In situ measurements of organics, meteoritic material, mercury, and other elements in aerosols at 5 to 19 kilometers

In situ measurements of the chemical composition of individual aerosol particles at altitudes between 5 and 19 kilometers reveal that upper tropospheric aerosols often contained more organic material than sulfate. Although stratospheric aerosols primarily consisted of sulfuric acid and water, many also contained meteoritic material. Just above the tropopause, small amounts of mercury were found in over half of the aerosol particles that were analyzed. Overall, there was tremendous variety in aerosol composition. One measure of this diversity is that at least 45 elements were detected in aerosol particles. These results have wide implications for the complexity of aerosol sources and chemistry. They also offer possibilities for understanding the transport of atmospheric aerosols.     

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.     

High-Latitude Stratospheric Aerosols Measured by the SAM II Satellite System in 1978 and 1979

Results of the first year of data collection by the SAM (Stratospheric Aerosol Measurement) II satellite system are presented. Almost 10,000 profiles of stratospheric aerosol extinction in the Arctic and Antarctic regions are used to construct plots of weekly averaged aerosol extinction versus altitude and time and stratospheric optical depth versus time. Corresponding temperature fields are presented. These data show striking similarities in the aerosol behavior for corresponding seasons. Wintertime polar stratospheric clouds that are strongly correlated with temperature are documented. They are much more prevalent in the Antarctic stratosphere during the cold austral winter and increase the stratospheric optical depths by as much as an order of magnitude for a period of about 2 months. These clouds might represent a sink for stratospheric water vapor and must be considered in the radiative budget for this region and time.     

Characterization of aerosols from eruptions of mount st. Helens

Measurements of mass concentration and size distribution of aerosols from eruptions of Mount St. Helens as well as morphological and elemental analyses were obtained between 7 April and 7 August 1980. In situ measurements were made in early phreatic and later, minor phreatomagmatic eruption clouds near the vent of the volcano and in plumes injected into the stratosphere from the major eruptions of 18 and 25 May. The phreatic aerosol was characterized by an essentially monomodal size distribution dominated by silicate particles larger than 10 micrometers in diameter. The phreatomagmatic eruption cloud was multimodal; the large size mode consisted of silicate particles and the small size modes were made up of mixtures of sulfuric acid and silicate particles. The stratospheric aerosol from the main eruption exhibited a characteristic narrow single mode with particles less than 1 micrometer in diameter and nearly all of the mass made up of sulfuric acid droplets.     

The persistently variable "background" stratospheric aerosol layer and global climate change

Recent measurements demonstrate that the "background" stratospheric aerosol layer is persistently variable rather than constant, even in the absence of major volcanic eruptions. Several independent data sets show that stratospheric aerosols have increased in abundance since 2000. Near-global satellite aerosol data imply a negative radiative forcing due to stratospheric aerosol changes over this period of about -0.1 watt per square meter, reducing the recent global warming that would otherwise have occurred. Observations from earlier periods are limited but suggest an additional negative radiative forcing of about -0.1 watt per square meter from 1960 to 1990. Climate model projections neglecting these changes would continue to overestimate the radiative forcing and global warming in coming decades if these aerosols remain present at current values or increase.     

Photolysis of sulfuric acid vapor by visible solar radiation

Atmospheric field measurements and models of the stratospheric sulfate aerosol layer led to the suggestion that sulfuric acid (H2SO4) must photolyze at high altitudes. We propose that excitation of vibrational overtones of H2SO4 and its hydrate in the near-infrared and visible leads to photolysis, forming sulfur trioxide (SO3) and water. On the basis of absorption cross sections calculated with ab initio methods calibrated to experimental measurements, we estimated J values that are sufficient to explain stratospheric and mesospheric sulfur dioxide (SO2) concentrations and the observation of the sulfate layer.     

Sulfuric acid-ammonium sulfate aerosol: optical detection in the St. Louis region

Nephelometric sensing of the deliquescence of ammonium sulfate produced by the reaction of sulfuric acid or ammonium bisulfate aerosol with ammonia provides a means for detecting these substances in air. Field experiments show them to be the dominant substances in the submicrometer, light-scattering aerosol in the St. Louis region.     

Venus clouds: structure and composition

The clouds of Venus consist of a fine sulfuric acid aerosol similar to that found in the earth's stratosphere. The acid aerosol on Venus appears to be uniformly mixed with the gas, at least in the visible layers, and possibly down to the cloud base.     

Sulfate aerosol: its geographical extent in the midwestern and southern United States

Sulfate particles (sulfuric acid and its neutralization products with ammonia) dominate the submicrometer-sized, light-scattering component of the aerosol in more than 90 percent of 2850 pairs of humidographic measurements made over a 3-month period at three rural midwestern and southern sites. The nearly continuous optical dominance by sulfate in the aerosol at these spatially varied locations, particularly in the Ozark Mountains, suggests that sulfate is a component of the submicrometer-sized aerosol that is distributed over a large geographical region and is not due to local sources.     

Physical Chemistry of the H2SO4/HNO3/H2O System: Implications for Polar Stratospheric Clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.     

Stratospheric sulfuric Acid layer: evidence for an anthropogenic component

Recent measurements of small aerosol particles in the stratosphere over Laramie, Wyoming, indicate low-concentration background conditions. A comparison of measurements made some 20 years ago with the present background concentration reveals the possibility of an increase of 9 percent per year. Since the aerosol particles are predominantly sulfuric acid droplets which form in the stratosphere from tropospheric sulfur-containing gases, such an increase may be related to man-made sulfur emissions.     

The Reaction of CIONO2 with Submicrometer Sulfuric Acid Aerosol

The measured reaction probability, gamma for the reaction of chlorine nitrate (CIONa(2)) with 60 percent (by weight) sulfuric acid aerosol increases monotonically with particle size at 250 kelvin. The reacto-diffusive length (l, the effective liquid depth over which reaction occurs) derived from these experiments is 0.037 +/- 0.007 micrometer (95 percent confidence level for precision). The reaction probability for the reaction of CIONO(2) with 60 percent sulfuric acid aerosol doped with approximately 7 x 10(-4) M hydrochloric acid at 250 kelvin is larger by about a factor of 4 than in the absence of hydrochloric acid and varies less with particle size (l = 0.009 +/- 0.005 micrometer). These results provide a test of the theory for gas-particle reactions and further insight into the reactivity of atmospheric aerosol.     

Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions

The observed mass-independent sulfur isotopic composition (Delta33S) of volcanic sulfate from the Agung (March 1963) and Pinatubo (June 1991) eruptions recorded in the Antarctic snow provides a mechanism for documenting stratospheric events. The sign of Delta33S changes over time from an initial positive component to a negative value. Delta33S is created during photochemical oxidation of sulfur dioxide to sulfuric acid on a monthly time scale, which indicates a fast process. The reproducibility of the results reveals that Delta33S is a reliable tracer to chemically identify atmospheric processes involved during stratospheric volcanism.     

Metastable phases in polar stratospheric aerosols

Phase changes in stratospheric aerosols were studied by cooling a droplet of sulfuric acid (H(2)SO(4)) in the presence of nitric acid (HNO(3)) and water vapor. A sequence of solid phases was observed to form that followed Ostwald's rule for phase nucleation. For stratospheric partial pressures at temperatures between 193 and 195 kelvin, a metastable ternary H(2)SO(4)-HNO(3) hydrate, H(2)SO(4) . HNO(3) . 5H(2)O, formed in coexistence with binary H(2)SO(4) . kH(2)O hydrates (k = 2, 3, and 4) and then transformed to nitric acid dihydrate, HNO(3) . 2H(2)O, within a few hours. Metastable HNO(3) . 2H(2)O always formed before stable nitric acid trihydrate, HNO(3).3H(2)O, under stratospheric conditions and persisted for long periods. The formation of metastable phases provides a mechanism for differential particle growth and sedimentation of HNO(3) from the polar winter stratosphere.     

Stratospheric Aerosol Effects from Soufriere Volcano as Measured by the SAGE Satellite System

During its April 1979 eruption series, Soufriere Volcano produced two major stratospheric plumes that the SAGE (Stratospheric Aerosol and Gas Experiment) satellite system tracked to West Africa and the North Atlantic Ocean. The total mass of these plumes, whose movement and dispersion are in agreement with those deduced from meteorological data and dispersion theory, was less than 0.5 percent of the global stratospheric aerosol burden; no significant temperature or climate perturbation is therefore expected.     

Smog aerosol: infrared spectra

Infrared spectra of smog aerosol are similar to those of sulfuric acid aerosol, but they do not show the prominent CH and carbonyl bands of organic aerosols from terpenes. Some features of the smog aerosol spectra are not present in the spectra from either type of synthetic aerosol.     

Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions

According to evidence from our laboratory, acidic surfaces on atmospheric aerosols lead to potentially multifold increases in secondary organic aerosol (SOA) mass. Experimental observations using a multichannel flow reactor, Teflon (polytetrafluoroethylene) film bag batch reactors, and outdoor Teflon-film smog chambers strongly confirm that inorganic acids, such as sulfuric acid, catalyze particle-phase heterogeneous reactions of atmospheric organic carbonyl species. The net result is a large increase in SOA mass and stabilized organic layers as particles age. If acid-catalyzed heterogeneous reactions of SOA products are included in current models, the predicted SOA formation will be much greater and could have a much larger impact on climate forcing effects than we now predict.     

Particle nucleation in the tropical boundary layer and its coupling to marine sulfur sources

New particle formation in a tropical marine boundary layer setting was characterized during NASA's Pacific Exploratory Mission-Tropics A program. It represents the clearest demonstration to date of aerosol nucleation and growth being linked to the natural marine sulfur cycle. This conclusion was based on real-time observations of dimethylsulfide, sulfur dioxide, sulfuric acid (gas), hydroxide, ozone, temperature, relative humidity, aerosol size and number distribution, and total aerosol surface area. Classic binary nucleation theory predicts no nucleation under the observed marine boundary layer conditions.     

Ablation, flux, and atmospheric implications of meteors inferred from stratospheric aerosol

Single-particle analyses of stratospheric aerosol show that about half of the particles contain 0.5 to 1.0 weight percent meteoritic iron by mass, requiring a total extraterrestrial influx of 8 to 38 gigagrams per year. The sodium/iron ratio in these stratospheric particles is higher and the magnesium/iron and calcium/iron ratios are lower than in chondritic meteorites, implying that the fraction of material that is ablated must lie at the low end of previous estimates and that the extraterrestrial component that resides in the mesosphere and stratosphere is not of chondritic composition.     

Clouds of venus: particle size distribution measurements

Data from the Pioneer Venus cloud particle size spectrometer experiment has revealed the Venus cloud system to be a complicated mixture of particles of various chemical composition distinguishable by their multimodal size distributions. The appearance, disappearance, growth, and decay of certain size modes has aided the preliminary identification of both sulfuric acid and free sulfur cloud regions. The discovery of large particles > 30 micrometers, significant particle mass loading, and size spectral features suggest that precipitation is likely produced; a peculiar aerosol structure beneath the lowest cloud layer could be residue from a recent shower.