cm-2 s-1 during PEM-Tropics A (September). While the larger net losses during PEM-Tropics A were primarily driven by higher concentrations of O3, the ability of the subtropical atmosphere to destroy O3 was ∼30% less effective during the PEM-Tropics A (September) campaign due to a drier atmosphere and higher overhead O3 column amounts. Copyright 2001 by the American Geophysical Union.

The first direct in situ measurements of HO2NO2 in the upper troposphere were performed from the NASA DC-8 during the Intercontinental Chemical Transport Experiment-North America 2004 with a chemical ionization mass spectrometer (CIMS). These measurements provide an independent diagnostic of HOx chemistry in the free troposphere and complement direct observations of HOx, because of the dual dependency of HO2NO2 on HOx and NOx. On average, the highest HO2NO2 mixing ratio of 76 pptv (median = 77 pptv, σ, = 39 pptv) was observed at altitudes of 8-9 km. Simple steady state calculations of HO2NO2, constrained by measurements of HOx, NOx, and J values, are in good agreement (slope = 0.90, R² = 0.60, and z = 5.5-7.5 km) with measurements in the midtroposphere where thermal decomposition is the major loss process. Above 8 km the calculated steady state HO2NO2 is in poor agreement with observed values (R² = 0.20) and is typically larger by a factor of 2.4. Conversely, steady state calculations using model-derived HOx show reasonable agreement with the observed HO2NO2 in both the midtroposphere (slope = 0.96, intercept = 7.0, and R² = 0.63) and upper troposphere (slope = 0.80, intercept = 32.2, and R² = 0.58). These results indicate that observed HO2 and HO2NO2 are in poor agreement in the upper troposphere but that HO2NO2 levels are consistent with current photochemical theory. Copyright 2007 by the American Geophysical Union.

A major observation recorded during NASA's western Pacific Exploratory Mission (PEM-West B) was the large shift in tropical NO levels as a function of geographical location. High-altitude NO levels exceeding 100 pptv were observed during portions of tropical flights 5-8, while values almost never exceeded 20 pptv during tropical flights 9 and 10. The geographical regions encompassing these two flight groupings are here labeled "high" and "low" NOx regimes. A comparison of these two regimes, based on back trajectories and chemical tracers, suggests that air parcels in both were strongly influenced by deep convection. The low NOx regime appears to have been predominantly impacted by marine convection, whereas the high NOx regime shows evidence of having been more influenced by deep convection over a continental land mass. DMSP satellite observations point strongly toward lightning as the major source of NOx in the latter regime. Photochemical ozone formation in the high NOx regime exceeded that for low NOx by factors of 2 to 6, whereas O3 destruction in the low NOx regime exceeded that for high NOx by factors of up to 3. Taking the tropopause height to be 17 km, estimates of the net photochemical effect on the O3 column revealed that the high NOx regime led to a small net production. By contrast, the low NOx regime was shown to destroy O3 at the rate of 3.4% per day. One proposed mechanism for off-setting this projected large deficit would involve the transport of O3 rich midlatitude air into the tropics. Alternatively, it is suggested that O3 within the tropics may be overall near self-sustaining with respect to photochemical activity. This scenario would require that some tropical regions, unsampled at the time of PEM-B, display significant net column O3 production, leading to an overall balanced budget for the "greater" tropical Pacific basin. Details concerning the chemical nature of such regimes are discussed.

Interactions between atmospheric hydrogen oxides and aircraft nitrogen oxides determine the impact of aircraft exhaust on atmospheric chemistry. To study these interactions, the Subsonic Assessment: Ozone and Nitrogen Oxide Experiment (SONEX) assembled the most complete measurement complement to date for studying HO(x) (OH and HO2) chemistry in the free troposphere. Observed and modeled HO(x) agree on average to within experimental uncertainties (±40%). However, significant discrepancies occur as a function of NO and at solar zenith angles >70°. Some discrepancies appear to be removed by model adjustments to HO(x)-NO(x) chemistry, particularly by reducing HO2NO2 (PNA) and by including heterogeneous reactions on aerosols and cirrus clouds.

Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1 - 12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH3COCHA3), methylethyl ketone (CH3COC2H5, MEK), methanol (CH3OH), ethanol (C2H5OH), acetaldehyde (CH3CHO), propionaldehyde C2H 5CHO), peroxyacylnitrates (PANs) (CnH 2n+1COO2NO2), and organic nitrates (CnH2n+1ONO2). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH 3OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (ΣOVOC) was nearly twice that of nonmethane hydrocarbons (Σ C2-C8 NMHC. Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH 3Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than predicted. At their observed levels, acetaldehyde mixing ratios are shown to be an important source of HCHO (and HOx) and PAN in the troposphere. On the basis of presently known chemistry, measured mixing ratios of aldehydes and PANs are mutually incompatible. We provide rough estimates of the global sources of several OVOC and conclude that collectively these are extremely large (150-500 Tg C yr-1) but remain poorly quantified. Copyright 2004 by the American Geophysical Union.

A comprehensive group of reactive nitrogen species (NO, NO2, HNO3, HO2NO2, PANs, alkyl nitrates, and aerosol-NO3^-) were measured over North America during July/August 2004 from the NASA DC-8 platform (0.1-12 km). Nitrogen containing tracers of biomass combustion (HCN and CH3CN) were also measured along with a host of other gaseous (CO, VOC, OVOC, halocarbon) and aerosol tracers. Clean background air as well as air with influences from biogenic emissions, anthropogenic pollution, biomass combustion, convection, lightning, and the stratosphere was sampled over the continental United States, the Atlantic, and the Pacific. The North American upper troposphere (UT) was found to be greatly influenced by both lightning NOx and surface pollution lofted via convection and contained elevated concentrations of PAN, ozone, hydrocarbons, and NOx. Observational data suggest that lightning was a far greater contributor to NOx in the UT than previously believed. PAN provided a dominant reservoir of reactive nitrogen in the UT while nitric acid dominated in the lower troposphere (LT). Peroxynitric acid (HO2NO2) was present in sizable concentrations peaking at around 8 km. Aerosol nitrate appeared to be mostly contained in large soil based particles in the LT. Plumes from Alaskan fires contained large amounts of PAN and aerosol nitrate but little enhancement in ozone. A comparison of observed data with simulations from four 3-D models shows significant differences between observations and models as well as among models. We investigate the partitioning and interplay of the reactive nitrogen species within characteristic air masses and further examine their role in ozone formation. Copyright 2007 by the American Geophysical Union.

Measurements of several short-lived photochemical species (e.g., OH, HO2, and CH2O) were obtained from the DC-8 and P3-B aircraft during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) campaign. To assess fast photochemical theory over the east Asian coast and western Pacific, these measurements are compared to predictions using a photochemical time-dependent box model constrained by coincident measurements of long-lived tracers and physical parameters. Both OH and HO2 are generally overpredicted by the model throughout the troposphere, which is a different result from previous field campaigns. The calculated-to-observed ratio of OH shows an altitude trend, with OH overpredicted by 80% in the upper troposphere and by 40-60% in the middle troposphere. Boundary layer and lower tropospheric OH ratios decrease from middle tropospheric values to 1.07 for the DC-8 and to 0.70 for the P3-B. HO2 measured on the DC-8 is overpredicted by a median of 23% and shows no trend in the agreement with altitude. Three subsets of data which compose 12% of the HO2 measurements represent outliers with respect to calculated-to-observed ratios: stratospherically influenced air, upper tropospheric data with NO > 135 pptv, and data from within clouds. Pronounced underpredictions of both HO2 and OH were found for stratospherically influenced air, which is in contrast to previous studies showing good agreement of predicted and observed HOx, in the stratosphere. Observational evidence of heterogeneous uptake of HO2 within low and middle tropospheric clouds is presented, though there is no indication of significant HO2 uptake within higher-altitude clouds. Model predictions of CH2O are in good agreement with observations in the median for background concentrations, but a large scatter exists. Factors contributing to this scatter are examined, including the limited availability of some important constraining measurements, particularly CH3OOH. Some high concentrations of CH2O near the coast are underpredicted by the box model as a result of the inherent neglect of transport effects of CH2O and its precursors via the steady state assumption; however, these occurrences are limited to ∼1% of the data. For the vast majority of the atmosphere, transport is unimportant in the budget of CH2O, which may be considered to be in steady state. Copyright 2004 by the American Geophysical Union.

We use aircraft observations obtained during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission to examine the distributions and source attributions of O 3 and NO y in the Arctic and sub-Arctic region. Using a number of marker tracers, we distinguish various air masses from the background troposphere and examine their contributions to NO x, O 3, and O 3 production in the Arctic troposphere. The background Arctic troposphere has a mean O 3 of ∼60 ppbv and NO x of ∼25 pptv throughout spring and summer with CO decreasing from ∼145 ppbv in spring to ∼100 ppbv in summer. These observed mixing ratios are not notably different from the values measured during the 1988 ABLE-3A and the 2002 TOPSE field campaigns despite the significant changes in emissions and stratospheric ozone layer in the past two decades that influence Arctic tropospheric composition. Air masses associated with stratosphere-troposphere exchange are present throughout the mid and upper troposphere during spring and summer. These air masses, with mean O 3 concentrations of 140-160 ppbv, are significant direct sources of O 3 in the Arctic troposphere. In addition, air of stratospheric origin displays net O 3 formation in the Arctic due to its sustainable, high NO x (75 pptv in spring and 110 pptv in summer) and NO y (∼800 pptv in spring and ∼1100 pptv in summer). The air masses influenced by the stratosphere sampled during ARCTAS-B also show conversion of HNO 3 to PAN. This active production of PAN is the result of increased degradation of ethane in the stratosphere-troposphere mixed air mass to form CH 3CHO, followed by subsequent formation of PAN under high NO x conditions. These findings imply that an adequate representation of stratospheric NO y input, in addition to stratospheric O 3 influx, is essential to accurately simulate tropospheric Arctic O 3, NO x and PAN in chemistry transport models. Plumes influenced by recent anthropogenic and biomass burning emissions observed during ARCTAS show highly elevated levels of hydrocarbons and NO y (mostly in the form of NO x and PAN), but do not contain O 3 higher than that in the Arctic tropospheric background except some aged biomass burning plumes sampled during spring. Convection and/or lightning influences are negligible sources of O 3 in the Arctic troposphere but can have significant impacts in the upper troposphere in the continental sub-Arctic during summer. © 2011 Author(s).