Simultaneous spectroscopic measurements of stratospheric species - O3, CH4, CO, CO2, N2O, H2O, HCl, and HF at northern and southern mid-latitudes
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Mature valencia orange trees were sprayed with hydrochloric acid solutions (pH 7.8, 2.0, 1.0, and 0.5) in the field at the full bloom stage and at one month after fruit set. Potted valencia orange and dwarf citrus trees, four species of plants native to Merritt Island, and four agronomic species were exposed to various pH levels of simulated acid rain under controlled conditions. The acid rain was generated from dilutions of hydrochloric acid solutions or by passing water through an exhaust generated by burning solid rocket fuel. The plants were injured severely at pH levels below 1.0, but showed only slight injury at pH levels of 2.0 and above. Threshold injury levels were between 2.0 and 3.0 pH. The sensitivity of the different plant species to acid solutions was similar. Foliar injury symptoms were representative of acid rain including necrosis of young tissue, isolated necrotic spots or patches, and leaf abscission. Mature valencia orange trees sprayed with concentrations of 1.0 pH and 0.5 pH in the field had reduced fruit yields for two harvests after the treatment. All experimental trees were back to full productivity by the third harvest after treatment.
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Solid rocket exhaust cloud dispersion cases, based on seven meteorological regimes for overland advection in the Cape Canaveral, Florida, area, are examined for launch vehicle environmental impacts. They include a space shuttle case and all seven meteorological cases for the Titan 3, which exhausts 60% less HC1. The C(HC1) decays are also compared with recent in cloud peak HC1 data from eight Titan 3 launches. It is stipulated that while good overall agreement provides validation of the model, its limitations are considerable and a dynamics model is needed to handle local convective situations.
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The paper deals with hydrogen-chloride and hydrogen-fluoride total column measurements, their estimated long-term rates of increase, seasonal cycles, and variability, deduced from the analysis of a set of high-resolution infrared solar spectra recorded at Kitt Peak. The Kitt Peak observations and methods of analysis are described, the results are presented and compared with previously reported measurements and trends. The data is analyzed by using a multilayer nonlinear least-squares spectral fitting procedure and a consistent set of spectroscopic line parameters. Model-calculated hydrogen-chloride and hydrogen-fluoride total columns obtained with a two-dimensional model are discussed, and the model results are compared with the measured hydrogen-chloride and hydrogen-fluoride total columns, seasonal cycles, and trends. It is pointed out that the observed trends of both molecules are in satisfactory agreement with the model results calculated from emission histories and photooxidation rates for the source molecules.
High resolution Fourier transform infrared interferometric atmospheric solar absorption measurements have been performed at the National Institute for Water and Atmospheric Research Laboratory at Lauder, New Zealand on a routine basis since October 1989. This laboratory has been selected as the Mid-latitude Charter Site of the Network for the Detection of Stratospheric Change and is at a latitude of 45 deg S. Particular attention has been paid to the absorption by atmospheric hydrogen chloride at 2925.9 cm(exp -1) and in this paper the results of the seasonal cycle in CHl above Lauder will be presented. Because of the very clean troposphere at this site, the CHl column measured from the ground is essentially a stratospheric column measurement.
Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.
Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.
The troposphere is the part of the atmosphere where people live. The troposphere goes up to about 12 km above the earth over places at middle latitudes like Washington, D.C. The next layer of air up in the atmosphere is called the stratosphere. The tropopause separates the troposphere and stratosphere. Most of the ozone in the atmosphere is in the stratosphere where it protects people from the harmful rays in sunlight. Near the earth s surface, ozone is a pollutant. In general, air travels from the troposphere to the stratosphere through upward motion in the tropics. Most of the air comes back down to the troposphere at middle latitudes. The so-called "stratospheric residual circulation" moves the air in the stratosphere from the tropics to the middle latitudes. In this way, the amount of air that moves out of the stratosphere into the troposphere at middle latitudes depends on the strength of the residual circulation. This overturning of the atmosphere is important as it brings chemicals produced by the activities of people into the stratosphere. Most notable are chlorofluorocarbons (CFCs) that destroy stratospheric ozone. The transport of air out of the stratosphere removes ozone-destroying chemicals, but also brings ozone into the troposphere.
The Airborne Laser Infrared Absorption Spectrometer II (ALIAS-II) is a lightweight, high-resolution (0.0003 cm-1), scanning, mid-infrared absorption spectrometer based on cooled (80 K) lead-salt tunable diode laser sources.
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A fire in a spacecraft poses detrimental consequences and risks mission success in addition to crew safety. This is compounded during long-duration missions when the crew has limited options to recover from a fire. A common spacecraft fire concern is the smoldering of wire insulation, typically made from Polyvinyl chloride (PVC) or Polytetrafluoroethylene (PTFE). This creates acid gases such as Hydrogen Chloride (HCl), Hydrogen Fluoride (HF) and Hydrogen Cyanide (HCN). These poisonous gases are hazardous to the crew. They also interact with common surfaces within the spacecraft more than dominant combustion products such as CO2 and H2O. This makes them more difficult to track for potential fire detection techniques, or for postfire clean-up. It is imperative to be able to understand and predict the fate of these poisonous species in a microgravity environment in order to design a safe vehicle. HCl interacts with a number of materials inside a spacecraft. Primary among these materials is aluminum, which is abundantly used due to its strong and light weight nature. Aluminum has a natural oxide layer that protects it from corrosion but is typically treated to enhance this oxide layer. Among these treatments is a chromate conversion coating (CCC), which provides a thin enough protective oxide layer to still conduct electricity, and a traditional anodized material that has a thicker oxide layer that does not conduct electricity. Nomex is another common material found inside a spacecraft. It is a flame-resistant woven polymer that is related to nylon. This commercially available material is used for cargo storage bags and as a fire barrier. Physics-based models were developed to predict the uptake of HCl by these materials. The ultimate objective of these models is to predict the fate of HCl within the spacecraft so that sensors can be placed in meaningful locations in future missions based on the model predictions. To support these modeling efforts, experiments were performed in a cast acrylic test cell that measured the difference between the inlet and outlet concentration of HCl after inserting a sample rod of the test material. Different uptake capacities were realized for each type of sample tested. A computational fluid dynamics model (CFD) model of the reactor was then constructed that used a one-step global reaction rate with calibratable reaction (or kinetic) constants. These constants were calibrated to match the HCl uptake on the CCC aluminum samples, and the same kinetic constants were then tested for the stock and anodized aluminum samples. Model predictions matched the experimental data for the stock aluminum, and to a much lesser extent, the anodized aluminum. The model was additionally validated at different flow rates, sample surface areas, and inlet concentrations, and showed good agreement for all stock and CCC samples. The model did not accurately predict the HCl uptake in the anodized samples compared to the other two types of aluminum. Adjusting the kinetic constants and transport properties did little to improve the prediction. X-Ray Photoelectron Spectroscopy (XPS) was used to determine that the oxide layer thickness of anodized aluminum is approximately 5,000 nm, compared to 250 nm for CCC and 50 nm for stock. XPS also revealed presence of chlorine further down in the aluminum oxide layer in anodized samples than CCC and stock samples after the samples were saturated with HCl, indicating that accounting for diffusion of HCl into the oxide layer is important for accurate prediction of HCl uptake onto anodized aluminum. Consequently, a multi-scale model was developed and tested. First, a single pore inside the anodized aluminum oxide layer was modeled and is referred to as the pore-scale model. In this model, HCl diffused through the pore and reacted with the aluminum oxide pore wall to create aluminum chloride. The sample was then saturated when the mass transfer resistance through the growing aluminum chloride layer became too large for the HCl to reach the aluminum oxide wall and continue the reaction. This pore-scale model was coupled to the reactor-scale model using a concentration-dependent diffusion coefficient, resulting in much more accurate predictions (approximately half the sum square error of the aforementioned reactor-scale model that produced good agreement for stock and CCC) for a variety of operating conditions. The amount of water vapor or relative humidity (RH) in the flow during a reactor experiment was determined to influence HCl uptake. Experiments were performed to understand the interaction of gaseous HCl with aluminum surfaces in the presence of water vapor. The results show that increasing levels of RH increased the capacity of aluminum to adsorb HCl but decreased the capacity of Nomex to uptake HCl. A series of tests were performed on individual aluminum samples after they had been saturated with a fixed concentration of HCl in dry air conditions with the goal of determining how their HCl uptake capacity changes after various treatments with water relative to the original saturation tests. HCl-saturated aluminum samples subjected to a second dry air flow at the same HCl concentration as the original test had an uptake of 23.5% of the original sample with no treatment in between. Saturated aluminum samples subjected to an air flow with a RH of 90% in between tests had an uptake of 35.6% of the original. Saturated aluminum samples submerged in distilled water for 12 hours in between tests had an uptake of 82.2% of the original sample. Previously saturated aluminum tested with HCl and a 50% RH air flow resulted in similar uptake characteristics in multiple repeated tests. The experiments show the profound effect water vapor has on HCl uptake onto aluminum surfaces. In the samples subjected to water vapor or liquid water, capillary condensation and capillary diffusion alters the transport of HCl significantly. A model was proposed that developed a relationship between RH and the coefficient of HCl diffusion in aluminum chloride. This produced an “S-shaped” curve with diffusion coefficient as a function of RH, with 45% RH represented as the point where the diffusion coefficient is halfway between no water saturation and 100% water saturation in the aluminum chloride product layer. No difference in uptake characteristics for the experiment or model were realized between 50% and 62% RH. The results from the large-scale microgravity experiment, Saffire, are discussed as they pertain to the fate of HCl throughout a spacecraft. HCl was released, both as a standalone event, and in concurrence with the burning of a structured cloth. These events only produced a small response in the far field HCl sensor, while a PMMA burn that did not produce HCl had a significantly greater response. A ground-based large-scale facility was constructed to flow acid gas at the scale and configuration realized in the Saffire experiments. A CFD model of this duct was constructed to test kinetic parameters developed in this work at a larger scale and different geometric configuration and to predict the results of the large-scale facility. The models developed in this work were used to interpret the results of the microgravity tests and lead the discussion on what further experiments and models are needed in order to predict the fate of acid gas in a spacecraft environment. To summarize, the major contributions of this work are as follows: the capacity to uptake HCl, with and without the presence of water vapor, was measured for a variety of real spacecraft surfaces. Several different models (single reactor-scale, multiscale, spacecraft-scale) were developed and with the aid of modeling, the rate of uptake for those surfaces was also predicted and validated. The kinetic parameters determined from the small-scale reactor experiments and models were used to predict large-scale and microgravity tests. Conclusions from this research will be used in the design of spacecraft vehicles and large-scale microgravity fire safety experiments. The models built by this work will aid designers in sensor placement and could be used to predict acid gas transport from fires in partial gravity, as would be seen in Lunar and Martian habitats.