G. V. Ferry

Photochemistry of HO x in the upper troposphere at northern midlatitudes

The factors controlling the concentrations of HOx radicals (= OH + peroxy) in the upper troposphere (8–12 km) are examined using concurrent aircraft observations of OH, HO2, H2O2, CH3OOH, and CH2O made during the Subsonic Assessment Ozone and Nitrogen Oxide Experiment (SONEX) at northern midlatitudes in the fall. These observations, complemented by concurrent measurements of O3, H2O, NO, peroxyacetyl nitrate (PAN), HNO3, CH4, CO, acetone, hydrocarbons, actinic fluxes, and aerosols, allow a highly constrained mass balance analysis of HOx and of the larger chemical family HOy (= HOx + 2 H2O2 + 2 CH3OOH + HNO2 + HNO4). Observations of OH and HO2 are successfully simulated to within 40% by a diel steady state model constrained with observed H2O2 and CH3OOH. The model captures 85% of the observed HOx variance, which is driven mainly by the concentrations of NOx (= NO + NO2) and by the strength of the HOx primary sources. Exceptions to the good agreement between modeled and observed HOx are at sunrise and sunset, where the model is too low by factors of 2–5, and inside cirrus clouds, where the model is too high by factors of 1.2–2. Heterogeneous conversion of NO2 to HONO on aerosols (γNO2 = 10−3) during the night followed by photolysis of HONO could explain part of the discrepancy at sunrise. Heterogeneous loss of HO2 on ice crystals (γice_HO2 = 0.025) could explain the discrepancy in cirrus. Primary sources of HOx from O(1D)+H2O and acetone photolysis were of comparable magnitude during SONEX. The dominant sinks of HOy were OH+HO2 (NOx 50 pptv). Observed H2O2 concentrations are reproduced by model calculations to within 50% if one allows in the model for heterogeneous conversion of HO2 to H2O2 on aerosols (γHO2 = 0.2). Observed CH3OOH concentrations are underestimated by a factor of 2 on average. Observed CH2O concentrations were usually below the 50 pptv detection limit, consistent with model results; however, frequent occurrences of high values in the observations (up to 350 pptv) are not captured by the model. These high values are correlated with high CH3OH and with cirrus clouds. Heterogeneous oxidation of CH3OH to CH2O on aerosols or ice crystals might provide an explanation (γice_CH3OH ∼ 0.01 would be needed).

Physical and optical properties of the Pinatubo volcanic aerosol: Aircraft observations with impactors and a Sun-tracking photometer

As determined in situ by impactor samplers flown on an ER-2 at 16.5- to 20.7-km pressure altitude and on a DC-8 at 9.5- to 12.6-km pressure altitudes, the 1991 Pinatubo volcanic eruption increased the particle surface area of stratospheric aerosols up to 50-fold and the particle volume up to 2 orders of magnitude. Particle composition was typical of a sulfuric acid-water mixture at ER-2 altitudes. Ash particles coated with sulfuric acid comprised a significant fraction of aerosol at DC-8 altitudes. Mie-computed light extinction increased up to 20-fold at midvisible and greater than 100-fold at near-IR wavelengths. The optical thickness measured through the aerosol layer by an autotracking Sun photometer aboard a DC-8 aircraft at 10.7- to 11.3-km pressure altitudes shows a spectral shape that is similar to the Mie-calculated spectral extinction at ER-2 altitudes. Surface area distributions calculated by inversion of spectral optical depth measurements show characteristics that are similar to the mean surface area distribution resulting from 35 in situ measurements.

The Arctic polar stratospheric cloud aerosol: Aircraft measurements of reactive nitrogen, total water, and particles

The reactive nitrogen (NOy), total water, and particle components of the polar stratospheric cloud (PSC) aerosol in the Arctic are studied using in situ aircraft measurements in the lower stratosphere. The results are compared to findings from the Antarctic derived using similar measurements and interpretive techniques. The Arctic data show that particle volume well above background values is present at temperatures above the frostpoint, confirming the result from the Antarctic that the observed PSCs are not water ice particles. NOy measurements inside a PSC are enhanced above ambient values consistent with anisokinetic sampling of particles containing NOy. Furthermore, relative changes in the measured particle volume along a flight track are well correlated with changes in the amount of NOy estimated to be in the particle phase. With the exception of data from one flight, assuming that the composition of the PSC particles is nitric acid trihydrate (NAT), the HNO3 content of the measured particle volume is consistent with the amount of HNO3 predicted to be available for condensation. To this extent, the Arctic observations are consistent with NAT as the composition of PSC particles, in agreement with the Antarctic findings. In the Arctic data over long segments of several flights, calculations show saturation with respect to NAT without significant PSC particle growth above background. PSCs in the Arctic are not observed in situ until the apparent saturation ratio of HNO3 with respect to NAT is greater than 10, in marked contrast to the Antarctic, where PSCs are observed in conditions of apparent HNO3 saturation of 1 and above. This difference cannot be resolved by known measurement uncertainties. Also, a discrepancy is noted in the comparison of the amount of condensed HNO3 derived from the particle distribution measurements with that derived from the NOy measurements, assuming a NAT composition for the particles. Although the relative variations in the derived quantities are similar, as in the Antarctic, the mean values consistently disagree by about a factor of 2. The differences suggest that there may be systematic errors in the data and/or physical assumptions used in the analysis. Several possibilities are discussed.

In Situ Observations of Aerosol and Chlorine Monoxide After the 1991 Eruption of Mount Pinatubo: Effect of Reactions on Sulfate Aerosol

Highly resolved aerosol size distributions measured from high-altitude aircraft can be used to describe the effect of the 1991 eruption of Mount Pinatubo on the stratospheric aerosol. In some air masses, aerosol mass mixing ratios increased by factors exceeding 100 and aerosol surface area concentrations increased by factors of 30 or more. Increases in aerosol surface area concentration were accompanied by increases in chlorine monoxide at mid-latitudes when confounding factors were controlled. This observation supports the assertion that reactions occurring on the aerosol can increase the fraction of stratospheric chlorine that occurs in ozone-destroying forms.

Observations of HO x and its relationship with NO x in the upper troposphere during SONEX

Simultaneous measurements of the oxides of hydrogen and nitrogen made during the NASA Subsonic Assessment, Ozone and Nitrogen Oxide Experiment (SONEX) afforded an opportunity to study the coupling between these two important families throughout the free troposphere and lowermost stratosphere. Moreover, the suite of measurements made during the campaign was unprecedented in its completeness, thus providing a uniquely detailed picture of the radical photochemistry that drives oxidation and ozone production in this part of the atmosphere. On average, observed hydrogen oxides (HOx = OH + HO2) agree well with both instantaneous and diel steady-state models; however, there is a persistent deviation of the observations that correlates with the abundance of nitrogen oxides (NOx = NO + NO2) in the sampled air mass. Specifically, the observed HOx tends to exceed the model predictions in the presence of high NOx concentrations, by as much as a factor of 5 (> 500 pptv NOx), and is sometimes as little as half that expected by steady state at lower NOx levels. While many possibilities for these discrepancies are discussed, it is argued that an instrumental artifact is not probable and that the discrepancy may bespeak a shortcoming of our understanding of HOx chemistry. The consistently elevated HOx in the presence of elevated NOx leads directly to greater ozone production than expected, thereby extending the NOx-limited regime of the upper troposphere. These results could thus have bearing on the predicted impacts of increasing NOx emissions into this region of the atmosphere from, for example, the growth of global air traffic.

Evolution of Pinatubo aerosol near 19 km altitude over western North America

Stratospheric aerosols, collected near 19 km altitude on wire impactors over western North America from August 20, 1991 to May 11, 1993, show strong influence of the June 1991 Mt. Pinatubo eruption. Lognormal size distributions are bimodal; each of the mode radii increases and reaches maximum value at about 15 months after eruption. The second (large particle) mode becomes well developed then, and about 40% of the droplets are larger than 0.4 {mu} radius. The eruption of Mt. Spurr (Alaska) may also have contributed to this. Sulfate mass loading decays exponentially (e-folding 216 days), similar to El Chichon. Silicates are present in samples only immediately after eruptions. Two years after eruption, sulfate mass loading is about 0.4 {mu}g/m{sup 3}, about an order of magnitude higher than background pre-volcanic values. Aerosol size distributions are still bimodal with a very well-defined large droplet mode. 25 refs., 3 figs., 1 tab.

Soot aerosol in the lower stratosphere: Pole-to-pole variability and contributions by aircraft

A NASA ER-2 high-altitude research aircraft intercepted the exhaust wake of a supersonic Concorde aircraft in the stratosphere near New Zealand on October 8, 1994. Black carbon (soot) aerosol (BCA) was sampled by wire impactors during the first five of 12 short-duration wake intercepts. BCA concentration in Concorde exhaust at 16.3 km altitude was 0.2 particles cm−3, the size distribution peaked at a geometric mean radius of 0.09 μm, and the mass loading was 2.0±1.4 ng m−3. With a plume dilution factor (DF) of 1.0×10−5, determined by the ratio of CO2 measured in the plume (above the ambient stratospheric background level) to CO2 in the engine exhaust plane, the Concorde BCA emission index was EI(BCA)=0.07±0.05 g BCA per kg fuel burned. Applying this EI to estimates of aircraft fuel burned by the current subsonic fleet in the stratosphere yields average stratospheric BCA loadings of 0.5 ng m−3, commensurate with observations in the northern stratosphere. Applying the Concorde EI to fuel consumption by a projected future fleet suggests a twofold-threefold increase of stratospheric BCA by the year 2015. A strong gradient in BCA concentration exists between the northern and the southern hemispheres, indicating interhemispheric mixing times longer than stratospheric residence times.

Aerosol abundances and optical characteristics in the pacific basin free troposphere

Abstract During NASAs Global Backscatter Experiment (GLOBE) mission flights in November 1989 and May 1990, a DC-8 research aircraft probed the Pacific Basin free troposphere for about 90 flight hours in each month between +72 and −62 degrees latitude, +130 and −120 degrees longitude, and up to 39,000 feet pressure altitudes. Aerosols were sampled continuously in situ by optical particle counters to measure concentration and particle size, and during 48 10-min intervals during each mission by wire impactors for concentration, size, composition, phase and shape analyses. The optical particle counters cover a particle diameter range between 0.3 and 20 μm; wire impactors extend the range down to 0.03 μm. Results of particle number, size, shape, together with the assumption of a refractive index corresponding to (NH 4 ) 2 SO 4 to account for the prevalence of aerosol sulfur, were utilized in a Mie algorithm to calculate aerosol extinction and backscatter for a range of wavelengths (0.385 E 0.525 =(2.03±1.20) × 10 −4 km −1 and backscatter β 0.525 =(6.45±3.49) × 10 −6 km −1 sr −1 in the visible, and E 10.64 =(8.13±6.47) × 10 −6 km −1 and β 10.64 =(9.98±10.69) × 10 −8 km −1 sr −1 in the infra-red, respectively. Large particles ( D > 0.3 μ m) contribute two-thirds to the total extinction in the visible (λ=0.525 μm), and almost 100% in the infra-red (λ= 10.64 μm). These results have been used to define an IR optical aerosol climatology of the Pacific Basin free troposphere, from which it follows that the infra-red backscatter coefficient at λ=9.25 μm wavelength fluctuates between 5.0 × 10 −10 and 2.0 × 10 −7 km −1 sr −1 with a modal value 2.0 × 10 −8 km −1 sr −1 .

Vertical transport of anthropogenic soot aerosol into the middle atmosphere

Gravito-photophoresis, a sunlight-induced force acting on particles which are geometrically asymmetric and which have uneven surface distribution of thermal accommodation coefficients, explains vertical transport of fractal soot aerosol emitted by aircraft in conventional flight corridors (10-12 km altitude) into the mesosphere (>80 km altitude). While direct optical effects of this aerosol appear nonsignificant, it is conceivable that they play a role in mesospheric physics by providing nuclei for polar mesospheric cloud formation and by affecting the ionization of the mesosphere to contribute to polar mesospheric summer echoes.

Stratospheric Aluminum Oxide

Balloons and U-2 aircraft were used to collect micrometer-sized strato-spheric aerosols. It was discovered that for the past 6 years at least, aluminum oxide spheres have been the major stratospheric particulate in the size range 3 to 8 micrometers. The most probable source of the spheres is the exhaust from solid-fuel rockets.