Andrew J. Weinheimer

Increasing springtime ozone mixing ratios in the free troposphere over western North America

In the lowermost layer of the atmosphere—the troposphere—ozone is an important source of the hydroxyl radical, an oxidant that breaks down most pollutants and some greenhouse gases. High concentrations of tropospheric ozone are toxic, however, and have a detrimental effect on human health and ecosystem productivity. Moreover, tropospheric ozone itself acts as an effective greenhouse gas. Much of the present tropospheric ozone burden is a consequence of anthropogenic emissions of ozone precursors resulting in widespread increases in ozone concentrations since the late 1800s. At present, east Asia has the fastest-growing ozone precursor emissions. Much of the springtime east Asian pollution is exported eastwards towards western North America. Despite evidence that the exported Asian pollution produces ozone, no previous study has found a significant increase in free tropospheric ozone concentrations above the western USA since measurements began in the late 1970s. Here we compile springtime ozone measurements from many different platforms across western North America. We show a strong increase in springtime ozone mixing ratios during 1995–2008 and we have some additional evidence that a similar rate of increase in ozone mixing ratio has occurred since 1984. We find that the rate of increase in ozone mixing ratio is greatest when measurements are more heavily influenced by direct transport from Asia. Our result agrees with previous modelling studies, which indicate that global ozone concentrations should be increasing during the early part of the twenty-first century as a result of increasing precursor emissions, especially at northern mid-latitudes, with western North America being particularly sensitive to rising Asian emissions. We suggest that the observed increase in springtime background ozone mixing ratio may hinder the USA’s compliance with its ozone air quality standard.

Sources and chemistry of NOx in the upper troposphere over the United States

The origin of NOx in the upper troposphere over the central United States is examined using aircraft observations obtained during the SUCCESS campaign in April–May of 1996. Correlations between NOy (sum of NOx and its oxidation products) and CO at 8–12 km altitude indicate that NOx originates primarily from convective transport of polluted boundary layer air. Lightning and aircraft emissions appear to be only minor sources of NOx. Chemical steady state model calculations constrained by local observations of NO underestimate the measured NOx/NOy concentration ratio at 8–12 km altitude by a factor of two on average. The magnitude of the underestimate is correlated with concentrations of condensation nuclei, which we take as a proxy for the age of air in the upper troposphere. We conclude that the NOx/NOy ratio is maintained above chemical steady state by frequent convective injections of fresh NOx from the polluted boundary layer and by the long lifetime of NOx in the upper troposphere (5–10 days). In contrast to previous studies, we find no evidence for fast heterogeneous recycling from HNO3 to NOx in the upper troposphere.

Airborne in-situ OH and HO2 observations in the cloud-free troposphere and lower stratosphere during SUCCESS

The hydroxyl (OH) and hydroperoxyl (HO2) radicals were measured for the first time throughout the troposphere and in the lower stratosphere with a new instrument aboard the NASA DC-8 aircraft during the 1996 SUCCESS mission. Typically midday OH was 0.1-0.5 pptv and HO2 was 3-15 pptv. Comparisons with a steady-state model yield the following conclusions. First, even in the lower stratosphere OH was sensitive to the albedo of low clouds and distant high clouds. Second, although sometimes in agreement with models, observed OH and HO2 were more than 4 times larger at other times. Evidence suggests that for the California upper troposphere on 10 May this discrepancy was due to unmeasured HOx sources from Asia. Third, observed HO2/OH had the expected inverse dependence with NO, but was inexplicably higher than modeled HO2/OH by an average of 30%. Finally, small-scale, midday OH and HO2 features were strongly linked to NO variations.

The Deep Convective Clouds and Chemistry (DC3) Field Campaign

AbstractThe Deep Convective Clouds and Chemistry (DC3) field experiment produced an exceptional dataset on thunderstorms, including their dynamical, physical, and electrical structures and their impact on the chemical composition of the troposphere. The field experiment gathered detailed information on the chemical composition of the inflow and outflow regions of midlatitude thunderstorms in northeast Colorado, west Texas to central Oklahoma, and northern Alabama. A unique aspect of the DC3 strategy was to locate and sample the convective outflow a day after active convection in order to measure the chemical transformations within the upper-tropospheric convective plume. These data are being analyzed to investigate transport and dynamics of the storms, scavenging of soluble trace gases and aerosols, production of nitrogen oxides by lightning, relationships between lightning flash rates and storm parameters, chemistry in the upper troposphere that is affected by the convection, and related source character...

Sources of HOx and production of ozone in the upper troposphere over the United States

The sources of HO x (OH+peroxy radicals) and the associated production of ozone at 8-12 km over the United States are examined by modeling observations of OH, HO 2 , NO, and other species during the SUCCESS aircraft campaign in April-May 1996. The HO x concentrations measured in SUCCESS are up to a factor of 3 higher than can be calculated from oxidation of water vapor and photolysis of acetone. The highest discrepancy was seen in the outflow of a convective storm. We show that convective injection of peroxides (CH 3 OOH and H 2 O 2 ) and formaldehyde (CH 2 O) from the boundary layer to the upper troposphere could resolve this discrepancy. More generally, the data collected over the central United States during SUCCESS suggest that local convection was a major source of HO x and NO x to the upper troposphere. The OH and HO 2 observations together with the observations of NO allow us to directly calculate the ozone production in the upper troposphere and its dependence on NO x . We find an average net ozone production of 2 ppbv day -1 between 8 and 12 km over the continental United States in the spring. Ozone production was NO x -limited under essentially all the conditions encountered in SUCCESS. The high levels of HO x present in the upper troposphere stimulate ozone production and increase the sensitivity of ozone to NO x emissions from aircraft and other sources.

Deep convection as a source of new particles in the midlatitude upper troposphere

downwind of the cirrus anvil, with maximum concentrations of 45,000 per standard cm 3 . Volatility and electron microscope measurements indicated that most of the particles were likely to be small sulfate particles. The enhancement extended over at least a 600-km region. Multivariate statistical analysis revealed that high CN concentrations were associated with surface tracers, as well as convective elements. Convection apparently brings gas-phase particle precursors from the surface to the storm outflow region, where particle nucleation is favored by the extremely low temperatures. Simple calculations showed that deep convective systems may contribute to a substantial portion of the background aerosol in the upper troposphere at midlatitudes. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0320 Atmospheric Composition and Structure: Cloud physics and chemistry; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry;

Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

The redistribution of HNO 3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) were accompanied by the observation of condensed-phase HNO 3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO 3 with two independent channels of detection connected to separate forward and downward facing inlets that allow a determination of the amount of HNO 3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO 3 at temperatures of 197-224 K and pressures of 122-224 hPa. Maximum levels of condensed-phase HNO 3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4 x 10 14 molecules cm -2 were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO 3 adsorption enthalpy of -11.0 kcal mol -1 , electively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO 3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 μm and particle fall velocities up to 10 m s -1 , some observed clouds have significant potential to redistribute HNO 3 in the upper troposphere.

Meridional distributions of NOx, NOy, and other species in the lower stratosphere and upper troposphere during AASE II

The meridional distribution of NOx in the lower stratosphere and upper troposphere is inferred from 10 flights of the NASA DC-8 in the northern winter of 1992, along with like distributions of NOy, NOx/NOy, CO, and C2Cl4. In the lowest few km of the stratosphere there is little vertical gradient in NOx over the range of latitudes measured (40°–90°N). There is a substantial latitudinal gradient, with 50 pptv above the pole and 120 pptv near 40°N. In the uppermost few km of the troposphere, background values range from 30 pptv over the pole to 90 pptv near 40°N. On two occasions higher values, up to 140 pptv in the mean, were seen 2–3 km below the tropopause in association with frontal systems. The meridional distributions of CO and C2Cl4 show the same feature, suggesting that the source of the elevated NOx is near the earths surface.

Impacts of biomass burning in Southeast Asia on ozone and reactive nitrogen over the western Pacific in spring

[1] 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 (NOx, 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 altitudetheincreasesinNOyandO3were810partspertrillionbyvolume(pptv)and26parts 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/NOx 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

Springtime photochemistry at northern mid and high latitudes

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( 1 D) 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. INDEX TERMS: 0317 Atmospheric Composition and Structure: Chemical kinetic and photochemical properties; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; KEYWORDS: springtime, ozone, HOx, oxidation, reactive nitrogen