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As part of the Deep Convective Cloud and Chemistry (DC3) experiment, the National Science Foundation/National Center for Atmospheric Research (NCAR) Gulfstream-V (GV) and NASA DC-8 research aircraft probed the chemical composition of the inflow and outflow of two convective storms (north storm, NS, south storm, SS) originating in the Colorado region on 22 June 2012, a time when the High Park wildfire was active in the area. A wide range of trace species were measured on board both aircraft including biomass burning (BB) tracers hydrogen cyanide (HCN) and acetonitrile (ACN). Acrolein, a much shorter lived tracer for BB, was also quantified on the GV. The data demonstrated that the NS had ingested fresh smoke from the High Park fire and as a consequence had a higher VOC OH reactivity than the SS. The SS lofted aged fire tracers along with other boundary layer ozone precursors and was more impacted by lightning NOx (LNOx) than the NS. The NCAR master mechanism box model was initialized with measurements made in the outflow of the two storms. The NS and SS were predicted to produce 11 and 14 ppbv of O3, respectively, downwind of the storm over 2 days. Sensitivity tests revealed that the ozone production potential of the SS was highly dependent on LNOx. Normalized excess mixing ratios, ΔX/ΔCO, for HCN and ACN were determined in both the fire plume and the storm outflow and found to be 7.0 ± 0.5 and 2.3 ± 0.5 pptv ppbv-1, respectively, and 1.4 ± 0.3 pptv ppbv-1 for acrolein in the outflow only.

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.

We employed a fast response thermal dissociation-chemical ionization mass spectrometer (TD-CIMS) system to measure eddy covariance fluxes of peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN) and peroxymethacryloyl nitrate (MPAN). Fluxes were measured for eight consecutive days in July 2003 at a Loblolly pine forest in North Carolina along with eddy covariance NOy fluxes. Covariances between PAN concentration and vertical wind velocity indicated consistent deposition fluxes that ranged up to approximately -14 ng N m-2 s-1. The average daytime flux peaked at -6.0 ng N m-2 s-1 and accounted for ∼20% of the daytime NOy flux. Calculations suggest minimum daytime surface resistances for PAN in the range of 70-130 s m-1. It was estimated that approximately half of daytime uptake was through plant stomates. Average PAN deposition velocities, Vd(PAN), showed a daytime maximum of ∼10.0 mm s-1; however, deposition did not cease during nighttime periods. Vd(PAN) was highly variable at night and increased when canopy elements were wet from either precipitation or dew formation. Diel patterns of deposition velocity of MPAN and PPN were similar to that of PAN. These results suggest that deposition of PAN, at least to coniferous forest canopies, is much faster than predicted with current deposition algorithms. Although deposition of PAN is unlikely to compete with thermal dissociation during warm summer periods, it will likely play an important role in removing PAN from the atmosphere in colder regions or during winter. The fate of PAN at the surface and within the plants remains unknown, but may present a previously ignored source of nitrogen to ecosystems. Copyright 2006 by the American Geophysical Union.

Simultaneous measurements of speciated, total reactive nitrogen (NOy) and particulate NO3 (particle diameter

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.

Aircraft measurements of ozone (O3) and its precursors (reactive nitrogen, CO, nonmethane hydrocarbons) were made over the western Pacific during the Transport and Chemical Evolution Over the Pacific (TRACE-P) campaign, which was conducted during February-April 2001. Biomass burning activity was high over Southeast Asia (SEA) during this period (dry season), and convective activity over SEA frequently transported air from the boundary layer to the free troposphere, followed by eastward transport to the sampling region over the western Pacific south of 30°N. This data set allows for systematic investigations of the chemical and physical processes in the outflow from SEA. Methyl chloride (CH3Cl) and CO are chosen as primary and secondary tracers, respectively, to gauge the degree of the impact of emissions of trace species from biomass burning. Biomass burning is found to be a major source of reactive nitrogen (NO x, PAN, HNO3, and nitrate) and O3 in this region from correlations of these species with the tracers. Changes in the abundance of reactive nitrogen during upward transport are quantified from the altitude change of the slopes of the correlations of these species with CO. NOx decreased with altitude due to its oxidation to HNO3. On the other hand, PAN was conserved during transport from the lower to the middle troposphere, consistent with its low water solubility and chemical stability at low temperatures. Large losses of HNO3 and nitrate, which are highly water soluble, occurred in the free troposphere, most likely due to wet removal by precipitation. This has been shown to be the major pathway of NOy loss in the middle troposphere. Increases in the mixing ratios of O3 and its precursors due to biomass burning in SEA are estimated using the tracers. Enhancements of CO and total reactive nitrogen (NOy), which are directly emitted from biomass burning, were largest at 2-4 km. At this altitude the increases in NOy and O3 were 810 parts per trillion by volume (pptv) and 26 parts per billion by volume (ppbv) above their background values of 240 pptv and 31 ppbv, respectively. The slope of the O3-CO correlation in biomass burning plumes was similar to those observed in fire plumes in northern Australia, Africa, and Canada. The O3 production efficiency (OPE) derived from the O3-CO slope and NOx/CO emission ratio (ER) is shown to be positively correlated with the C2H4 /NOx ER, indicating that the C2H4/NO x ER is a critical parameter in determining the OPE. Comparison of the net O3 flux across the western Pacific region and total O3 production due to biomass burning in SEA suggests that about 70% of O3 produced was transported to the western Pacific. Copyright 2004 by the American Geophysical Union.

A steady state model, constrained by a number of measured quantities, was used to derive peroxy radical levels for the conditions of the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign. The analysis is made using data collected aboard the NCAR/NSF C-130 aircraft from February through May 2000 at latitudes from 40° to 85°N, and at altitudes from the surface to 7.6 km. HO2 + RO2 radical concentrations were measured during the experiment, which are compared with model results over the domain of the study showing good agreement on the average. Average measurement/model ratios are 1.04 (σ = 0.73) and 0.96 (σ = 0.52) for the MLB and HLB, respectively. Budgets of total peroxy radical levels as well as of individual free radical members were constructed, which reveal interesting differences compared to studies at lower latitudes. The midlatitude part of the study region is a significant net source of ozone, while the high latitudes constitute a small net sink leading to the hypothesis that transport from the middle latitudes can explain the observed increase in ozone in the high latitudes. Radical reservoir species concentrations are modeled and compared with the observations. For most conditions, the model does a good job of reproducing the formaldehyde observations, but the peroxide observations are significantly less than steady state for this study. Photostationary state (PSS) derived total peroxy radical levels and NO/NO2 ratios are compared with the measurements and the model; PSS-derived results are higher than observations or the steady state model at low NO concentrations.

The distribution of reactive nitrogen species over the South Pacific during austral springtime appears to be dominated by biomass burning emissions and possibly lightning and stratospheric inputs. The absence of robust correlations of reactive nitrogen species with source-specific tracers (e.g., C2H2 [combustion], CH3Cl [biomass burning], C2Cl4 [industrial], 210Pb [continental], and 7Be [stratospheric]) suggests significant aging and processing of the sampled air parcels due to losses by surface deposition, OH attack, and dilution processes. Classification of the air parcels based on CO enhancements indicates that the greatest influence was found in plumes at 3-8 km altitude in the distributions of HNO3 and peroxyacetyl nitrate (PAN). Here mixing ratios of these species reached 600 parts per trillion by volume (pptv), values surprisingly large for a location several thousand kilometers removed from the nearest continental areas. The mixing ratio of total reactive nitrogen (the NOy sum), operationally defined in this paper as measured (NO + HNO3 + PAN + CH3ONO2 +C2H5ONO2) + modeled (NO2), had a median value of 285 pptv within these plumes compared with 120 pptv in nonplume air parcels. Particle NO3- was not included in this analysis of the NOy sum due to its 10- to 15-min sampling time resolution, but, in general, it was

A large number of oxygenated organic chemicals (peroxyacyl nitrates, alkyl nitrates, acetone, formaldehyde, methanol, methylhydroperoxide, acetic acid and formic acid) were measured during the 1997 Subsonic Assessment (SASS) Ozone and Nitrogen Oxide Experiment (SONEX) airborne field campaign over the Atlantic. In this paper, we present a first picture of the distribution of these oxygenated organic chemicals (Ox-organic) in the troposphere and the lower stratosphere, and assess their source and sink relationships. In both the troposphere and the lower stratosphere, the total atmospheric abundance of these oxygenated species (ΣOx-organic) nearly equals that of total nonmethane hydrocarbons (ΣNMHC), which have been traditionally measured. A sizable fraction of the reactive nitrogen (10-30%) is present in its oxygenated organic form. The organic reactive nitrogen fraction is dominated by peroxyacetyl nitrate (PAN), with alkyl nitrates and peroxypropionyl nitrate (PPN) accounting for

A suite of compounds with a wide range of photochemical lifetimes (3 months to several decades) was measured in the tropical and midlatitude upper troposphere and lower stratosphere during the Stratospheric Tracers of Atmospheric Transport (STRAT) experiment (fall 1995 and winter, summer, and fall 1996) and the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) deployment in late summer 1997. These species include various chlorofluorocarbons, hydrocarbons, halocarbons, and halons measured in whole air samples and CO measured in situ by tunable diode laser spectroscopy. Mixing ratio profiles of long-lived species in the tropical lower stratosphere are examined using a one-dimensional (1-D) photochemical model that includes entrainment from the extratropical stratosphere and is constrained by measured concentrations of OH. Profiles of tracers found using the 1-D model agree well with all the observed tropical profiles for an entrainment time scale of 8.5-4+6 months, independent of altitude between potential temperatures of 370 and 500 K. The tropical profile of CO is used to show that the annually averaged ascent rate profile, on the basis of a set of radiative heating calculations, is accurate to approximately ±44%, a smaller uncertainty than found by considering the uncertainties in the radiative model and its inputs. Tropical profiles of ethane and C2Cl4 reveal that the concentration of Cl is higher than expected on the basis of photochemical model simulations using standard gas phase kinetics and established relationships between total inorganic chlorine and CFC-11. Our observations suggest that short-lived organic chlorinated compounds and HCl carried across the tropical tropopause may provide an important source of inorganic chlorine to the tropical lower stratosphere that has been largely unappreciated in previous studies. The entrainment timescale found here is considerably less than the value found by a similar study that focused on observations obtained in the lower stratosphere during 1994. Several possible explanations for this difference are discussed. Copyright 1999 by the American Geophysical Union.

A comprehensive suite of brominated organic compounds was measured from whole air samples collected during the 1996 NASA Stratospheric Tracers of Atmospheric Transport aircraft campaign and the 1996 NASA Global Tropospheric Experiment Pacific Exploratory Mission-Tropics aircraft campaign. Measurements of individual species and total organic bromine were utilized to describe latitudinal and vertical distributions in the troposphere and lower stratosphere, fractional contributions to total organic bromine by individual species, fractional dissociation of the long-lived species relative to CFC-11, and the Ozone Depletion Potential of the halons and CH3Br. Spatial differences in the various organic brominated compounds were related to their respective sources and chemical lifetimes. The difference between tropospheric mixing ratios in the Northern and Southern Hemispheres for halons was approximately equivalent to their annual tropospheric growth rates, while the interhemispheric ratio of CH3Br was 1.18. The shorter-lived brominated organic species showed larger tropospheric mixing ratios in the tropics relative to midlatitudes, which may reflect marine biogenic sources. Significant vertical gradients in the troposphere were observed for the short-lived species with upper troposphere values 40-70% of the lower troposphere values. Much smaller vertical gradients (3-14%) were observed for CH3Br, and no significant vertical gradients were observed for the halons. Above the tropopause, the decrease in organic bromine compounds was found to have some seasonal and latitudinal differences. The combined losses of the individual compounds resulted in a loss of total organic bromine between the tropopause and 20 km of 38-40% in the tropics and 75-85% in midlatitudes. The fractional dissociation of the halons and CH3Br relative to CFC-11 showed latitudinal differences, with larger values in the tropics. Copyright 1999 by the American Geophysical Union.