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At least 361 records · Page 20

Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates

CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercritical fluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.

White, Gary L.↗

The Distribution of Hydrogen, Nitrogen, and Chlorine Radicals in the Lower Stratosphere: Implications for Changes in O3 due to Emission of NO(y) from Supersonic Aircraft

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for [OH] and [HO2] are reduced if we allow for higher yields of O(sup 1)D) from 03 photolysis and for heterogeneous production of HNO2. The data suggest more efficient catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [O3] in the lower stratosphere may be larger in response to inputs of NO(sub y) from supersonic aircraft than estimated by current assessment models.

Salawitch, R. J.↗

Vertical ozone profile comparisons between ozonesondes and remote instrumentation

The ozone profiles measured with the halogen occultation experiment (HALOE) instrument and the microwave limb sounder (MLS) instrument, on NASA's upper atmosphere research satellite (UARS), are compared to those obtained with the electrochemical concentration cell (ECC) ozone sonde. The process used to assure the quality of the ozone sonde measurements, the comparisons between the ozone sonde and other measuring instruments, and the reliability of measurements in space are discussed.

Schmidlin, F. J.↗

HALOE Science Investigation

This cooperative agreement has investigated a number of spectroscopic problems of interest to the Halogen Occultation Experiment (HALOE). The types of studies performed are in two parts, namely, those that involve the testing and characterization of correlation spectrometers and those that provide basic molecular spectroscopic information. In addition, some solar studies were performed with the calibration data returned by HALOE from orbit. In order to accomplish this a software package was written as part of this cooperative agreement. The HALOE spectroscopic instrument package was used in various tests of the HALOE flight instrument. These included the spectral response test, the early stages of the gas response test and various spectral response tests of the detectors and optical elements of the instruments. Considerable effort was also expended upon the proper laboratory setup for many of the prelaunch tests of the HALOE flight instrument, including the spectral response test and the gas response test. These tests provided the calibration and the assurance that the calibration was performed correctly.

Benner, D. Chris↗

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCl, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approx.17-47 km) altitude range and over 10 degree latitude bins from 70degS to 70degN. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) 11 data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NO(y)) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NO(y) correlation, and (3) from the CH4-NO(y) correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NO(x)/NO(y) ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approx. 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45degS and 45degN are also presented. Our analysis indicates that ground-based and HALOE v. 18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45degS suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Danilin, M. Y.↗

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCI, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approximately 17-47 km) altitude range and over 10 degree latitude bins from 70 deg S to 70 deg N. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOy) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and CIONO2; (2) from the N2O-NOy correlation, (3) from the CH4-NOy correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NOx/NOy ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approximately 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45 deg S and 45 deg N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 deg S suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Danilin, M. Y.↗

Chlorine Deactivation in the Lower Stratospheric Polar Regions during late Winter: Results from UARS

Recovery from enhanced chlorine conditions in the lower stratospheric polar regions of both hemispheres is investigated using data from the Upper Atmosphere Research Satellite (UARS). Microwave Limb Sounder (MLS) measurements of ClO within the polar vortices are used to infer ClO(sub x) (ClO + 2Cl202) abundances that are then correlated with simultaneous Cryogenic Limb Array Etalon Spectrometer (CLAES) measurements of ClON02 and Halogen Occultation Experiment (HALOE) measurements of HCl obtained starting within 5 days of the end of the MLS and CLAES high-latitude observing periods in each hemisphere. Time series of vortex-averaged mixing ratios are calculated on two potential temperature surfaces (585 K and 465 K) in the lower stratosphere for approximately month-long intervals during late winter: August 17 - September 17, 1992, in the southern hemisphere and February 12 - March 16, 1993, in the northern hemisphere. The observed mixing ratios are adjusted for the effects of vertical transport using diabatic vertical velocities estimated from CLAES tracer data. In the northern hemisphere, the decrease in ClO, is balanced on both surfaces by an increase in ClON02- In the southern hemisphere, continuing polar stratospheric cloud activity prevents ClO from undergoing sustained decline until about September 3. In contrast to the northern hemisphere, there is no significant chemical change in vortex-averaged ClON02 at 465 K, and there is an apparent decrease in ClON02 at 585 K, even after the enhanced ClO abundances have started to recede. Results from the SLIMCAT chemical transport model initialized with UARS data and run with OH + ClO yields HCl + 02 as an 8% channel suggest that the primary recovery product in the south during this time period is not ClON02, but HCl. HALOE HCl mixing ratios are extrapolated back to the time of the MLS and CLAES data. At 585 K, the chlorine budget can be made to balance by extrapolating HCl back to a value of 0.6 parts per billion by volume (ppbv) at the beginning of the study period; at 465 K, the contribution from extrapolated HCl is not sufficient to offset the loss in ClOx, and there is a slight imbalance between the decrease in reactive chlorine and the change in chlorine reservoirs. The difficulty in closing the chlorine budget in the southern hemisphere may arise from complications caused by ongoing activation, incomplete photochemical assumptions, and/or inadequate data quality.

Santee, M. L.↗

New Materials for EMI Shielding

Graphite fibers intercalated with bromine or similar mixed halogen compounds have substantially lower resistivity than their pristine counterparts, and thus should exhibit higher shielding effectiveness against electromagnetic interference. The mechanical and thermal properties are nearly unaffected, and the shielding of high energy x-rays and gamma rays is substantially increased. Characterization of the resistivity of the composite materials is subtle, but it is clear that the composite resistivity is substantially lowered. Shielding effectiveness calculations utilizing a simple rule of mixtures model yields results that are consistent with available data on these materials.

Gaier, James R.↗

A Study of Flame Propagation on Water-Mist Laden Gas Mixtures in Microgravity

The use of water mists (very fine water sprays) for fire suppression is currently receiving increased attention as a replacement technology for halogen-based chemical agents-such as Halon 1301 (CF3Br)--the manufacturing of which has been banned by the Montreal Protocol due to their high ozone depletion potential. Water mist technology has been found effective for a wide range of applications such as Class B pool fires, shipboard machinery, aircraft cabins, computers, and electronic equipment. There are five distinct mechanisms by which water droplets may interact with a flame. First, the high enthalpy of vaporization of water (2450 kJ/kg) leads to heat removal from the flame front as the liquid droplets turn to steam. Second, as water vaporizes its volume increases approximately three orders of magnitude, which leads to the dilution of the oxygen and vaporized fuel required to maintain the flame. The third effect is the recombination of H-atoms and other radicals on the droplet surface. A fourth effect of water mists in fires is the retardation of surface propagation rates due to the wetting of walls and surfaces. The last potential impact of fine water mists affects the radiative propagation of the fire by forming an optically thick barrier to infrared radiation which prevents ignition of the unburned regions. Unfortunately, little fundamental information exists on the interaction of a flame with a water mist. To date, there is no widely accepted interpretation of the critical concentration of droplets required to suppress a flame or of the fundamental mechanisms involved in flame extinguishment by water mists. One of the main obstacles to obtaining such understanding is the difficulty of providing a simple, well-defined experimental setup for the flame front/water mist interaction. Some of the difficulty stems from the problem of generating, distributing and maintaining a homogeneous concentration of droplets throughout a chamber while gravity depletes the concentration and alters the droplet size by coalescence and agglomeration mechanisms. Experiments conducted in the absence of gravity provide an ideal environment to study the interaction of water mists and flames by eliminating these distorting effects. In addition, microgravity eliminates the complex flow patterns induced between the flame front and the water droplets. The long duration and quality of microgravity in space flights provide the required conditions to perform the setup and monitoring of flame suppression experiments. Consequently, a series of experiments have been identified to be performed on the Combustion Module (CM-2) in the Space Shuttle. These consist of measuring the extinguishing capability of a water mist on a premixed flame propagating along a tube. These experiments should provide the necessary data to obtain further understanding of the water mist suppression phenomena that can be later used to design and manufacture appropriate fire suppression systems. In preparation for the orbital flights, experiments have been conducted on low-gravity ground facilities to obtain the preliminary data necessary to define the scientific objectives and technical issues of the spacecraft experiments.

Abbud-Madrid, A.↗

Stratospheric Assimilation of Chemical Tracer Observations Using a Kalman Filter: Chi-Square Validated Results and Analysis of Variance and Correlation Dynamics - Pt. 2

A Kalman filter system designed for the assimilation of limb-sounding observations of stratospheric chemical tracers, which has four tunable covariance parameters, was developed in Part I (Menard et al. 1998) The assimilation results of CH4 observations from the Cryogenic Limb Array Etalon Sounder instrument (CLAES) and the Halogen Observation Experiment instrument (HALOE) on board of the Upper Atmosphere Research Satellite are described in this paper. A robust (chi)(sup 2) criterion, which provides a statistical validation of the forecast and observational error covariances, was used to estimate the tunable variance parameters of the system. In particular, an estimate of the model error variance was obtained. The effect of model error on the forecast error variance became critical after only three days of assimilation of CLAES observations, although it took 14 days of forecast to double the initial error variance. We further found that the model error due to numerical discretization as arising in the standard Kalman filter algorithm, is comparable in size to the physical model error due to wind and transport modeling errors together. Separate assimilations of CLAES and HALOE observations were compared to validate the state estimate away from the observed locations. A wave-breaking event that took place several thousands of kilometers away from the HALOE observation locations was well captured by the Kalman filter due to highly anisotropic forecast error correlations. The forecast error correlation in the assimilation of the CLAES observations was found to have a structure similar to that in pure forecast mode except for smaller length scales. Finally, we have conducted an analysis of the variance and correlation dynamics to determine their relative importance in chemical tracer assimilation problems. Results show that the optimality of a tracer assimilation system depends, for the most part, on having flow-dependent error correlation rather than on evolving the error variance.

Menard, Richard↗

The Upper Atmosphere Research Satellite: From Coffee Table Art to Quantitative Science

The Upper Atmosphere Research Satellite (UARS) has provided an unprecedented set of observations of constituents of the stratosphere. When used in combination with data from other sources and appropriate modeling tools, these observations are useful for quantitative evaluation of stratospheric photochemical processes. This is illustrated by comparing ozone observations from airborne Differential Absorption Lidar (DIAL), from the Polar Ozone and Aerosol Measurement (POAM), from the Microwave Limb Sounder (MLS), and from the Halogen occultation Experiment (HALOE) with ozone fields generated with a three dimensional model. For 1995-96, at polar latitudes, observations from DIAL flights on December 9 and January 30, and POAM and MLS between late December and late January are compared with ozone fields from the GSFC 3D chemistry and transport model. Data from the three platforms consistently show that the observed ozone has a negative trend relative to the modeled ozone, and that the trend is uniform in time between early and mid winter, with no obvious dependence on proximity to the vortex edge. The importance of chlorine catalyzed photochemistry to this ozone loss is explored by comparing observations from MLS and HALOE with simulations for other northern winters, particularly 1997-98.

Douglass, Anne R.↗

Seasonal Variability of Middle Latitude Ozone in the Lowermost Stratosphere Derived from Probability Distribution Functions

We present a study of the distribution of ozone in the lowermost stratosphere with the goal of understanding the relative contribution to the observations of air of either distinctly tropospheric or stratospheric origin. The air in the lowermost stratosphere is divided into two population groups based on Ertel's potential vorticity at 300 hPa. High [low] potential vorticity at 300 hPa suggests that the tropopause is low [high], and the identification of the two groups helps to account for dynamic variability. Conditional probability distribution functions are used to define the statistics of the mix from both observations and model simulations. Two data sources are chosen. First, several years of ozonesonde observations are used to exploit the high vertical resolution. Second, observations made by the Halogen Occultation Experiment [HALOE] on the Upper Atmosphere Research Satellite [UARS] are used to understand the impact on the results of the spatial limitations of the ozonesonde network. The conditional probability distribution functions are calculated at a series of potential temperature surfaces spanning the domain from the midlatitude tropopause to surfaces higher than the mean tropical tropopause [about 380K]. Despite the differences in spatial and temporal sampling, the probability distribution functions are similar for the two data sources. Comparisons with the model demonstrate that the model maintains a mix of air in the lowermost stratosphere similar to the observations. The model also simulates a realistic annual cycle. By using the model, possible mechanisms for the maintenance of mix of air in the lowermost stratosphere are revealed. The relevance of the results to the assessment of the environmental impact of aircraft effluence is discussed.

Cerniglia, M. C.↗

A Composite View of Lower Stratospheric Ozone Developed Using a Chemistry Transport Model and Observations from Airborne Lidar and Satellite

An ozone simulation from the Goddard three-dimensional chemistry and transport model for the 1995-96 northern hemisphere winter is compared with ozone observations from airborne Differential Absorption Lidar (DIAL), from the Polar Ozone and Aerosol Measurement (POAM), from the Microwave Limb Sounder (MLS), and from the Halogen Occultation Experiment (HALOE). The 3D model uses winds from the Goddard Data Assimilation System. The 3D model reproduces the latitude dependence of the horizontal and vertical ozone gradients of the subtropical DIAL observations. Comparisons with subtropical satellite observations, which lack the spatial resolution of DIAL but provide near continuous coverage throughout the subtropics, show that the model also reproduces longitude and temporal dependence in the tropical-midlatitude boundary. At polar latitudes, observations from DIAL flights on December 9 and January 30, and POAM and MLS between late December and late January are compared with the 3D model. Data from the three platforms consistently show that the observed ozone has a negative trend relative to the modeled ozone, and that the trend is uniform in time between early and mid winter, with no obvious dependence on proximity to the vortex edge.

Douglass, A. R.↗

The Influence of Extremely Large Solar Proton Events in a Changing Stratosphere. Stratospheric Influence of Solar Proton Events

Two periods of extremely large solar proton events (SPEs) occurred in the past thirty years, which forced significant long-term polar stratospheric changes. The August 2-10, 1972 and October 19-27, 1989 SPEs happened in stratospheres that were quite different chemically. The stratospheric chlorine levels were relatively small in 1972 (approximately 1.2 ppbv) and were fairly substantial in 1989 at about (approximately 3 ppbv). Although these SPEs produced both HO(x) and NO(y) constituents in the mesosphere and stratosphere, only the NO(y) constituents had lifetimes long enough to affect ozone for several months to years past the events. Our recently improved two-dimensional chemistry and transport atmospheric model was used to compute the effects of these gigantic SPEs in a changing stratosphere. Significant upper stratospheric ozone depletions > 10% are computed to last for a few months past these SPEs. The long-lived SPE-produced NO(y) constituents were transported to lower levels during winter after these huge SPEs and caused impacts in the middle and lower stratosphere. During periods of high halogen loading these impacts resulted in interference with the chlorine and bromine loss cycles for ozone destruction. The chemical state of the atmosphere, including the stratospheric sulfate aerosol density, substantially affected the predicted stratospheric influence of these extremely large SPEs.

Jackman, Charles H.↗

Seasonal Variability of Middle Latitude Ozone in the Lowermost Stratosphere Derived from Probability Distribution Functions

We present a study of the distribution of ozone in the lowermost stratosphere with the goal of characterizing the observed variability. The air in the lowermost stratosphere is divided into two population groups based on Ertel's potential vorticity at 300 hPa. High (low) potential vorticity at 300 hPa indicates that the tropopause is low (high), and the identification of these two groups is made to account for the dynamic variability. Conditional probability distribution functions are used to define the statistics of the ozone distribution from both observations and a three-dimensional model simulation using winds from the Goddard Earth Observing System Data Assimilation System for transport. Ozone data sets include ozonesonde observations from northern midlatitude stations (1991-96) and midlatitude observations made by the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) (1994- 1998). The conditional probability distribution functions are calculated at a series of potential temperature surfaces spanning the domain from the midlatitude tropopause to surfaces higher than the mean tropical tropopause (approximately 380K). The probability distribution functions are similar for the two data sources, despite differences in horizontal and vertical resolution and spatial and temporal sampling. Comparisons with the model demonstrate that the model maintains a mix of air in the lowermost stratosphere similar to the observations. The model also simulates a realistic annual cycle. Results show that during summer, much of the observed variability is explained by the height of the tropopause. During the winter and spring, when the tropopause fluctuations are larger, less of the variability is explained by tropopause height. This suggests that more mixing occurs during these seasons. During all seasons, there is a transition zone near the tropopause that contains air characteristic of both the troposphere and the stratosphere. The relevance of the results to the assessment of the environmental impact of aircraft effluence is also discussed.

Rood, Richard B.↗

Reactivities of Precision Cleaning Solvents with Hypergolic Propellants

The reactivities of several selected halogenated precision cleaning solvents with hypergolic propellants has been determined by analysis of the rates of formation of halide ion decomposition products. The solvents were Asahiklin AK 225, Asahiklin AK 225 AES, HFE 7100, HFE 7100 DE, Vertrel XF, Vertrel MCA, Vertrel MCA Plus, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), and trans-1,2-dichloroethylene (DCE). The propellants were hydrazine (HZ), monomethylhydrazine (MMH), and mixed oxides of nitrogen (MON-3). The Vertrel solvents showed significant reactivity with HZ. All of the solvents except DCE exhibited significant reactivity with MMH, particularly HFE 7100 DE and CFC-113. HFE 7100 DE, Vertrel MCA, and Vertrel MCA Plus also showed significant reactivity with MON-3 oxidizer.

Davis, Dennis D.↗

The GEOS Ozone Data Assimilation System: Design and Validation

An ozone data assimilation system has been developed at the Data Assimilation Office of the NASA/Goddard Space Flight Center to provide global three-dimensional analyzed ozone mixing ratio and total column ozone. The Total Ozone Mapping Spectrometer (TOMS) total column ozone and the Solar Backscatter Ultraviolet (SBUV) or SBUV/2 partial ozone profile data are assimilated. The analyzed winds from the Goddard Earth Observing System Data Assimilation System (GEOS-DAS) drive the ozone transport. Following every transport model timestep, the model prediction is combined with the observations using a global, physical-space based, statistical analysis scheme. Due to the smaller size of the ozone system than that of a global meteorological data assimilation system, new statistical analysis methodology, including anisotropic and flow-dependent forecast error correlation models, can be implemented and tested in the ozone system more easily. Sample results from the winter 1992 validation period are presented. There is a close agreement between the analyzed fields and the independent observations from ozone sondes and the Halogen Occultation Experiment (HALOE).

Stajner, I.↗

Phenol Analysis -- Some Analytical Considerations

Contamination of potable water supplies with halogenated phenols in concentrations of 2-10 parts per billion (ppb) produces objectionable tastes and odors capable of influencing consumer acceptability. Routine analysis by the distillation/ 4-aminoantipyrine method is limited by lack of sensitivity and subject to interference by aryl amines. This has been overcome by developing a continuous liquid-liquid extraction system to selectively isolate phenols and eliminate major interfering substances. Stable reagents have been formulated to reduce blank color and extend sensitivity. Equipment suitable for analysis of phenols at the 1 ppb level or less in 20 minutes is described.

Starkey, R. J., Jr.↗