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At least 289 records · Page 16

Optical Spectroscopy of Venus Aerosol Analogs and Substrate Survivability

Aerosol Rapid Analysis Combined Entry Probe/Sonde Technology (AERACEPT) is a dual descent probe and in-situ sampler of cloud and aerosol particles, used as part of the Nephele mission concept to study Venus cloud layers. Various optical spectroscopic characterization methods, including Raman spectroscopy and Surface Enhanced Raman Spectroscopy (SERS), Laser induced Breakdown Spectroscopy (LIBS), and absorbance and fluorescence spectroscopy are being assessed for viability for compatibility with AERACEPT. Specifically, the detection limits, sensitivity, specificity, and analysis cadence of these techniques for a set of Venus aerosol analogs and their mixtures are tested. We report on preliminary optical spectroscopy results of the Venus aerosol analogs, as well as optical substrate survivability in heated and acidic conditions, substrate physical robustness, and analyte wettability on substrates.

Venus↗

Local electronic structure of histidine in aqueous solution

Here, the local electronic structure of aqueous histidine, an amino acid important in nature and biology, is revealed by aerosol X-ray photoemission spectroscopy. A detailed picture of the photoionization dynamics emerges by tuning the pH of the aqueous solution from which the aerosols are generated, allowing us to report the X-ray photoelectron spectroscopy (XPS) of histidine. Assignment of the experimental photoelectron spectra of the C1s and N1s levels allows the determination of the protonation state of histidine in these aqueous aerosols and is confirmed by density functional calculations. XPS spectra show that at pH = 1, both imidazole and amine group nitrogens are protonated, at pH = 7, the amine group nitrogen is protonated and the carboxyl group carbon is deprotonated resulting in a zwitterionic structure, and at pH = 13, only the carboxyl group remains deprotonated. Comparison of these results with previous experimental and theoretical results suggests that X-ray spectroscopy on aqueous aerosols can provide a convenient and simple way of probing their electronic structure in aqueous solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The 1977 intertropical convergence zone experiment

Data are presented from the 1977 Intertropical Convergence Zone (ITCZ) Experiment conducted in the Panama Canal Zone in July 1977. Measurements were made daily over a 16-day period when the ITCZ moved across the Canal Zone. Two aircraft (Learjet and U-2) flew daily and provided data from horizontal traverses at several altitudes to 21.3 km of ozone, temperature, pressure, water vapor, aerosols, fluorocarbons, methane, nitrous oxide, nitric oxide, and nitric acid. Balloonsondes flown four times per day provided data on ozone, wind fields, pressure, temperature, and humidities to altitudes near 30 km. Rocketsondes provided daily data to altitudes near 69 km. Satellite photography provided detailed cloud information. Descriptions of individual experiments and detailed compilations of all results are provided.

Poppoff, I. G.↗

Stratospheric Backscatter, Extinction, and Lidar Ratio Profiling After the Mt. Pinatubo Eruptions

Since August 1991 the stratospheric aerosol layer is continuously monitored with a combination Raman elastic-backscatter lidar, groundbased systems. XeCl excimer laser is used as the radiation source. Signals elastically backscattered from air molecules and particles and inelastically Raman backscattered from nitrogen molecules are detected. The measurements of these two signal profiles up to 35 km height allows the separate and independent determination of aerosol extinction and backscatter properties in the perturbed lower stratosphere. The extinction coefficient is derived from the nitrogen Raman signal profile, while the backscatter coefficient is obtained from the elastic-to-inelastic backscatter signal ratio. In this way, also the extinction-to-backscatter, or lidar, ratio profile is determined. For the first time, lidar ratios are determined in the perturbed stratospheric layer by the use of remote sensing only. The lidar ratio contains information about the size range of the stratospheric particles which are assumed to be sulfuric acid droplets, and it is needed in the calculation of aerosol optical properties from data taken with a typical backscatter lidar.

Ansmann, Albert↗

Atmospheric nuclei in the remote free-troposphere

An extensive flight series to survey aerosol present in the upper-troposphere was undertaken aboard the NASA DC-8 as part of the Global Backscatter Experiment. Aerosol with diameters greater than 3 nm were counted and sized with a combination of condensation nuclei counters and optical particle counters. Aerosol number and mass concentrations were separately identified with regard to both refractory and volatile components. Regions of the free-troposphere with the lowest mass concentrations were generally found to have the highest number concentrations and appeared to be effective regions for new particle production. These new particle concentrations appear inversely related to available aerosol surface area, and their volatility suggests a sulfuric acid composition. The long lifetime of these new particles aloft can result in their growth to sizes effective as CN and CCN that can be mixed throughout the troposphere.

Clarke, Antony D.↗

Photochemical modelling of Venus clouds using Pioneer Venus data

In order to understand the evolution of water on Venus, we must know the hydrogen escape flux as a function of the tropospheric water abundance. We have studied the connection between total stratospheric hydrogen and exobase hydrogen available to non-thermal escape processes and examined the details of the photochemical trap for water at the Venus cloud tops. Our immediate goal is to calculate the stratospheric water abundance as a function of the tropospheric water abundance. Photochemical production of H2SO4 acts as a sink for both water and sulfur and is capable of keeping stratospheric abundances low if a proper balance exists between the tropospheric abundances. If production of H2SO4 were the only sink for H2O and SO2, the excess in tropospheric abundance of one over the other would reach the stratosphere, and the functional dependence of stratospheric H2O on tropospheric H2O would be linear near the present state. On Venus, however, sulfuric acid condenses at cloud top temperatures and the resulting aerosols can absorb additional water of hydration. This complicates the water budget, increasing the efficiency of sulfur as a sink for water. We have investigated the balance between tropospheric H2O and SO2 and how delicate the balance is. Our major conclusions from this work are the following: (1) H2O and SO2 are mutually limiting if proper tropospheric balance is maintained; (2) changes in tropospheric abundances on the order of 5 ppm are significant; and (3) changes in mixing rates near the cloud tops can cause dramatic changes in SO2 without causing dramatic changes in H2O.

Mcelroy, Michael B.↗

Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

Rossi, Michel J.↗

Modeling Aerosol Nucleation

The goal of this work has been to understand how nitric acid condenses on cirrus ice cloud particles by analyzing data obtained during the SAGE III Ozone Loss and Validation Experiment (SOLVE) research mission based out of Kiruna, Sweden. Ms. Gamblin simultaneously analyzed gas phase nitric acid data along with particulate NO, data, particulate, vapor and gas-phase water data from several different instruments, particle size data, which included surface area and volume measurements, ozone concentration data as well as temperature, pressure and GPS coordinates of the sampled air parcel. All parameters where held constant with only one allowed to vary in order to determine what controls the extent to which nitric acid will condensation on ice. In addition, this data was compared to theoretical values of nitric acid condensation on ice based upon recent laboratory data. Comparison of these two data sets shows the field data does not agree with what is expected in the laboratory at comparable temperatures and nitric acid pressures. The most significant difference is that surface coverages in the atmosphere were found to be elevated relative to surface coverages measured in the laboratory. The results of this study were accepted for publication by Geophysical Research Letters.

Toon, Owen B.↗

Airborne lidar observations in the wintertime Arctic stratosphere - Polar stratospheric clouds

Polar stratospheric cloud (PSC) distributions in the wintertime Arctic stratosphere and their optical characteristics were measured with a multiwavelength airborne lidar system as part of the 1989 Airborne Arctic Stratospheric Expedition. PSCs were observed on 10 flights between January 6 and February 2, 1989, into the polar vortex. The PSCs were found in the 14-27 km altitude range in regions where the temperatures were less than 195 K. Two types of aerosols with different optical characteristics (Types 1a and 1b) were observed in PSCs thought to be composed of nitric acid trihydrate. Water ice PSCs (Type 2) were observed to have high scattering ratios (greater than 10) and high aerosol depolarizations (greater than 10 percent) at temperatures less than 190 K.

Browell, E. V.↗

A novel approach to characterize the full spectrum and radiative properties of aerosols

Organic aerosols play a significant role in the absorption and radiative budget of the atmosphere, but current modeling approaches do not adequately capture the photo-chemical and oxidative bleaching that occurs during their lifetimes. Most climate models inaccurately assume constant optical properties of these particles, therefore leading to errors in their predictions. In this study we present an approach to better parameterize the optical properties of atmospheric aerosols, including brown carbon (BrC). Using thin-film spectrometry, the full spectrum of reflectivity and emissivity was used to calculate the complex refractive index for multiple species of organic aerosols. This is in contrast to previous techniques which only probe single wavelengths. Since BrC is a complex molecular mixture, we initially focused on single species absorption using four molecular surrogates. Dye-doped polyacrylic-acid thin-films were prepared on glass slides and compared to an aerosolized collection method. Verification of the collection method will open the door to characterizing the complex refractive index of smoke and ambient aerosol.

58 GEOSCIENCES↗

Olivine Weathering aud Sulfate Formation Under Cryogenic Conditions

High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide‐spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa‐like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo‐concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0degC in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars‐like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above ‐40degC. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial sulfur‐rich volcanism, and sulfur‐rich surface deposits also makes it very likely that sulfate aerosols have also been an important component of the martian atmosphere. Thus mixtures of ice, dust, and sulfate aerosols are likely to have been common on the martian surface. Given the fact that it is not difficult to achieve surface temperatures above ‐40degC on Mars throughout its history, it seems likely that sulfate formation on Mars is controlled by the availability of sulfate aerosols and not by the martian climate. The current polar regions of Mars and Earth provide interesting analogs. Large regions of sulfaterich material have been detected on and around the modern north polar region of Mars. The prevalence of ice‐dust mixtures in this region and the existence of sulfates within the ice cap itself are strong evidence for the origin of the sulfates from inside the ice deposits. In addition sulfates have been found in ice deposits in Greenland and Mount Fuji on Earth that have been attributed to forming within the ice deposit. These sulfates can form either through interaction with dust particles in the atmosphere or through weathering inside the ice itself.

Niles, Paul B.↗

Condensed Acids In Antartic Stratospheric Clouds

Report dicusses nitrate, sulfate, and chloride contents of stratospheric aerosols during 1987 Airborne Antarctic Ozone Experiment. Emphasizes growth of HNO3*3H2O particles in polar stratospheric clouds. Important in testing theories concerning Antarctic "ozone hole".

Pueschel, R. F.↗

H2SO4-HNO3-H2O ternary system in the stratosphere

Estimation of the equilibrium vapor pressure over the ternary system H2SO4-HNO3-H2O to study the possibility of stratospheric aerosol formation involving HNO3. It is shown that the vapor pressures for the ternary system H2SO4-HNO3-H2O with weight composition around 70-80% H2SO4, 10-20% HNO3, 10-20% H2O at -50 C are below the order of 10 to the minus 8th mm Hg. It is concluded that there exists more than sufficient nitric acid and water vapor in the stratosphere to participate in ternary system aerosol formation at -50 C. Therefore, HNO3 should be present in stratospheric aerosols, provided that H2SO4 is also present.

Kiang, C. S.↗

A novel methodology for assessing the hygroscopicity of aerosol filter samples

Abstract. Due to US regulations, concentrations of hygroscopic inorganic sulfate and nitrate have declined in recent years, leading to an increased importance of the hygroscopic nature of organic matter (OM). The hygroscopicity of OM is poorly characterized because only a fraction of the multitude of organic compounds in the atmosphere is readily measured, and there is limited information on their hygroscopic behaviors. Hygroscopicity of aerosol is traditionally measured using a humidified tandem differential mobility analyzer (HTDMA) or electrodynamic balance (EDB). EDB measures water uptake by a single particle. For ambient and chamber studies, HTDMA measurements provide water uptake and particle size information but not chemical composition. To fill this information gap, we developed a novel methodology to assess the water uptake by particles collected on Teflon filters. This method uses the same filter sample for both hygroscopicity measurements and chemical characterization, thereby providing an opportunity to link the measured hygroscopicity with ambient particle composition. To test the method, hygroscopic measurements were conducted in the laboratory for ammonium sulfate, sodium chloride, glucose, and malonic acid, which were collected on 25 mm Teflon filters using an aerosol generator and sampler. Constant-humidity solutions (CHSs), including potassium chloride, barium chloride dihydrate, and potassium sulfate, were employed in a saturated form to maintain the relative humidity (RH) at approximately 84 %, 90 %, and 97 % in small chambers. Our preliminary experiments revealed that, without the pouch, water uptake measurements were not feasible due to rapid water loss during weighing. Additionally, we observed some absorption by the aluminum pouch itself. To account for this, concurrent measurements were conducted for both the loaded and the blank filters at each RH level. Thus, the dry loaded and blank Teflon filters were placed in aluminum pouches with one side open and in RH-controlled chambers for more than 24 h. The wet loaded samples and wet blanks were then weighed using an ultramicrobalance to determine the water uptake by the respective compound and the blank Teflon filter. The net amount of water absorbed by each compound was calculated by subtracting the water uptake of the blank filter from that of the wet loaded filter. Hygroscopic parameters, including the water-to-solute (W / S) ratio, molality, mass fraction solute (mfs), and growth factors (GFs), were calculated from the measurements. The results obtained are consistent with those reported by the Extended Aerosol Inorganics Model (E-AIM) and previous studies utilizing HTDMA and EDB for these compounds, highlighting the accuracy of this new methodology. This new approach enables the hygroscopicity and chemical composition of individual filter samples to be assessed so that in complex mixtures, such as chamber and ambient samples, the total water uptake can be parsed between the inorganic and organic components of the aerosol.

54 ENVIRONMENTAL SCIENCES↗

Detection of an Atmosphere on a Rocky Exoplanet

We report the detection of an atmosphere on a rocky exoplanet, GJ 1132 b, which is similar to Earth in terms of size and density. The atmospheric transmission spectrum was detected using Hubble WFC3 measurements and shows spectral signatures of aerosol scattering, HCN, and CH{sub 4} in a low mean molecular weight atmosphere. We model the atmospheric loss process and conclude that GJ 1132 b likely lost the original H/He envelope, suggesting that the atmosphere that we detect has been reestablished. We explore the possibility of H{sub 2} mantle degassing, previously identified as a possibility for this planet by theoretical studies, and find that outgassing from ultra-reduced magma could produce the observed atmosphere. In this way we use the observed exoplanet transmission spectrum to gain insights into magma composition for a terrestrial planet. The detection of an atmosphere on this rocky planet raises the possibility that the numerous powerfully irradiated super-Earth planets, believed to be the evaporated cores of sub-Neptunes, may, under favorable circumstances, host detectable atmospheres.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interhemispheric survey of minor upper atmospheric constituents during October - November 1976

The CV-990 aircraft coordinated several flights with a NASA U-2 aircraft, NOAA ground station measurements in Alaska, Hawaii, and American Samoa, and with Australian and New Zealand ground stations, aircraft, and a balloon experiment in the Southern hemisphere. Data were obtained for species including ozone, total ozone, the oxides of nitrogen, the chlorofluoromethanes, water vapor, nitric acid, carbon monoxide, carbon dioxide, hydrogen chloride, Aitken nuclei, ammonia, aerosols, temperatures, and winds. Individual experiment results and selected analyses are presented. The experimental data include total column densities, latitude variations, interhemisphere differences, and vertical profiles.

Gauntner, D. J.↗

On the temporal variation of stratospheric aerosol size and mass during the first 18 months following the 1982 eruptions of El Chichon

Baloon-borne particle counters at Laramie and in southern Texas are used to investigate the size and mass distribution of the aerosol which formed in the stratosphere during the first 18 months following the volcanic eruption of El Chichon. The latter appears to have reached a peak at Laramie in early 1983 and began a decline in May. Measurements of average aerosol radius versus time are used to estimate a sulfuric acid concentration of about 10 to the 7th per cu cm 40 days after the eruption and a net acid vapor lifetime of 25-50 days in the 18-25-km altitude region.

Hofmann, D. J.↗

Middle atmosphere trace constituents; Proceedings of Workshop 9 of the Twenty-sixth COSPAR Plenary Meeting, Toulouse, France, June 30-July 11, 1986

Papers are presented on a reference model for stratospheric NO2, a proposed reference model for nitric acid, proposed reference models for ozone, and a background stratospheric aerosol reference model. Other topics include a comparison between the observed and calculated distributions of trace species in the middle atmosphere, recent measurements of trace constituents from rocket and balloon probes, NO2 field observations in the stratosphere during the MAP/GLOBUS Campaign in 1983 and 1985, and the vertical distribution of ozone in the equatorial zone. Also considered are precision measurements of stratospheric ozone profiles by rocket-borne optical ozonesondes, vertical profiles of source gases at tropical latitudes, and measurements of stratospheric trace constituent distributions from balloon-borne far infrared observations.

Keating, G. M.↗