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Uptake of Hypobromous Acid (HOBr) by Aqueous Sulfuric Acid Solutions: Low-Temperature Solubility and Reaction

Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.

Iraci, Laura T.↗

The missing base molecules in atmospheric acid–base nucleation

Abstract Transformation of low-volatility gaseous precursors to new particles affects aerosol number concentration, cloud formation and hence the climate. The clustering of acid and base molecules is a major mechanism driving fast nucleation and initial growth of new particles in the atmosphere. However, the acid–base cluster composition, measured using state-of-the-art mass spectrometers, cannot explain the measured high formation rate of new particles. Here we present strong evidence for the existence of base molecules such as amines in the smallest atmospheric sulfuric acid clusters prior to their detection by mass spectrometers. We demonstrate that forming (H2SO4)1(amine)1 is the rate-limiting step in atmospheric H2SO4-amine nucleation and the uptake of (H2SO4)1(amine)1 is a major pathway for the initial growth of H2SO4 clusters. The proposed mechanism is very consistent with measured new particle formation in urban Beijing, in which dimethylamine is the key base for H2SO4 nucleation while other bases such as ammonia may contribute to the growth of larger clusters. Our findings further underline the fact that strong amines, even at low concentrations and when undetected in the smallest clusters, can be crucial to particle formation in the planetary boundary layer.

54 ENVIRONMENTAL SCIENCES↗

The chemistry of Venus' atmosphere

A model for the Venus atmosphere involving photochemistry of oxygen, hydrogen, chlorine and sulfur species is presented. Sulfur reaction schemes and hydrogen and chlorine reaction schemes were included. The impact of sulfur on the oxygen budget and the subsequent production of H2SO4 molecules for the Venus cloud deck were explored. A major new reaction scheme for production of H2SO4 molecules involving sulfur and oxygen chemistry was established shown to dominate over the odd hydrogen scheme proposed earlier. The efficiency of the scheme in formation of H2SO4 is only about 50%, with the remaining sulfur residing in SO2 molecules. The calculated downward flux of H2SO4 may be sufficient to maintain a steady state sulfuric acid cloud if the resident time of H2SO4 droplets in the cloud is as long as a few years. If however, the resident time is half a year or shorter, additional chemistry capable of more efficient conversion of SO2 to SO3 is required.

Sze, N. D.↗

Experimental studies of the ion-induced binary nucleation

The aerosol nucleation phenomenon is studied in a binary mixture of H2O and H2SO4 vapors in a carrier stream of N2 gas in the presence of ions produced by a low energy beta source. Cluster spectra of the form (H2SO4)n.(H2O)m.H(+) are identified from the measurements of the cluster masses using a quadrupole mass spectrometer. Results show that the number of H2SO4 molecules in the clusters ranged from 0 to 6 whereas the number of H2O molecules ranged from 1 to 20 depending on the concentration of H2SO4 and H2O vapors in the reaction chamber. Among other conclusions, it is noted that a large number of clusters of the type investigated are formed in the presence of an ionization source even when the partial pressures of H2SO4 and H2O are very low. The cluster composition is found to be strongly dependent on the r.h. and r.a. values in the reaction cell. The cluster spectrum (n, m, l) contains a large number of low n- and low m-value clusters when the reaction cell pressure is high.

Singh, J. J.↗

Understanding the variation in the millimeter-wave emission of Venus

Recent observations of the millimeter-wave emission from Venus at 112 GHz (2.6 mm) have shown significant variations in the continuum flux emission that may be attributed to the variability in the abundances of absorbing constituents in the Venus atmosphere. Such constituents include gaseous H2SO4, SO2, and liquid sulfuric acid (cloud condensates). Recently, Fahd and Steffes have shown that the effects of liquid H, SO4, and gaseous SO2 cannot completely account for this measured variability in the millimeter-wave emission of Venus. Thus, it is necessary to study the effect of gaseous H2SO4 on the millimeter-wave emission of Venus. This requires knowledge of the millimeter-wavelength (MMW) opacity of gaseous H2SO4, which unfortunately has never been determined for Venus-like conditions. We have measured the opacity of gaseous H2SO4 in a CO2 atmosphere at 550, 570, and 590 K, at 1 and 2 atm total pressure, and at a frequency of 94.1 GHz. Our results, in addition to previous centimeter-wavelength results are used to verify a modeling formalism for calculating the expected opacity of this gaseous mixture at other frequencies. This formalism is incorporated into a radiative transfer model to study the effect of gaseous H2SO4 on the MMW emission of Venus.

Fahd, Antoine K.↗

Long-term variations in abundance and distribution of sulfuric acid vapor in the Venus atmosphere inferred from Pioneer Venus and Magellan radio occultation studies

Radio occultation experiments have been used to study various properties of planetary atmospheres, including pressure and temperature profiles, and the abundance profiles of absorbing constituents in those planetary atmospheres. However, the reduction of amplitude data from such experiments to determine abundance profiles requires the application of the inverse Abel transform (IAT) and numerical differentiation of experimental data. These two operations preferentially amplify measurement errors above the true signal underlying the data. A new technique for processing radio occultation data has been developed that greatly reduces the errors in the derived absorptivity and abundance profiles. This technique has been applied to datasets acquired from Pioneer Venus Orbiter radio occultation studies and more recently to experiments conducted with the Magellan spacecraft. While primarily designed for radar studies of the Venus surface, the high radiated power (EIRP) from the Magellan spacecraft makes it an ideal transmitter for measuring the refractivity and absorptivity of the Venus atmosphere by such experiments. The longevity of the Pioneer Venus Orbiter has made it possible to study long-term changes in the abundance and distribution of sulfuric acid vapor, H2SO4(g), in the Venus atmosphere between 1979 and 1992. The abundance of H2SO4(g) can be inferred from vertical profiles of 13-cm absorptivity profiles retrieved from radio occultation experiments. Data from 1979 and 1986-87 suggest that the abundance of H2SO4(g) at latitudes northward of 70 deg decreased over this time period. This change may be due to a period of active volcanism in the late 1970s followed by a relative quiescent period, or some other dynamic process in the Venus atmosphere. While the cause is not certain, such changes must be incorporated into dynamic models of the Venus atmosphere. Potentially, the Magellan spacecraft will extend the results of Pioneer Venus Orbiter and allow the continued monitoring of the abundance of distribution of H2SO4(g) in the Venus atmosphere, as well as other interesting atmospheric properties. Without such measurements it will be difficult to address other issues such as the short-term spatial variability of the abundance of H2SO4(g) at similar latitudes in Venus atmosphere, and the identities of particles responsible for large-scale variations observed in NIR images.

Jenkins, J. M.↗

The reaction probability of N2O5 with sulfuric acid aerosols at stratospheric temperatures and compositions

We have measured the rate of reaction of N2O5 with H2O on monodisperse, submicrometer H2SO4 particles in a low-temperature flow reactor. Measurements were carried out at temperatures between 225 K and 293 K on aerosol particles with sizes and compositions comparable to those found in the stratosphere. At 273 K, the reaction probability was found to be 0.103 +/- 0.0006, independent of H2SO4 composition from 64 to 81 wt%. At 230 K, the reaction probability increased from 0.077 for compositions near 60% H2SO4 to 0.146 for compositions near 70% H2SO4. Intermediate conditions gave intermediate results except for low reaction probabilities of about 0.045 at 260 K on aerosols with about 78% H2SO4. The reaction probability did not depend on particle size. These results imply that the reaction occurs essentially at the surface of the particle. A simple model for this type of reaction that reproduces the general trends observed is presented. the presence of formaldehyde did not affect the reaction rate.

Fried, Alan↗

The Measurement of Sulfur Oxidation Products and Their Role in Homogeneous Nucleation

The loss rate of H2SO4 vapor onto submicron particles was measured for three different particle substrates. The experimental technique involved direct flow tube measurements of H2SO4 decay rates onto a polydisperse aerosol using chemical ionization mass spectroscopic detection. The aerosols of this study were partially hydrated crystalline salts with diameters in the size range of 20 to 400 nm. The mass accommodation coefficients, a, were calculated from the first-order rate constants for H2SO4 loss to be 0.73 + 0.21 and 0.79 + 0.23 for loss onto (NH4)2SO4 and NaCl, respectively. Measurements of the loss rate of H2SO4 onto a NaCl aerosol coated with stearic acid resulted in lower mass accommodation coefficients with values of 0.31 and 0.19 for aerosol with high and low stearic acid coverage, respectively. The observed decrease in a on an aerosol with a hydrocarbon coating suggests that aerosol composition is a key factor in H2SO4 adsorption on to a particle surface.

Eisele, F. L.↗

Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid: A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols

Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.

Zhang, Renyi↗

Soot and Sulfuric Acid from Aircraft: Is There Enough to Cause Detrimental Environmental E-kCTSs?

Aerosol from aircraft can affect the environment in three ways: First, soot aerosol has been implicated to cause Icing-tern ozone depletion at mid-latitudes in the lower stratosphere at a rate of approx. 5% per decade. This effect is in addition and unrelated to the polar ozone holes which are strongly influenced by heterogeneous chemistry on polar stratospheric clouds. Second, the most obvious effect of jet aircraft is the formation of visible contrails in the upper troposphere. The Salt Lake City region experienced an 8% increase in cirrus cloud cover over a 15-year period which covariates with an increase in regional commercial air traffic. If soot particles act as freezing nuclei to cause contrail formation heterogeneously, they would be linked to a secondary effect to cloud modification that very likely is climatologically important. Third, a buildup of soot aerosol could reduce the single scatter albedo of stratospheric aerosol from 0.993+0.004 to 0.98, a critical value that has been postulated to separate stratospheric cooling from warming. Thus arises an important question: Do aircraft emit sufficient amounts of soot to have detrimental effects and warrant emission controls? During the 1996 SUCCESS field campaign, we sampled aerosols in the exhaust wake of a Boeing 757 aircraft and determined emission indices for sulfuric acid (EI(sub H2SO4) = 9.0E-2 and 5.0E-1 g/kg (sub FUEL) for 75 and 675 ppm fuel-sulfur, respectively) and soot aerosol (2.2E-3 less than EI(sub SOOT) = l.lE-2 g/kg (sub FUEL)). The soot particle analysis accounted for their fractal nature, determined electron-microscopically, which enhanced the surface area by a factor of 26 and the volume 11-fold over equivalent-volume spheres. The corresponding fuel-sulfur to H2SO4 conversion efficiency was 10% (for 675 ppmm fuel-S) and 37% (for 75 ppmm fuel-S). Applying the H2SO4 emission index to the 1990 fuel use by the worlds commercial fleets of 1.3E11 kg, a conversion efficiency of 30% of 500 ppmm fuel-S would have led to an annual contribution to the atmospheric sulfur budget by aircraft of 2.E7 kg H2SO4. This is about one part in 1.E4 of anthropogenic sulfate from other sources. The soot emission index given above yielded a 1990 injection of soot aerosol by aircraft of 1.E6 kg. Thus, soot amounts to only five percent of the aerosol generated by aircraft. Its reactivity with ozone would have to be 20 times that of sulfuric acid particles to make it chemically significant. Nevertheless, the findings, of stratospheric soot loadings commensurate with aircraft fuel consumption, based on the emission index given above and the assumption of stratospheric residence times of the order of one year implicate aircraft as stratospheric polluters. A trend similar to soot of H2SO4 aerosol loading could not be deciphered, neither from in situ measurements nor SAGE II satellite extinction, against the "noise" due to volcanic eruptions. Observation of soot particles at 20 km altitude which, if emitted by aircraft were generated at 10-12 km altitude, suggests a displacement of those particles against gravity. Because eddy mixing is virtually absent in the lower stratosphere and isentropic mixing explains lofting to only about 15 km, radiometric forces acting on morphologically and chemically asymmetric soot particles must be considered a possibility. The consequence could be an extended residence time of soot against that of sulfuric acid aerosol that would lower the single scatter albedo with time.

Pueschel, R. F.↗

Physical properties of the stratospheric aerosols

A comparison of the equilibrium vapor pressure over nitric acid solutions with observed water and nitric acid partial pressures in the stratosphere implies that nitric acid cannot be present as an aerosol particle in the lower stratosphere. A similar comparison for sulfuric acid solutions indicates that sulfuric acid aerosol particles are 75% H2SO4 by weight in water, in good agreement with direct observations. The freezing curve of H2SO4 solutions requires that the H2SO4 aerosol particles be solid or supercooled. The equilibrium vapor pressure of H2SO4 in the stratosphere is of the order of 20 picotorr. At stratospheric temperatures, ammonium sulfate is in a ferroelectric phase. As a result, polar molecules may form a surface coating on these aerosols, which may be a fertile ground for further chemical reaction.

Toon, O. B.↗

Stratospheric condensation nuclei and possible solar influences

Balloon-borne measurements of condensation nuclei and H2SO4 molecules in large negative ion clusters have been made in the stratosphere at around 30 km altitude. The nuclei observed were in the 0.01-0.1 micron diameter range. Consideration was given to sunspot activity as a triggering event for ionization of upper atmospheric H2SO4 species and subsequent formation of the nuclei. A numerical model was defined for a steady state between the H2SO4 association and ion recombination in order to determine a critical nucleation rate. It is concluded that condensation nuclei are produced in ion nucleation in an H2SO4 supersaturated polar cloud chamber, with the process being initiated by solar flare particle ionization.

Hofmann, D. J.↗

Heterogeneous Interactions of ClONO2 and HCl with Sulfuric Acid Tetrahydrate: Implications for the Stratosphere

The reaction probabilities for ClONO2+H2O- HOCl + HNO3 and ClONO2+ HCl Cl2 +HNO3 have been investigated on sulfuric acid tetrahydrate (SAT, H2SO4-4H2O)surfaces at temperatures between 190 and 230 K and at reactant concentrations that are typical in the lower stratosphere, using a fast-flow reactor coupled to a quadrupole mass spectrometer. The results indicate that the reaction probabilities as well as HCl uptake depend strongly on the thermodynamic state of SAT surface: they decrease significantly with decreasing H2O partial pressure at a given temperature, and decrease with increasing temperature at a given H2O partial pressure, as the SAT changes from the H2O-rich form to the H2SO4-rich form. For H2O-rich SAT at 195 K gamma(sub 1) approx. = -0.01 and gamma(sub 2) greater or equal to 0.1, whereas the values for H2SO4-rich SAT decrease by more than 2 orders of magnitude. At low concentrations of HCl, close to those found in the stratosphere, the amount of HCl taken up by H2O-rich SAT films corresponds to a coverage of the order of a tenth of a monolayer (approx. = 10(exp 14) molecules/sq cm); H2SO4-rich SAT films take up 2 orders of magnitude less HCl (les than 10(exp 12) molecules/sq cm). Substantial HCl uptake at high HCl concentrations is also observed, as a result of surface melting. The data reveal that frozen stratospheric sulfate aerosols may play an important role in chlorine activation in the winter polar stratosphere via processes similar to those occurring on the surfaces of polar stratospheric cloud particles.

Zhang, Renyi↗

A New Parameterization of H2SO4/H2O Aerosol Composition: Atmospheric Implications

Recent results from a thermodynamic model of aqueous sulfuric acid are used to derive a new parameterization for the variation of sulfuric acid aerosol composition with temperature and relative humidity. This formulation is valid for relative humidities above 1 % in the temperature range of 185 to 260 K. An expression for calculating the vapor pressure of supercooled liquid water, consistent with the sulfuric acid model, is also presented. We show that the Steele and Hamill [1981] formulation underestimates the water partial pressure over aqueous H2SOI solutions by up to 12% at low temperatures. This difference results in a corresponding underestimate of the H2SO4 concentration in the aerosol by about 6 % of the weight percent at approximately 190 K. In addition, the relation commonly used for estimating the vapor pressure of H2O over supercooled liquid water differs by up to 10 % from our derived expression. The combined error can result in a 20 % underestimation of water activity over a H2SO4 solution droplet in the stratosphere, which has implications for the parameterization of heterogeneous reaction rates in stratospheric sulfuric acid aerosols. The influence of aerosol composition on the rate of homogeneous ice nucleation from a H2SO4 solution droplet is also discussed. This parameterization can also be used for homogeneous gas phase nucleation calculations of H2SO4 solution droplets under various environmental conditions such as in aircraft exhaust or in volcanic plumes.

Tabazadeh, Azadeh↗

Global to Microscale Evolution of the Pinatubo Volcanic Aerosol Derived from Diverse Measurements and Analyses

We assemble data on the Pinatubo aerosol from space, air, and ground measurements, develop a composite picture, and assess the consistency and uncertainties of measurement and retrieval techniques. Satellite infrared spectroscopy, particle morphology, and evaporation temperature measurements agree with theoretical calculations in showing a dominant composition of H2SO4-H20 mixture, with H2SO4 weight fraction of 65-80% for most stratospheric temperatures and humidities. Important exceptions are (1) volcanic ash, present at all heights initially and just above the tropopause until at least March 1992, and (2) much smaller H2SO4 fractions at the low temperatures of high-latitude winters and the tropical tropopause. Laboratory spectroscopy and calculations yield wavelength- and temperature-dependent refractive indices for the H2SO4-H20 droplets. These permit derivation of particle size information from measured optical depth spectra, for comparison to impactor and optical-counter measurements. All three techniques paint a generally consistent picture of the evolution of R(sub eff), the effective radius. In the first month after the eruption, although particle numbers increased greatly, R(sub eff) outside the tropical core was similar to preeruption values of approx. 0.1 to 0.2 microns, because numbers of both small (r < 0.2 microns) and large (r > 0.6 microns) particles increased. In the next 3-6 months, extracore R(sub eff) increased to approx. 0.5 microns, reflecting particle growth through condensation and coagulation. Most data show that R(sub eff) continued to increase for about 1 year after the eruption. R(sub eff) values up to 0.6 - 0.8 microns or more are consistent with 0.38 - 1 micron optical depth spectra in middle to late 1992 and even later. However, in this period, values from in situ measurements are somewhat less. The difference might reflect in situ undersampling of the very few largest particles, insensitivity of optical depth spectra to the smallest particles, or the inability of flat spectra to place an upper limit on particle size. Optical depth spectra extending to wavelengths lambda > 1 micron are required to better constrain R(sub eff), especially for R(sub eff) > 0.4 microns. Extinction spectra computed from in situ size distributions are consistent with optical depth measurements; both show initial spectra with lambda(sub max) <= 0.42 microns, thereafter increasing to 0.78 <= lambda(sub max) <= 1 micron. Not until 1993 do spectra begin to show a clear return to the preeruption signature of lambda(sub max) <= 0.42 microns. The twin signatures of large R(sub eff) (> 0.3 microns) and relatively flat extinction spectra (0.4 - 1 microns) are among the longest-lived indicators of Pinatubo volcanic influence. They persist for years after the peaks in number, mass, surface area, and optical depth at all wavelengths <= 1 microns. This coupled evolution in particle size distribution and optical depth spectra helps explain the relationship between global maps of 0.5- and 1.0-micron optical depth derived from the Advanced Very High Resolution Radiometer (AVHRR) and Stratospheric Aerosol and Gas Experiment (SAGE) satellite sensors. However, there are important differences between the AVHRR and SAGE midvisible optical thickness products. We discuss possible reasons for these differences and how they might be resolved.

Russell, P. B.↗

Pinatubo Aerosol Global-to-Micro-Scale Evolution: A Unified Picture From Space, Air, and Ground Measurements

We combine a variety of measurements to develop a composite picture of the post-Pinatubo aerosol and assess the consistency and uncertainties of the measurement and retrieval techniques Satellite infrared spectroscopy, particle morphology, and evaporation temperature measurements are in accord with theoretical calculations In showing a dominant particle composition of H2SO4-H2O mature with H2SO4 weight traction of 65-80% for most stratospheric temperatures and humidities. Important exceptions are: (1) the presence of volcanic ash at all attitudes initially and in a layer just above the tropopause until at least March 1992, and (2) much smaller H2SO4 weight fractions at the low temperatures attained In high latitude winters and at the tropical tropopause. Laboratory spectroscopy and theoretical calculations yield wavelength- and temperature-dependent refractive indices for the dominant H2SO4-H2O droplets. These in turn permit derivation of particle size spectra from measured optical depth spectra for comparison to direct measurements by impactors and optical counters, All three techniques paint a generally consistent picture of the evolution of R(sub eff) the effective, or area-weighted, particle radius. In the first month after the eruption, although particle numbers increased by orders of magnitude, R(sub eff) was similar to the pre-eruption value of 0.1 to 0.2 microns because both small (r less than 0.2 microns) and large (r greater than 0.6 microns) particles increased in number. Over the next 3-6 months, R(sub eff) increased to about 0.5 microns, reflecting particle growth through condensation and coagulation. In general, R(sub eff) continued to increase for about a year after the eruption. Extinction spectra computed from in situ size distribution measurements are consistent with optical depth measurements, which show spectra with maxima initially at wavelengths of 0.42 microns or less, and thereafter progressively increasing to between 0.78 and 1 micron. Not until 1993 does optical depth spectra begin to show a clear return to the preeruption signature of maximizing at the shortest visible wavelengths or in the near UV. This coupled evolution in particle size distribution and optical depth spectra helps explain the relationship between the global maps of 0.5- and 1.0-kilometer optical depth derived from the AVHRR and SAGE satellite measurements. It also sets a context for evaluating remaining uncertainties in each of these satellite data products. We also show how the effects of wavelength-dependent refractive index on backscatter spectra can influence particle sizes retrieved from multiwavelength lidar measurements.

Russell, Philip B.↗

A Unified Picture of Pinatubo Aerosol Global-to Micro-Scale Evolution, From Space, Air, and Ground Measurements

We combine a variety of measurements to develop a composite picture of the post-Pinatubo aerosol and assess the consistency and uncertainties of the measurement and retrieval techniques. Satellite infrared spectroscopy, particle morphology, and evaporation temperature measurements are in accord with theoretical calculations in showing a dominant particle composition of H2SO4-H2O mixture, with H2SO4 weight fraction of 65-80% for most stratospheric temperatures and humidities. Important exceptions are: (1) the presence of volcanic ash at all altitudes initially and in a layer just above the tropopause until at least March 1992, and (2) much smaller H2SO4 weight fractions at the low temperatures attained in high latitude winters and at the tropical tropopause, Laboratory spectroscopy and theoretical calculations yield wavelength- and temperature-dependent refractive indices for the dominant H2SO4-H2O droplets. These in turn permit derivation of particle size spectra from measured optical depth spectra, for comparison to direct measurements by impactors and optical counters. All three techniques paint a generally consistent picture of the evolution of R(sub eff), the effective, or area-weighted, particle radius. In the first month after the eruption, although particle numbers increased by orders of magnitude, R(sub eff) was similar to the preemption value of 0.1 to 0.2 microns, because both small (r less than 0.2 microns) and large (r greater than 0.6 micron particles increased in number. Over the next 3-6 months, R(sub eff) increased to about 0.5 microns reflecting particle growth through condensation and coagulation. In general, R(sub eff) continued to increase for about a year after the eruption. Extinction spectra computed from in situ size distribution measurements are consistent with optical depth measurements, which show spectra with maxima initially at wavelengths of 0.42 microns or less, and thereafter progressively increasing to between 0.78 and 1 micron. Not until 1993 do optical depth spectra begin to show a clear return to the preemption signature of maximizing at the shortest visible wavelengths or in the near UV. This coupled evolution in particle size distribution and optical depth spectra helps explain the relationship between the global maps of 0.5- 1.0- micron optical depth derived from the AVHRR and SAGE satellite measurements.

Russell, Philip B.↗

Soot Aerosol from Aircraft: Is there Enough to Cause Middle-Latitude Lower Stratospheric Ozone

Soot aerosol from aircraft has been implicated to cause long-term ozone depletion at mid-latitudes in the lower stratosphere at a rate of approx. equals 5%,per decade. During the 1996 SUCCESS field campaign, we sampling aerosols in the exhaust wake of a Boeing 757 aircraft and determined emission indices for sulfuric acid (EIH2SO4=4.8E-2 and 5.7E- 1. g/kgFUEL for 75 and 675 ppm fuel-sulfur, respectively) and soot (EIsoot=7.5E-4 g/kgFUEL). The corresponding fuel-sulfur to H2SO4 conversion efficiency was 25 % and 30%,respctively. Applying the H2SO4 emission index to the 1990 fuel by the world's commercial fleets of 1.3E11 kg, a conversion efficiency of 30% would have led to an annual contribution to the atmospheric sulfur budget by aircraft of 2.E7 kg H2SO4, if the fuels averaged 500 ppmm.The soot emission index given above yielded a 1990 injection of soot aerosol by aircraft of 1.E5 kg. Thus, soot amounts to only one half of one percent of the aerosol generated by aircraft. The fractal nature of soot may increase its actual surface area by about a factor of 10. The findings, however, of (1) stratospheric soot loadings commensurate with aircraft fuel consumption, based on the emission index given above and the assumption of stratospheric residence times of the order of one year; and (2) a trend in stratospheric soot loading of approx.6% per year since 1981, similar to the annual increase of aircraft operations since that time, implicate aircraft as stratospheric polluters. A trend similar to soot of H2SO4 aerosol loading could not be deciphered, neither from in situ measurements nor SAGE II extinction, against the "noise" due to volcanic eruptions, The current single scatter albedo of the stratospheric aerosol is omega = 0.993+/-0.004.

Pueschel, R. F.↗