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NASA NTRS1988

Antarctic polar stratospheric aerosols: The roles of nitrates, chlorides and sulfates

Nitric and hydrochloric acids have been postulated to condense in the winter polar stratosphere to become an important component of polar stratospheric clouds. One implication is that the removal of NO(y) from the gas phase by this mechanism allows high Cl(x) concentrations to react with O3, because the formation of ClNO3 is inhibited. Contributions of NO3 and Cl to the stratospheric aerosol were determined during the 1987 Airborne Antarctic Ozone Experiment by testing for the presence of nitrates and chlorides in the condensed phase. Aerosol particles were collected on four 500 micron diameter gold wires, each pretreated differently to give results that were specific to certain physical and chemical aerosol properties. One wire was carbon-coated for concentration and size analyses by scanning electron microscopy; X-ray energy dispersive analyses permitted the detection of S and Cl in individual particles. Three more wires were coated with Nitron, barium chloride and silver nitrate, respectively, to detect nitrate, sulfate and chloride in aerosol particles. All three ions, viz., sulfates, nitrates and chlorides were detected in the Antarctic stratospheric aerosol. In terms of number concentrations, the aerosol was dominated by sulfates, followed by chlorides and nitrates. An inverse linear regression can be established between nitrate concentrations and ozone mixing ratio, and between temperature and nitrates.

Pueschel, R. F.↗

NASA NTRS1988

Filter measurements of chemical composition during the airborne Antarctic ozone experiment

During the Airborne Antarctic Ozone Experiment campaign, a filter sampler was flown to measure the bulk composition of aerosol and gas phases. The background sulfate aerosol was measured in regions inside and outside of the chemically perturbed region (CPR) of the polar vortex. The mass ratio of sulfate outside to inside was 2.8. This is indicative of a cleansing mechanism effecting the CPR or of a different air mass inside versus outside. The absolute value of the sulfate mixing ratio shows that the background aerosol has not been influenced by recent volcanic eruptions. The sulfate measured on the ferry flight returning to NASA Ames shows a decrease towards the equator with increasing concentrations in the northern hemisphere. Nitrate in the aerosol phase was observed on two flights. The largest amount of nitrate measured in the aerosol was 44 percent of the total amount of nitrate observed. Other samples on the same flights show no nitrate in the aerosol phase. The presence of nitrate in the aerosol is correlated with the coldest temperatures observed on a given flight. Total nitrate (aerosol plus acidic vapor nitrate) concentrations were observed to increase at flight altitude with increasing latitude north and south of the equator. Total nitrate was lower inside the CPR than outside. Chloride and flouride were not detected in the aerosol phase. From the concentrations of acidic chloride vapor, the ratio of acidic vapor Cl to acidic vapor F and a summing of the individual chloride containing species to yield a total chloride concentration, there is a suggestion that some of the air sampled was dechlorinated. Acidic vapor phase fluoride was observed to increase at flight altitude with increasing latitude both north and south of the equator. The acidic vapor phase fluoride was the only compound measured with the filter technique that exhibited larger concentrations inside the CPR than outside.

Grandrud, B. W.↗

NASA NTRS1980

Ground cloud hydrogen chloride measurements from three Titan launches at the Kennedy Space Center during 1978 and 1979

Total hydrogen chloride and gaseous hydrogen chloride concentrations were measured in the exhaust cloud produced at three Titan 3 launches at the Kennedy Space Center in March 1978, December 1978, and November 1979 to determine the degree of hydrogen chloride partitioning in a solid rocket exhaust cloud between gaseous hydrogen chloride and hydrochloric acid aerosol as a function of ambient relative humidity. Moderately low relative humidity conditions were present during a daytime launch on Mar 25, 1978, and high relative humidity conditions were present during a nighttime launch on December 13, 1978. Gaseous hydrogen chloride concentrations and meteorological data, as a function of time after launch, are presented. Hydrogen chloride is present in both the gaseous and aerosol phase in the exhaust cloud. Total HCl concentrations ranged from 18 parts per million by volume (ppm) several minutes after launch down to 1 ppm after the cloud stabilization period, depending on the meteorological conditions. Gaseous HCl concentrations ranged from 2 to 3 ppm several minutes after launch to less than 1 ppm after cloud stabilization. These measured concentrations indicated significant HCl aerosol formation.

Seabacher, D. I.↗

NASA NTRS1977

Non Urban Troposphere Composition Symposium, Hollywood, Fla., November 10-12, 1976, Proceedings

Papers are presented which originate from a conference on 'The Non-Urban Troposphere Composition', held in 1976. Attention is given to distributions of nitrous oxide in the atmosphere, and to tropospheric and stratospheric compositions which are perturbed by NO(x) emissions from high-altitude aircraft. Ozone is studied in terms of in situ measurements; various meteorological analyses of tropopause folding, ozone measurements in the Boston area, and ozone measurements in rural areas are presented. A one-dimensional model used to study tropospheric photochemistry numerically is presented as are vertical profiles of tropospheric and stratospheric molecular hydrogen. The oxidation of ammonia, methane, and hydrogen sulfide is assessed in nonurban tropospheres along with nonurban measurements of ethane and methane for various atmospheric conditions. With reference to the particle size distribution of chloride in the marine aerosol, organic and inorganic chlorine concentrations are evaluated, and measurements of sea-air CO2 flux by eddy correlation are investigated.

Source record↗

NASA NTRS1973

Hydrochloric acid aerosol formation by the interaction of hydrogen chloride with humid air

The conditions in which hydrochloric acid aerosol is predicted by the interaction of hydrogen chloride gas with the water vapor in humid air are analyzed. The liquid gas phase equilibrium for the HCL-H2O system is expressed in terms of relative humidity and hydrogen chloride concentration as parts per million, units commonly used in pollution studies. Presented are the concentration (wt %) of HC1 in the aerosol and the concentration of aerosol (ppm) predicted.

Rhein, R. A.↗

NASA NTRS1980

Analysis of the measured effects of the principal exhaust effluents from solid rocket motors

The feasibility of conducting environmental chamber tests using a small rocket motor to study the physical processes which occur when the exhaust products from solid motors mix with the ambient atmosphere was investigated. Of particular interest was the interaction between hydrogen chloride, aluminum oxide, and water vapor. Several types of instruments for measuring HCl concentrations were evaluated. Under some conditions it was noted that acid aerosols were formed in the ground cloud. These droplets condensed on Al2O3 nuclei and were associated with the rocket exhaust cooling during the period of plume rise to stabilization. Outdoor firings of the solid rocket motors of a 6.4 percent scaled model of the space shuttle were monitored to study the interaction of the exhaust effluents with vegetation downwind of the test site. Data concerning aluminum oxide particles produced by solid rocket motors were evaluated.

Dawbarn, R.↗

NASA NTRS2000

Electrospraying and Electrospinning of Polymers for Biomedical Applications. Poly(Lactic-Co-Glycolic Acid) and Poly(Ethylene-Co-Vinylacetate)

Significant opportunities exist for the processing of polymers (homopolymers and blends) using electric fields. Specific attention is given here to electrospinning, but we note that electroaerosol formation and field-modulated film casting represent additional processing options. Of particular interest is the ability to generate polymer fibers of sub-micron dimensions using electrospinning, down to about 0.05 microns (50 nm), a size range that has been traditionally difficult to access. In our work, poly(lactic-co-glycolic acid), PLA/PGA, poly(lactic acid) PLA, and poly(ethylene-co-vinylacetate) (PEVA) have been deposited from solutions in methylene chloride or chloroform by electrospraying or electrospinning to afford morphologically tailored materials for tissue engineering and related applications. Low solution concentrations tend to favor electrostatic spraying ('electro-aerosolization') while higher concentrations lead to spinning on fibrous mats. Preliminary observations of muscle cell growth on PLA electrospun mats are reported.

Stitzel, Joel D.↗

NASA NTRS2013

Materials Combustion Testing and Combustion Product Sensor Evaluations in FY12

NASA Centers continue to collaborate to characterize the chemical species and smoke particles generated by the combustion of current space-rated non-metallic materials including fluoropolymers. This paper describes the results of tests conducted February through September 2012 to identify optimal chemical markers both for augmenting particle-based fire detection methods and for monitoring the post-fire cleanup phase in human spacecraft. These studies follow up on testing conducted in August 2010 and reported at ICES 2011. The tests were conducted at the NASA White Sands Test Facility in a custom glove box designed for burning fractional gram quantities of materials under varying heating profiles. The 623 L chamber was heavily instrumented to quantify organics (gas chromatography/mass spectrometry), inorganics by water extraction followed by ion chromatography, and select species by various individual commercially-available sensors. Evaluating new technologies for measuring carbon monoxide, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and other species of interest was a key objective of the test. Some of these sensors were located inside the glovebox near the fire source to avoid losses through the sampling lines; the rest were located just outside the glovebox. Instruments for smoke particle characterization included a Tapered Element Oscillating Microbalance Personal Dust Monitor (TEOM PDM) and a TSI Dust Trak DRX to measure particle mass concentration, a TSI PTrak for number concentration and a thermal precipitator for collection of particles for microscopic analysis. Materials studied included Nomex®, M22759 wire insulation, granulated circuit board, polyvinyl chloride (PVC), Polytetrafluoroethylene (PTFE), Kapton®, and mixtures of PTFE and Kapton®. Furnace temperatures ranged from 340o to 640o C, focusing on the smoldering regime. Of particular interest in these tests was confirming burn repeatability and production of acid gases with different fuel mixture compositions, as well as the dependence of aerosol concentrations on temperature.

Smoke↗

NASA NTRS2013

Materials Combustion Testing and Combustion Product Sensor Evaluations in FY12

NASA Centers continue to collaborate to characterize the chemical species and smoke particles generated by the combustion of current space-rated non-metallic materials including fluoropolymers. This paper describes the results of tests conducted February through September 2012 to identify optimal chemical markers both for augmenting particle-based fire detection methods and for monitoring the post-fire cleanup phase in human spacecraft. These studies follow up on testing conducted in August 2010 and reported at ICES 2011. The tests were conducted at the NASA White Sands Test Facility in a custom glove box designed for burning fractional gram quantities of materials under varying heating profiles. The 623 L chamber was heavily instrumented to quantify organics (gas chromatography/mass spectrometry), inorganics by water extraction followed by ion chromatography, and select species by various individual commercially-available sensors. Evaluating new technologies for measuring carbon monoxide, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and other species of interest was a key objective of the test. Some of these sensors were located inside the glovebox near the fire source to avoid losses through the sampling lines; the rest were located just outside the glovebox. Instruments for smoke particle characterization included a Tapered Element Oscillating Microbalance Personal Dust Monitor (TEOM PDM) and a TSI Dust Trak DRX to measure particle mass concentration, a TSI PTrak for number concentration and a thermal precipitator for collection of particles for microscopic analysis. Materials studied included Nomex(R), M22759 wire insulation, granulated circuit board, polyvinyl chloride (PVC), Polytetrafluoroethylene (PTFE), Kapton(R), and mixtures of PTFE and Kapton(R). Furnace temperatures ranged from 340 to 640 C, focusing on the smoldering regime. Of particular interest in these tests was confirming burn repeatability and production of acid gases with different fuel mixture compositions, as well as the dependence of aerosol concentrations on temperature.

Combustion↗

NASA NTRS1979

Hydrogen chloride partitioning in a Titan III exhaust cloud diluted with ambient air

Measurements and analysis are presented of the partitioning of HCl between hydrochloric acid aerosol and gaseous HCl in a Titan III exhaust cloud, as the cloud is diluted with humid ambient air. Partitioning was determined by measuring the gaseous HCl concentration with a recently developed airborne Gas Filter Correlation detector and simultaneously with a chemiluminescence detector which measures total HCl. Although equilibrium predictions for HCl aerosol formation indicated that no HCl aerosol should exist in the exhaust cloud for the meteorological conditions of this launch, the measurements indicated significant HCl aerosol formation. These measurements will provide verification for advanced modeling programs now under development.

Sebacher, D. I.↗

NASA NTRS1996

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↗

NASA NTRS1990

Precipitation chemistry in central Amazonia

Rain samples from three sites in central Amazonia were collected over a period of 6 weeks during the 1987 wet season and analyzed for ionic species and dissolved organic carbon. A continuous record of precipitation chemistry and amount was obtained at two of these sites, which were free from local or regional pollution, for a time period of over 1 month. The volume-weighted mean concentrations of most species were found to be about a factor of 5 lower during the wet season compared with previous results from the dry season. Only sodium, potassium, and chloride showed similar concentrations in both seasons. When the seasonal difference in rainfall amount is taken into consideration, the deposition fluxes are only slightly lower for most species during the wet season than during the dry season, again with the exception of chloride, potassium, and sodium. Sodium and chloride are present in the same ratio as in sea salt; rapid advection of air masses of marine origin to the central Amazon Basin during the wet season may be responsible for the observed higher deposition flux of these species. Statistical analysis suggests that sulfate is, to a large extent, of marine (sea salt and biogenic) origin, but that long-range transport of combustion-derived aerosols also makes a significant contribution to sulfate and nitrate levels in Amazonian rain. Organic acid concentrations in rain were responsible for a large fraction of the observed precipitation acidity; their concentration was strongly influenced by gas/liquid interactions.

Andreae, M. O.↗

NASA NTRS1976

Studies of the exhaust products from solid propellant rocket motors

This study was undertaken to determine the feasibility of conducting environmental chamber tests on the physical processes which occur when a solid rocket motor exhaust mixes with the ambient atmosphere. Of particular interest was the interaction between hydrogen chloride, aluminum oxide, and water vapor. The program consisted of three phases: (1) building a small rocket motor and using it to provide the exhaust species in a controlled environment; (2) evaluating instruments used to detect and measure HCl concentrations and if possible determining whether the HCl existed in the gaseous state or as an acid aerosol; (3) monitoring a series of 6.4-percent scale space shuttle motor tests and comparing the results to the environmental chamber studies. Eighteen firings were conducted in an environmental chamber with the initial ambient relative humidity set at values from 29 to 100 percent. Two additional firings were made in a large shed, and four were made on an open concrete apron. Six test firings at MSFC were monitored, and the ground level concentrations are reported. Evidence is presented which shows that the larger Al2O3 (5 to 50 micrometers) particles from the rocket motor can act as condensation nuclei. Under appropriate ambient conditions where there is sufficient water vapor this results in the formation of an acid aerosol. Droplets of this acid were detected both in the environmental chamber and in the scaled shuttle engine tests.

Dawbarn, R.↗

NASA NTRS1973

Some environmental considerations relating to the interaction of the solid rocket motor exhaust with the atmosphere: Predicted chemical composition of exhaust species and predicted conditions for the formation of HCl aerosol

The exhaust products of a solid rocket motor using as propellant 14% binder, 16% aluminum, and 70% (wt) ammonium perchlorate consist of hydrogen chloride, water, alumina, and other compounds. The equilibrium and some frozen compositions of the chemical species upon interaction with the atmosphere were computed. The conditions under which hydrogen chloride interacts with the water vapor in humid air to form an aerosol containing hydrochloric acid were computed for various weight ratios of air/exhaust products. These computations were also performed for the case of a combined SRM and hydrogen-oxygen rocket engine. Regimes of temperature and relative humidity where this aerosol is expected were identified. Within these regimes, the concentration of HCL in the aerosol and weight fraction of aerosol to gas phase were plotted. Hydrochloric acid aerosol formation was found to be particularly likely in cool humid weather.

Rhein, R. A.↗

NASA NTRS1999

Electrochemical Measurement of Atmospheric Corrosion

Corrosion of Shuttle thruster components in atmospheres containing high concentrations of nitrogen tetroxide (NTO) and water is an important issue in ground operations of bipropellant systems in humid locations. Measurements of the corrosivities of NTO-containing atmospheres and the responses of different materials to these atmospheres have been accomplished using an electrochemical sensor. The sensor is composed of alternating aluminum/titanium strips separated by thin insulating layers. Under high humidity conditions a thin film of water covers the surface of the sensor. Added NTO vapor reacts with the water film to form a conductive medium and establishes a galvanic cell. The current from this cell can be integrated with respect to time and related to the corrosion activity. The surface layer formed from humid air/NTO reacts in the same way as an aqueous solution of nitric acid. Nitric acid is generally considered an important agent in NTO corrosion situations. The aluminum/titanium sensor is unresponsive to dry air, responds slightly to humid air (> 75% RH), and responds strongly to the combination of humid air and NTO. The sensor response is a power function (n = 2) of the NTO concentration. The sensor does not respond to NTO in dry air. The response of other materials in this type of sensor is related to position of the material in a galvanic series in aqueous nitric acid. The concept and operation of this electrochemical corrosion measurement is being applied to other corrosive atmospheric contaminants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, and acidic aerosols.

DeArmond, Anna H.↗

NASA NTRS2024

Sea Salt Reactivity Over the Northwest Atlantic: an in-Depth Look Using the Airborne ACTIVATE Dataset

Chloride (Cl−) displacement from sea salt particles is an extensively studied phenomenon with implications for human health, visibility, and the global radiation budget. Past works have investigated Cl− depletion over the northwest Atlantic (NWA); however, an updated, multi-seasonal, and geographically expanded account of sea salt reactivity over the region is needed. This study uses chemically resolved mass concentrations and meteorological data from the airborne Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE) to quantify seasonal, spatial, and meteorological trends in Cl− depletion and to explore the importance of quantifying (1) non-sea salt sources of Na+ and (2) mass concentrations of lost Cl− (instead of relative amounts displaced). Lost Cl− mass concentrations are lowest in December–February and March, moderate around Bermuda in June, and highest in May (median losses of 0.04, 0.04, 0.66, and 1.76µgm−3, respectively), with losses in May that are high enough to potentially accelerate tropospheric oxidation rates. Inorganic acidic species can account for all Cl− depletion in December–February, March, and June near Bermuda but none of the lost Cl− in May, suggesting that organic acids may be of importance for Cl− displacement in certain months. Contributions of dust to Na+ are not important seasonally but may cause relevant overestimates of lost Cl− in smoke and dust plumes. Higher percentages of Cl− depletion often do not correspond to larger mass concentrations of lost Cl−, so it is highly recommended to quantify the latter to place depletion reactions in context with their role in atmospheric oxidation and radiative forcing.

ACTIVATE↗

NASA NTRS1984

Hydrogen chloride and aerosol ground cloud characteristics resulting from Space Shuttle launches

Airborne measurements of gaseous HCl, gaseous and aerosol HCl, particulates, relative humidity and temperature were obtained in ground clouds produced during three Space Shuttle launches. Partitioning of HCl between HCl aerosol and gaseous HCl was investigated as the solid rocket exhaust cloud diluted with ambient air to evaluate the conditions under which aerosol formation occurs in the troposphere in the presence of hygroscopic HCl vapor. Equilibrium predictions for aqueous HCl aerosol formation generally agree with the measured HCl partitioning over HCl concentrations from 0.5 to 36 ppm. HCl concentration dispersion within four cloud segments at time t (min) was evaluated using the expression C = C(0) (t to the alpha power) where C(0) varied from 145 to 2250 ppm and alpha varied from -1.14 to -1.73. Aerosol fallout from the exhaust clouds was measured with time by monitoring HCl concentrations and aerosol distributions 100 m below the cloud as it drifted away from the launch site. Significant amounts of HCl were found to be removed by fallout of particles in the 80-220 micron diameter range up to 30 min after launch.

Sebacher, D. I.↗

NASA NTRS1980

Hydrochloric acid aerosol and gaseous hydrogen chloride partitioning in a cloud contaminated by solid rocket exhaust

Partitioning of hydrogen chloride between hydrochloric acid aerosol and gaseous HCl in the lower atmosphere was experimentally investigated in a solid rocket exhaust cloud diluted with humid ambient air. Airborne measurements were obtained of gaseous HCl, total HCl, relative humidity and temperature to evaluate the conditions under which aerosol formation occurs in the troposphere in the presence of hygroscopic HCl vapor. Equilibrium predictions of HCl aerosol formation accurately predict the measured HCl partitioning over a range of total HCl concentrations from 0.6 to 16 ppm.

Sebacher, D. I.↗