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.

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.

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.

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 <10% of the NOy sum. Comparison of the two air parcel classifications for NOx and alkyl nitrate distributions showed no perceivable plume influence, but recycling of reactive nitrogen may have masked this direct effect. In the marine boundary layer, the NOy sum averaged 50 pptv in both air parcel classifications, being somewhat isolated from the polluted conditions above it by the trade wind inversion. In this region, however, alkyl nitrates appear to have an important marine source where they comprise 20-80% of the NOy sum in equatorial and high-latitude regions over the South Pacific. Copyright 2000 by the American Geophysical Union.

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.

Physical and chemical properties of the atmosphere at 0-8 km were measured during the Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiments from February to May 2000 at mid (40°-60°N) and high latitudes (60°-80°N). The observations were analyzed using a diet steady state box model to examine HOx and O3 photochemistry during the spring transition period. The radical chemistry is driven primarily by photolysis of O3 and the subsequent reaction of O(1D) and H2O, the rate of which increases rapidly during spring. Unlike in other tropospheric experiments, observed H2O2 concentrations are a factor of 2-10 lower than those simulated by the model. The required scavenging timescale to reconcile the model overestimates shows a rapid seasonal decrease down to 0.5-1 day in May, which cannot be explained by known mechanisms. This loss of H2O2 implies a large loss of HOx resulting in decreases in O3 production (10-20%) and OH concentrations (20-30%). Photolysis of CH2O, either transported into the region or produced by unknown chemical pathways, appears to provide a significant HOx source at 6-8 km at high latitudes. The rapid increase of in situ O3 production in spring is fueled by concurrent increases of the primary HOx production and NO concentrations. Long-lived reactive nitrogen species continue to accumulate at mid and high latitudes in spring. There is a net loss of NOx to HNO3 and PAN throughout the spring, suggesting that these long-term NOx reservoirs do not provide a net source for NOx in the region. In Situ O3 chemical loss is dominated by the reaction of O3 and HO2, and not that of O(1D) and H2O. At midlatitudes, there is net in situ chemical production Of O3 from February to May. The lower free troposphere (1-4 km) is a region of significant net O3 production. The net production peaks in April coinciding with the observed peak of column O3 (0-8 km). The net in situ O3 production at midlatitudes can explain much of the observed column O3 increase, although it alone cannot explain the observed April maximum. In contrast, there is a net in situ O3 loss from February to April at high latitudes. Only in May is the in situ O3 production larger than loss. The observed continuous increase of column O3 at high latitudes throughout the spring is due to transport from other tropospheric regions or the stratosphere not in situ photochemistry.

We construct a global atmospheric budget for acetaldehyde using a 3-D model of atmospheric chemistry (GEOS-Chem), and use an ensemble of observations to evaluate present understanding of its sources and sinks. Hydrocarbon oxidation provides the largest acetaldehyde source in the model (128 Tg al?1, a factor of 4 greater than the previous estimate), with alkanes, alkenes, and ethanol the main precursors. There is also a minor source from isoprene oxidation. We use an updated chemical mechanism for GEOSChem, and photochemical acetaldehyde yields are consistent with the Master Chemical Mechanism. We present a new approach to quantifying the acetaldehyde air-sea flux based on the global distribution of light absorption due to colored dissolved organic matter (CDOM) derived from satellite ocean color observations. The resulting net ocean emission is 57 Tg a?1, the second largest global source of acetaldehyde. A key uncertainty is the acetaldehyde turnover time in the ocean mixed layer, with quantitative model evaluation over the ocean complicated by known measurement artifacts in clean air. Simulated concentrations in surface air over the ocean generally agree well with aircraft measurements, though the model tends to overestimate the vertical gradient. PAN:NOx ratios are well-simulated in the marine boundary layer, providing some support for the modeled ocean source. We introduce the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) for acetaldehyde and ethanol and use it to quantify their net flux from living terrestrial plants. Including emissions from decaying plants the total direct acetaldehyde source from the land biosphere is 23 Tg a?1 Other terrestrial acetaldehyde sources include biomass burning (3 Tg?1) and anthropogenic emissions (2 Tg a?1). Simulated concentrations in the continental boundary layer are generally unbiased and capture the spatial gradients seen in observations over North America, Europe, and tropical South America. However, the model underestimates acetaldehyde levels in urban outflow, suggesting a missing source in polluted air. Ubiquitous high measured concentrations in the free troposphere are not captured by the model, and based on present understanding are not consistent with concurrent measurements of PAN and NOx: We find no compelling evidence for a widespread missing acetaldehyde source in the free troposphere. We estimate the current US source of ethanol and acetaldehyde (primary + secondary) at 1.3 Tg a ?1and 7.8 Tg ?1 approximately 60% and 480% of the corresponding increases expected for a national transition from gasoline to ethanol fuel. © Author(s) 2010.