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A significant increase in sulfuric acid aerosol concentration was detected above 10 km pressure altitude during a cross-corridor flight out of Shannon, Ireland, on October 23, 1997.

The light absorption coefficient, Beta(a) of the stratospheric aerosol is an important quantity that determines its radiative effects. When combined with the aerosol scattering coefficient, Beta(a) it becomes possible to evaluate the aerosol single scatter albedo, omega = Beta(s)/(Beta(s) + Beta(a)) which is essential for modeling the overall radiative effects of the stratospheric aerosol. Pollack1 determined that omega = 0.98 is a critical value that separates stratospheric cooling from warming.

The distribution of black carbon (soot) aerosol (BCA) in the atmosphere is of interest for several reasons: (1) Because BCA has the highest absorption cross section of any compound known, it can absorb solar radiation to cause atmospheric warming. (2) Because it is a strong adsorber of gases, it can catalyze heterogeneous reactions to change the chemical composition of the atmosphere.(3) If aircraft are a major source of BCA, it is an important tracer of aircraft emissions. Analysis for BCA of impactor samples from Arctic and Antarctic deployments, utilizing particle morphology of scanning electron microscopy images, permits the following conclusions: (1) The BCA concentration in the northern stratosphere varies between 0 and 2.6 ng m-3 averaging 0.6 ng/cu m. (2) This BCA loading is commensurate with estimated fuel consumptions in the stratosphere by the current commercial fleet and an emission index E=0.03 g BCA per kg fuel burnt which was measured in jet exhaust at al titude.Thus, most stratospheric BCA in the northern stratosphere results from aircraft emissions. The background BCA concentration in the southern stratosphere varies between 0 and 0.6 ng cu m averaging 0.1 ng/cu m. This strong meridional gradient implies that stratospheric BCA residence time- is shorter than are mixing times between hemispheres. Projected annual fuel consumption of a future supersonic commercial fleet is 7E13 g. This fleet would increase stratospheric BCA loadings by a factor of 2-3, because almost all fuel would be burnt above the tropopause. An improved EI(BCA) by a factor of ten would result in an increase of stratospheric BCA loadings by approximately 50 %.

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 micron 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 eruption. Two years after eruption, sulfate mass loading is about 0.4 micrograms/cu m, 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.

During NASA's 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 microns; wire impactors extend the range down to 0.03 microns. Results of particle number, size, shape, together with the assumption of a refractive index corresponding to (NH4)2SO4 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 less than lambda less than 10.64 microns). Computations for 22 randomly selected size distributions yield coefficients of extinction E(0.525) = (2.03 +/- 1.20) x 10(exp -4) km(exp -1) and backscatter beta(0.525) = (6.45 +/- 3.49) x 10(exp -6) km(exp -1) sr(exp -1) in the visible, and E(10.64) = (8.13 +/- 6.47) x 10(exp -6) km(exp -1) and beta(10.64) = (9.98 +/- 10.69) x 10(exp -8) km(exp -1) sr(exp -1) in the infrared, respectively. Large particles (D greater than 0.3 microns) contribute two-thirds to the total extinction in the visible (lambda = 0.525 microns), and almost 100% in the infrared (lambda = 10.64 microns). These results have been used to define an IR optical aerosol climatology of the Pacific Basin free troposphere, from which it follows that the infrared backscatter coefficient at lambda = 9.25 microns wavelength fluctuates between 5.0 x 10(exp -10) and 2.0 x 10(exp -7) km(exp -1) sr(exp -1) with a modal value 2.0 x 10(exp -8) km(exp -1) sr(exp -1).

The NASA ER-2 aircraft flew on January 24, 1989, from Stavanger to Spitsbergen, Norway, at the 430-440 K potential temperature surface (19.2-19.8 km pressure altitude). Aerosols were sampled continuously by an optical particle counter (PMS-FSSP300) for concentration and size analyses, and during five 10-min intervals by four wire and one replicator impactor for concentration, size, composition, and phase analysis. During sampling, the air saturation of H2O with respect to ice changed from 20 to 100 percent, and of HNO3 with respect to nitric acid trihydrate (NAT) from subsaturation to supersaturation. Data from both instruments indicate a condensation of hydrochloric acid and, later, nitric acid on the background aerosol particles as the ambient temperature decreases along the flight track. This heterogeneous nucleation mechanism generates type I polar stratospheric cloud particles of 10-fold enhanced optical depth, which could play a role in stratospheric ozone depletion.

The paper uses particle size and volume measurements obtained with the forward scattering spectrometer probe model 300 during January and February 1989 in the Airborne Arctic Stratospheric Experiment to investigate processes important in the formation and growth of polar stratospheric cloud (PSC) particles. It is suggested on the basis of comparisons of the observations with expected sulfuric acid droplet deliquescence that in the Arctic a major fraction of the sulfuric acid droplets remain liquid until temperatures at least as low as 193 K. It is proposed that homogeneous freezing of the sulfuric acid droplets might occur near 190 K and might play a role in the formation of PSCs.

In situ aircraft measurements in the lower stratosphere are used to investigate the reactive nitrogen, NO(y), total water, and particle components of the polar stratospheric cloud (PSC) aerosol in the Arctic. 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. NO(y) measurements inside a PSC are enhanced above ambient values consistent with anisokinetic sampling of particles containing NO(y). In the Arctic data over long segments of several flights, calculations show saturation with respect to nitric acid trihydrate without significant PSC particle growth above background.

Measurements were made of stratospheric sulfate aerosols using a passive cavity aerosol spectrometer and a condensation nucleus counter on a NASA ER-2 aircraft in the Airborne Arctic Stratospheric Experiment of 1989. The problems of representative and accurate sampling and particle evaporation were explicitly addressed in the design of the inlets and reduction of the data. The measurements suggest that the sulfate aerosol is bimodal in the polar vortex above the mass mixing ratio maximum in the sulfate layer. It appears that a nuclei mode of small, newly formed particles exists in this region. A stronger case is made for a nuclei mode in the upper few kilometers of the troposphere and in the lower few kilometers of the stratosphere. This mode is probably a global phenomenon occurring in all seasons. Comparison of denitrified and nondenitrified air suggests that denitrification removes some of the larger sulfate particles.

Representative measurement of aerosol from aircraft-aspirated systems requires special efforts in order to maintain near isokinetic sampling conditions, estimate aerosol losses in the sample system, and obtain a measurement of sufficient duration to be statistically significant for all sizes of interest. This last point is especially critical for aircraft measurements which typically require fast response times while sampling in clean remote regions. This paper presents size-resolved tests, intercomparisons, and analysis of aerosol inlet performance as determined by a custom laser optical particle counter. Measurements discussed here took place during the Global Backscatter Experiment (1988-1989) and the Central Pacific Atmospheric Chemistry Experiment (1988). System configurations are discussed including (1) nozzle design and performance, (2) system transmission efficiency, (3) nonadiabatic effects in the sample line and its effect on the sample-line relative humidity, and (4) the use and calibration of a virtual impactor.

Stratospheric aerosol collections by wire impactors, taken mainly over the western U.S. from early 1984 to late 1986, show the diminishing effects of El Chichon's 1982 eruption, and provide a set of data for judging subsequent volcanic effects. Decrease in sulfate burden during the study time is due to preferential gravitational settling-out of large (above 0.5-micron diameter) sulfate aerosol droplets. As a result of settling from higher levels, lower altitude (12.2-15.2 km) air early in 1984 tends to contain more sulfate than higher level (19.8-21.3 km) air. As of late 1986, however, high- and low-altitude sulfate contents have decreased and are similar, suggesting large-particle settling has been completed. The later sulfate collection size distributions resemble unimodal background spectra, whereas earlier ones are bimodal. Average sulfate load for all altitudes decreases during the period of study from 0.4 to 0.08 microgram/cu m. The latter value is somewhat higher than a volcanically unenriched pre-El Chichon level, suggesting that even as of 1987, stratospheric background had not been obtained.

Particle-size distributions measured from the NASA ER-2 with the new Forward Scattering Spectrometer Probe 300 in a type I polar stratospheric cloud (PSC) on January 24, 1989 show a volume mode near 0.8 micron in diameter. The large increase in particle concentration and volume after cloud entry did not occur until the apparent saturation ratio of nitric acid with respect to nitric acid trihydrate reached 10, but at ratios near 1 subtle changes in the size distribution suggest some type I particles were present. Particle concentrations in cloud of 15-17/cu cm were greater than the CN concentrations of 5-7/cu cm just outside of cloud, suggesting nucleation on more than just sulfate particles. Some particles greater than 4 microns in diameter were observed in a region which was saturated with respect to ice.

The ER-2 Condensation Nucleus Counter (ER-2 CNC) was operated in the Airborne Arctic Stratospheric Expedition (AASE) in January and February 1989. The ER-2 CNC measures the mixing ratio of particles, CN, with diameters from approximately 0.02 to approximately 1 micron. The spatial distribution of CN in the Arctic polar vortex was found to resemble that measured in the Antarctic in the Spring of 1987. The vertical profile of CN in the vortex was lowered by subsidence. At altitudes above the minimum in the CN mixing ratio profile, CN mixing ratios correlated negatively with that of N2O, demonstrating new particle production. CN serve as nuclei in the formation of Polar Stratospheric Clouds (PSCs) and the concentration of CN can affect PSC properties.

In-situ particle measurements made aboard the NASA ER-2 in the Arctic on 890130 (YYMMDD) show Type 1 PSC particles over much of the flight, with instances of embedded Type 2 PSCs. The Type 2 particles were observed at temperatures warmer than the local frost-point temperature of water; extended up to the upper size cutoff of the instrument (about 24-micron diameter); and are shown to contain too large a volume to be primarily NAT. Based on measured vertical temperature profiles, it is concluded that the Type 2 particles observed on this day were formed above the aircraft in a region where saturation with respect to ice was achieved and were sufficiently large to have fallen into the path of the ER-2. Although the amount of material in the particles, expressed as water, is small by comparison to the total (vapor + aerosol) water concentration, the flux of water from the falling particles is of sufficient magnitude, if sustained, to lead to dehydration of the source region. These observations verify the mechanism for dehydration of polar vortex air masses by precipitation of ice particles.

A new instrument, the Forward Scattering Spectrometer Probe (FSSP) 300, was used on the NASA ER-2 during the Airborne Arctic Stratospheric Expedition (AASE) to count and size particles in the size range 0.4-24 microns in diameter. A brief description of the instrument is presented, and observations for each ER-2 flight are summarized. Measurements were made in both type I and type II polar stratospheric clouds as well as in the background sulfuric-acid particles. Total particle concentrations up to 16/cu cm with total particle volumes up to 10 cubic micron/cu cm were observed in some of the polar-stratospheric-cloud events.

Polar stratospheric cloud (PSC) particles are collected on impactors and studied with regard to physical and chemical properties to help explain the importance of heterogeneous chemical reactions for stratospheric ozone depletion. The nitric, hydrochloric, and sulfuric acid content of stratospheric aerosol particles collected at 18 km altitude was determined. It is suggested that nitric acid is a component of polar stratospheric clouds. This is important for two reasons: (1) it proves that chlorine activation takes place at the surface of PSC particles by converting chemically inert chlorine nitrate to chlorine radicals that can react with ozone; and (2) if the PSC particles are large enough to settle out from the stratosphere, the possibility of nitric acid removal can result in the denitrification of the stratosphere.

The use of the active scattering spectrometer probe (ASAS-X) to measure sulfuric acid aerosols on U-2 and ER-2 research aircraft has yielded results that are at times ambiguous due to the dependence of particles' optical signatures on refractive index as well as physical dimensions. The calibration correction of the ASAS-X optical spectrometer probe for stratospheric aerosol studies is validated through an independent and simultaneous sampling of the particles with impactors; sizing and counting of particles on SEM images yields total particle areas and volumes. Upon correction of calibration in light of these data, spectrometer results averaged over four size distributions are found to agree with similarly averaged impactor results to within a few percent: indicating that the optical properties or chemical composition of the sample aerosol must be known in order to achieve accurate optical aerosol spectrometer size analysis.

Results are presented on measurements of NO and the sum of reactive nitrogen species, NO(y), which include NO, NO2, NO3, N2O5, HNO3, and ClONO2 (in addition to ClO, O3, H2O, and N2O measurements), obtained aboard the NASA ER-2 aircraft flying over the Antarctica between the latitudes of 53 and 72 deg S during the Airborne Antarctic Ozone Experiment. The boundary of the chemically perturbed region (CPR), as indicated by a sharp increase in the level of ClO, occurred near 66 deg S; outside or equatorward of the CPR, the NO(y) mixing ratios ranged between 6 and 12 ppbv, with values decreasing poleward and reaching total NO(y) levels of 4 ppbv or less within 5-deg poleward of the boundary. Data presented in this paper clearly associate the Antarctic ozone decrease with perturbed conditions of ClO, NO(y), and H2O, which are in turn associated with processes defined as nonstandard heterogeneous chemistry, denitrification, and dehydration, respectively.

Particle Measuring Systems laser particle spectrometer (ASAS-X and FSSP) probes were used to measure aerosol particle concentrations and size distributions during 11 ER-2 flights between Punta Arenas (53 deg S) and Antarctica (up to 72 deg S) from August 17 to September 22, 1987. The time resolution was 10 s, corresponding to a spatial resolution of 2 km. The data were divided into two size classes (0.05-0.25 and 0.53-5.5 micron radius) to separate the small particle from the coarse particle populations. Results show that the small-particle concentrations are typical for a background aerosol during volcanic quiescence. This concentration is generally constant along a flight track; in only one instance a depletion of small particles during a polar stratospheric cloud (PSC) encounter was measured, suggesting a nucleation of type I PSC particles on background aerosols. Temporary increases of the coarse particle concentrations indicated the presence of tenuous polar stratospheric clouds that were encountered most frequently at the southernmost portion of a flight track and when the aircraft descended to lower altitudes. During 'particle events', particle modes were found at 0.6-micron radius, corresponding to type I PSCs, and occasionally, at 2.0-micron radius corresponding to type II PSCs.

Filter samples obtained as part of the AAOE to determine the total nitrate, sulfate, acidic chloride, and acidic fluoride content along the flight path of the NASA ER-2 are studied. These compounds were obtained in the aerosol and vapor phase. The ratio of particulate sulfate observed outside the chemically perturbed region (CPR) of the vortex to that inside the CPR was 2.6. The ratio of total acidic chloride to total acidic flouride within the CPR is near 1, indicating the removal of chloride from the air mass or the partitioning of chloride into an unmeasured species.

The 1987 Airborne Antarctic Ozone Experiment, in which the NO3, Cl, and SO4 contents of stratospheric aerosols were estimated, is discussed. The aerosol size and chemical composition measurements were carried out on samples collected during August 17 to September 4, 1987. The data indicate that condensed nitrate is found below a threshold temperature of 193.6 + or - 3.0 K, which is generally found at latitudes exceeding 64 deg S. A negative correlation exists between condensed nitrate and ozone correlation.

Stratospheric aerosols collected over the western U.S. from late 1982 to early 1984 show the strong effects of El Chichon's eruption. Although mineral particles disappeared during this period, large acid droplets were still common. Because these have never been seen in prevolcanic, background-level collections, they apparently result from increased droplet growth made possible by the unusual abundance of sulfate. Aerosol size distributions show a wide variety of multimodal curves due to mixing of air masses containing aerosols of various ages or histories. Toward the end of the study time there are fewer large aerosols because of gravitational settling and poleward transport. The result is a steady reduction in sulfate, as most aerosol mass is concentrated in a small number of large droplets. Even the later sulfate levels are, however, five times typical prevolcanic background contents. Thus the influence of El Chichon on high-altitude was still considerable 22 months after eruption.

Comparisons are made between aerosol size distributions measured by instrumented aircraft and the SAGE II sensor on the ERB satellite performing limb scans of the same atmospheric region. Particle radii ranging from 0.0001-200 microns were detected, with good agreement being obtained between the size distributions detected by impactors and probes at radii over 0.15 micron. The distributions were used to calculate aerosol extinction values which were compared with values from SAGE II scans.

Dominant effects of the El Chichon eruption on stratospheric aerosols at 19.8 to 20.7 km are: (1) vapor depositional growth of the small-aerosol (background) mode; (2) development of a large-particle mode by sedimentation from the highest altitudes in the cloud; (3) a change in the large-particle mode from sulfate-coated silicates to sulfate aerosols, some with silicate cores; (4) a 100-fold increase in sulfate mass in the large particle mode. Terminal velocities of large silicate particles, maximum r = 2.3 micron, sampled 1 month after eruption, and calibrated with the aid of lidar data, indicate initial injection to 26 to 27 km. Smaller velocities of sulfate aerosols, median r = 0.5 micron, are compatible with major growth in 2 to 3 months at 27 to 28 km. Aerosol settling accounts for the descent of the main lidar return to 26.5 km in August and to 20 to 21 km in December.

Samples of stratospheric aerosols collected with U-2 aircraft for several months following the first three major eruptions of Mount St. Helens were analyzed for ash and liquid acid content. Ash grain sizes and compositions vary depending on collection altitude, location within the drifting cloud, and days following their injection. s computers Size distributions of ash particles vary with altitude. Generally small particles are depleted more rapidly at low altitudes (12 km) than at higher altitudes (17-18 km). Although samples collected 1 day after the first eruption of May 18, 1980, were dry, flow marks on the aircraft indicated parts of the cloud contained heavy acid concentrations. Indeed, all other samples obtained within 1 to 4 days after later eruptions (May 25 and June 12, 1980) were covered with copious amounts of liquid acid. Proportions of liquid to ash varied considerably depending on sampling location and cloud age. Because the acid-coated ash globules were large, they rapidly fell from the stratosphere until, by late June 1980, only a residue of acid droplets remained. Size distributions and concentrations of these droplets varied considerably.

Stratospheric aerosol samples were collected using a wire impactor during the year following the eruption of Mt. St. Helens. Analysis of samples shows that aerosol volume increased for 6 months due to gas-to-particle conversion and then decreased to background levels in the following 6 months.

Samples from the stratosphere obtained by U-2 aircraft after the first three major eruptions of Mount St. Helens contained large globules of liquid acid and ash. Because of their large size, these globules had disappeared from the lower stratosphere by late June 1980, leaving behind only smaller acid droplets. Particle size distributions and mineralogy of the stratospheric ash grains demonstrate inhomogeneity in the eruption clouds.

A sampling and analysis technique that uses the binomial distribution to characterize stratospheric aerosol populations at the 95% level of confidence is described. Particle samples obtained over Alaska during July 15-19, 1979, are used; the results show the presence of more small particles at lower altitude than at high altitudes. Calculations of the surface area and volume distributions for all aerosol samples collected are given. Evidence from these data suggests either that Aitken nuclei are injected or diffused across the tropopause and rise into the stratosphere, where they mature into larger particles, or nuclei form in the lower stratosphere and become mature aerosols at high altitude. Samples obtained at another site give the same results, supporting the view that the process of injection or nucleation and maturing of aerosols with altitude may be global and need not occur only in locations exhibiting unique meteorologic features.

Stratospheric aerosols were collected at Poker Flat, Alaska, in July, 1979, to determine particle properties, confirm coincident satellite SAGE measurements, and compare similar results obtained with different airborne samplers. Because of the steep slopes in size-distribution curves for larger particles, it is found that properties such as concentrations, aerosol mass, and optical extinction are very sensitive to small errors in radii. It is calculated that the concentration measurements agree with photoelectric particle counter results when a 16% radius change is introduced. An 8% radius change matches our calculated sulfate mass with filter mass measurements. And a 13% radius change results in agreement between the calculated optical extinction and coincident SAGE satellite results. Recognizing that different instruments can produce 10-20% differences in measured sizes, it is believed the results of these comparative measurements of SAGE and in situ instruments are essentially in agreement.

Trace ammonia in laboratory air reacts easily with sulfuric acid aerosol samples to form crystalline ammonium sulfate. Argon atmospheres, however, protect sampling surfaces from ammonia contamination. It is found that atmospheric aerosols treated in this way contain only sulfuric acid. After an hour exposed to laboratory air, these same samples convert to ammonium sulfate. Aerosol particles have been collected, using argon control, to determine if the absence of crystalline sulfate is common. But so far there is no evidence that aerosols are neutralized by ammonia in the stratosphere.

We have obtained stratospheric aerosols from tropical to northern latitudes using special collectors on U-2 aircraft during 1976 and 1977. Aerosols characterized by large numbers of small particles are found in the tropical zone suggesting this is a region of particle growth; whereas aerosols containing mostly larger particles are distributed throughout the Northern Hemisphere indicating a well-mixed, mature population. We find the aerosol layer extends from higher altitudes near the equator to lower ones toward the pole. Although this gradient suggests mature aerosols may leave the stratosphere at high latitudes, the data are, as yet, inconclusive. Comparisons of our data with those of other investigators using different instruments are generally encouraging, suggesting that if similar populations were sampled, the results would be similar. When our calculated sulfate mass mixing ratios are compared with those measured directly by others, we find better agreement is achieved if we assume more dilute sulfate and water mixtures than previously proposed.

Photographic observation of noctilucent cloud occurrence over geographical location during sounding rocket flight

Noctilucent cloud particle size composition and origin from sounding rocket flight and control collecting surfaces

Four classified types of particles in stratospheric balloon collections include chains, aggregates, crystals, and irregular solids which are often liquid coated. An analysis has been made of many individual particles using an X-ray detector on a scanning electron microscope. Chain type particles are composed entirely of elements lighter than sodium. All other particle types are composed mostly of various combinations of the elements Al, Si, Na, K, Ca, Fe, Mg, Ti, and S. The most common element group is Al, Si, Ca or K, and Fe, followed by sulfur or calcium alone. At lower altitudes (12-15 km), liquid is usually associated with the particles and sulfur is prominent. At higher altitudes (23-36 km), liquids and sulfur are usually absent. However, when liquids are occasionally found, so is sulfur. Particles collected with NASA aircraft at 12 km also contain mostly the Al, Si, Ca, Fe element group with associated sulfur, or sulfur alone.