Regolith Inhibits Salt and Ice Crystallization in Mg(ClO 4 ) 2 Brine, Implying More Persistent and Potentially Habitable Brines on Mars
Explore the source record for details and available documents.
Andrew O. Shumway↗
SEARCH · Engineering Papers
Results for “I(ClO)4”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Chlorine chemistry on polar stratospheric cloud particles in the Arctic winter
Simultaneous in situ measurements of hydrochloric acid (HCl) and chlorine monoxide (ClO) in the Arctic winter vortex showed large HCl losses of up to 1 ppbv, which were correlated with high ClO levels of up to 1.4 ppbv. Air parcel trajectory analysis identified that this conversion of inorganic chlorine occurred at air temperatures of less than 196 -/+ 4 kelvin. High ClO was always accompanied by loss of HCl mixing ratios equal to 1/2(ClO+ 2Cl2O2). These data indicate that the heterogeneous reaction HCl + ClONO2 - Cl2 + HNO3 on particles of polar stratospheric clouds establishes the chlorine partitioning, which, contrary to earlier notions, begins with an excess of ClONO2, not HCl.
Webster, C. R.↗
Is there any chlorine monoxide in the stratosphere?
A ground based search for the 856.50137/cm R(9.5) and for the 859.76765 R(12.5) transitions of stratospheric (Cl-35)O was made in the solar absorption mode using an infrared heterodyne spectrometer. Lines due to stratospheric HNO3 and tropospheric OCS were detected, at about 0.3% absorption levels. The expected lines of ClO in this same region were not detected, even though the optical depth of the ClO lines should be on the order of 0.2% using currently accepted ClO abundances. These infrared measurements suggest that stratospheric ClO is at least a factor of 7 less abundant than is indicated by indirect in situ fluorescence measurements, and the upper limit of 2.4x10 to the 13th power molecules/sq cm to the integrated column density of ClO is a factor of over 4 less than is indicted by microwave measurements. Results imply that the release of fluorocarbon precursors of ClO may be significantly less important for the destruction of stratospheric ozone than was previously thought.
Rogers, J. D.↗
A new high-sensitivity superconducting receiver for mm-wave remote-sensing spectroscopy of the stratosphere
We describe a recently constructed ground-based mm-wave spectrometer incorporating a superconducting tunnel junction as a heterodyne mixer-receiver. Under conditions of low tropospheric water vapor, the superior sensitivity of this receiver allows spectral line measurements of stratospheric molecules with mixing ratios as small as a few tenths of a part per billion (e.g., ClO, HCN) to be made in 4 to 6 hours, with a signal to noise ratio of at least 30:1. We expect to be able to halve this time by further improvement of the mixer's intrinsic noise level.
Dezafra, R. L.↗
Spectroscopy of Chlorosyl Fluoride, FClO
FClO has been proposed as an intermediate in reactions involving ClF, Cl2O, and ClF3O, and it has been suggested as a molecule of atmospheric interest. It has been prepared in situ by the hydrolysis of ClF3. The pure rotational spectrum of FClO has been studied by conventional millimeter wave techniques and by microwave Fourier transform spectroscopy. Selected transitions were searched for using predictions based on an analysis of the nu(sub 1) band. FClO is an asymmetric prolate top, kappa = -0.8950 for F(35)ClO, with a rather small dipole component of 0.093 (4) D along the a-axis and a larger one of 1.93 (5) D along the b-axis. Transitions with 0 <= J <= 54 and 0 <= K(sub a) <= 18 were observed. Cl hyperfine splitting was generally observable throughout the spectrum with F-19 spin-rotation splitting observable as well in the microwave region. Structural parameters, harmonic force constants, and nuclear magnetic shielding parameters were derived and will be compared with data of related molecules, such as ClF3, ClF, FClO2, and FClO3. High resolution infrared spectra were taken in the regions of the FCl stretching mode and bending mode around 600 and 310/cm, respectively. A preliminary analysis indicates that the FCl stretch, near 596.86/cm for F(35)ClO, is in resonance with the dark overtone of delta near 617/cm. A brief progress report will be given.
Mueller, Holger S. P.↗
Long extension reeling in the stratosphere - A progress report
Results of the second flight of the Harvard Reel Down balloon-born winching system, in which a more complex photochemical detection package was twice lowered from a float altitude of 39 km and reeled back to the winch, are reported. Modifications over the original package design include improvements to the winch platform and reconstruction of the suspended detection package for specific ClO measurement and for tight weight control. Controlled velocities of 4-7 m/sec were implemented for both of the scans, and the package was brought to a brief stop during the first scan to evaluate dynamic effects. The results demonstrate the operational effectiveness of the system.
Hazen, N.↗
Measurements of nitric oxide and total reactive nitrogen in the Antarctic stratosphere - Observations and chemical implications
Results are presented on measurements of NO and the sum of reactive nitrogen species, NO(y), which include NO, NO2, NO3, N2O5, HNO3, and ClONO2 (in addition to ClO, O3, H2O, and N2O measurements), obtained aboard the NASA ER-2 aircraft flying over the Antarctica between the latitudes of 53 and 72 deg S during the Airborne Antarctic Ozone Experiment. The boundary of the chemically perturbed region (CPR), as indicated by a sharp increase in the level of ClO, occurred near 66 deg S; outside or equatorward of the CPR, the NO(y) mixing ratios ranged between 6 and 12 ppbv, with values decreasing poleward and reaching total NO(y) levels of 4 ppbv or less within 5-deg poleward of the boundary. Data presented in this paper clearly associate the Antarctic ozone decrease with perturbed conditions of ClO, NO(y), and H2O, which are in turn associated with processes defined as nonstandard heterogeneous chemistry, denitrification, and dehydration, respectively.
Fahey, D. W.↗
Venus lower thermosphere studies
Studies undertaken in this project have sought to understand lower thermospheric structure and dynamics (less than or equal to 145 km), particularly the processes responsible. This is a region just below the reach of in-situ instruments onboard PVO (Pioneer Venus Orbiter) during the first few diurnal cycles. PVO remote airglow observations (nitric oxide, O2, visible, O 1304A) have been coupled with ground-based observations (CO densities, winds, temperatures, O2 IR nightglow) to address the behavior of lower thermospheric winds and chemistry over 95 to 150 km. This interpretation of PVO and related data is accomplished by using the NCAR Venus thermospheric general circulation model (VTGCM) (Bougher et al., 1988; 1990). This model has been modified over the last two years to improve its ability to calculate O, CO, and O2 densities, temperatures, nightglow, and subsolar-to-antisolar and zonal winds over 95 to 150 km (Bougher and Borucki, 1992). Our VTGCM studies show that: (1) O2 visible and IR nightglow distributions can be used to trace lower thermosphere / upper mesosphere winds over 100-130 km. Typically, weak zonal winds (less than or equal to 25 m/sec) and nightglow maximum patches near 0100 LT prevail. Occasionally, strong zonal winds (30-60 m/sec) and airglow patches peaking near 0300 LT characterize the Venus lower thermosphere. (2) It is clear that the dynamics of the Venus 90-130 km region is highly variable on time scales as short as an hour. This is most likely due to the time variable nature of upward propagating gravity waves, which grow in amplitude and eventually break. The resulting turbulence gives rise to local time variable eddy diffusion and momentum drag, both of which strongly impact global density and nightglow distributions. (3) The oxygen chemistry (O, O2, etc.) over 90-120 km is strongly dependent on HO(x) and CLO(x) tracer species that must be properly included in any coupled chemical dynamical model. (4) The density profiles of light species (O, CO, N, He) are strongly affected by large-scale transport by the winds. Strong eddy diffusion is not a suitable model parameterization for approximating these light species, especially for extrapolation into the region below 140 km where PVO in-situ data is lacking. Instead, the fully coupled chemical dynamical VTGCM model should be used to improve estimates of densities within the VTS3 empirical model (Hedin et al., 1983) below 140 km.
Bougher, Stephen W.↗
Stratospheric ClO profiles from McMurdo Station, Antarctica, spring 1992
We describe ground-based measurements of ClO made at McMurdo Station, Antarctica, during September and October 1992. Vertical profiles were retrieved from molecular rotational emission spectra at 278 GHz. Peak mixing ratios of 1.6 +/- 0.3 ppbv were seen in mid-September at approximately 18 km altitude, suggestive of somewhat larger quantities than were measured at the same site and season in 1987. As the core of the polar vortex moved away from McMurdo by early October, the ClO mixing ratio at this altitude dropped to less than 0.2 ppbv, coincident with increasing temperature, ozone, and NO2. The diurnal variation of ClO was also observed. The lower stratospheric layer from 15 to 27 km was found to reach approximately midday abundance by 2 - 3 hours after sunrise. The column abundance in this layer began to decrease by the period 4 - 2 hours before sunset and had declined to approximately one quarter of its midday value by 2 - 0 hours before sunset. In contrast, the ClO column in the upper stratosphere, from 28 to 50 km, built up slowly until midday and remained large while sunlight persisted.
Emmons, L. K.↗
High-Altitude Aircraft and Balloon-Borne Observations of OH, HO2, ClO, BrO, NO2, ClONO2, ClOOCl, H2O, and O3 in Earth's Stratosphere
Using observations from balloon-borne instruments and aircraft-borne instruments the investigation arrived at the following developments.: (1) Determination of the dominant catalytic cycles that destroy ozone in the lower stratosphere; (2) The partial derivatives of the rate limiting steps are observables in the lower stratosphere; (3) Recognition that the "Low NOx" condition is the regime that holds the greatest potential for misjudgement of Ozone loss rates; (4) Mapping of the Bromine radical contribution to the ozone destruction rate in the lower stratosphere; (5) Observation of OH, HO2 and ClO in the plume of the Concorde SST in the stratosphere; (6) Determination of the diurnal behavior of OH in the lower stratosphere; (7) Observed OH and H02 in the Troposphere and the interrelationship between Ozone and OH, HO2, CO and NO; (8) Analysis of the Catalytic Production of Ozone and Reactions that Couple OH and H02 in the Troposphere; (9) The continuing development of the understanding of the Tropopause temperatures, water vapor mixing ratios, and vertical advection and the mixing in of mid-latitude air; (10) Performed Multiple Tracer Analyses as a diagnostic of water vapor intrusion into the "Middle World" (i.e., the lowermost stratsophere); (11) Flight testing of a new instrument for the In Situ detection of ClON02 from the ER-2; (12) Laser induced fluorescence detection of NO2. There is included an in depth discussion of each of these developments and observations.
Anderson, James G.↗
Induced ClO vacuum ultraviolet fluorescence
Some vibronic transitions of ClO such as G(v-prime = 11 )-X(v-double prime = 10), G(v-prime = 5)-X(v-double prime = 3) and H(v-prime = 4)-X(v-double prime = 2), which promote overtones of X(2pi3/2) to bound Rydberg states, are nearly resonant with the 130.6 nm O-atom emission line and possess sizable Franck-Condon factors. On this basis broadband detection of 'O atom' fluorescence in experiments involving vibrationally excited ClO(X) is ascribed to the radiative decay of ClO(G, H) rather than to the formation of O atoms; these observations raise the probability of monitoring ClO(X; v = 0) by VUV-induced fluorescence.
Colussi, A. J.↗
Impact of January 2005 Solar Proton Events on Chlorine Species
Sudden changes in stratospheric chlorine species in the polar northern atmosphere, caused by the Solar Proton Events (SPEs) of 17 and 20 January 2005, have been investigated and compared with version 4 of the Whole Atmosphere Community Climate Model (WACCM4). We used Aura Microwave Limb Sounder (MLS) measurements to monitor the variability of ClO, HCl, HOCl and Michelson Interferometer for Passive Atmospheric Sounder (MIPAS) on ENVISAT to retrieve ClONO2. SPE-induced chlorine activation has been identified. HCl decrease occurred at nearly all the investigated altitudes with the lowest values (of less than 0.25 ppbv) on 21 January. HOCl was found to be the main active chlorine species under nighttime conditions (with increases of more than 0.2 ppbv) whereas both HOCL and CLO enhancements (about 0.1 ppbv) have been observed at the polar night terminator. Further, small ClO decreases (of less than 0.1 ppbv) and ClONO2 enhancements (~0.2 ppbv) have been observed at higher latitudes (i.e., at nighttime) roughly above 2hPa. While WACCM4 reproduces most of the SPE-induced variability in the chlorine species fairly well, in some particular regions discrepancies between the modeled and measured temporal evolution of the abundances of chlorine species were found. HOCl changes are modelled very well with respect to both magnitude and geographic distribution. ClO decreases are reproduced at high latitudes, whereas ClO enhancements in the terminator region are underestimated and attributed to background variations. WACCM4 also reproduces the HCl depletion in the mesosphere but it does not show the observed decrease below about 2 hPa. Finally, WACCM4 simulations indicate that the observed ClONO2 increase is dominated by background variability, although SPE-induced production might contribute by 0.1 ppbv.
Damiani, A.↗
Impact of January 2005 Solar Proton Events on Chlorine Species
Sudden changes in stratospheric chlorine species in the polar northern atmosphere, caused by the Solar Proton Events (SPEs) of 17 and 20 January 2005, have been investigated and compared with version 4 of the Whole Atmosphere Community Climate Model (WACCM4). We used Aura Microwave Limb Sounder (MLS) measurements to monitor the variability of ClO, HCl, HOCl and Michelson Interferometer for Passive Atmospheric Sounder (MIPAS) on ENVISAT to retrieve ClONO2. SPE-induced chlorine activation has been identified. HCl decrease occurred at nearly all the investigated altitudes (i.e., 10-0.5 hPa) with the strongest decrease (of about 0.25 ppbv) on 21 January. HOCl was found to be the main active chlorine species under nighttime conditions (with increases of more than 0.2 ppbv) whereas both HOCl and ClO enhancements (about 0.1 ppbv) have been observed at the polar night terminator. Further, small ClO decreases (of less than 0.1 ppbv) and ClONO2 enhancements (about 0.2 ppbv) have been observed at higher latitudes (i.e., at nighttime) roughly above 2 hPa. While WACCM4 reproduces most of the SPE-induced variability in the chlorine species fairly well, in some particular regions discrepancies between the modeled and measured temporal evolution of the abundances of chlorine species were found. HOCl changes are modelled very well with respect to both magnitude and geographic distribution. ClO decreases are reproduced at high latitudes, whereas ClO enhancements in the terminator region are underestimated and attributed to background variations. WACCM4 also reproduces the HCl depletion in the mesosphere but it does not show the observed decrease below about 2 hPa. Finally, WACCM4 simulations indicate that the observed ClONO2 increase is dominated by background variability, although SPE-induced production might contribute by 0.1 ppbv.
Damiani, A.↗
Indicators of transport and vertical motion from correlations between in situ measurements in the Airborne Antarctic Ozone Experiment
Analysis of small-scale structure in the in situ measurements made from the ER-2 during the Airborne Antarctic Ozone Experiment shows the existence of a region at the boundary of the chemiclly perturbed region where the mixing ratios and small-scale structure of trace gases are influenced by transport across the boundary. This transition region is characterized by horizontal interchange and vertical layering of air parcels from within and outside of the chemically perturbed region and negative small-scale correlations between ClO and ozone. The horizontal transport in this region creates large surface areas between dissimilar air masses, providing the potential for substantial mixing. Correlations between ClO and O3 show that the transition region extends to 2-4 deg of latitude to either side of the boundary of the chemically perturbed region. A + or - 4-deg-wide transition region would contain nearly as much air as the chemically perturbed region proper. Analysis of water vapor and nitrous oxide data suggests that diabatic descent is associated with dehydration. This could be caused by strong radiative cooling of those polar stratospheric clouds in which enough water condenses for the particles to fall and dehydrate the air.
Murphy, D. M.↗
Chemistry of the CO dimer at low temperatures
Researchers conducted a series of experiments on the chlorine-catalyzed photodecomposition of O sub 3 both in the gas and in inert solvents such as CF sub 4 and CO sub 2 in the temperature range about 190 to 225 K. The liquid medium was chosen in order to minimize possible surface loss of long-lived ClO dimer, and to aid in the stabilization of transient excited intermediates. The mechanism of dimer formation was as follows: (1) Cl sub 2 + hv yields Cl + Cl; (2) Cl + O sub 3 yields ClO + O sub 2; (3) ClO + ClO yields Cl sub 2 O sub 2. The experiments were done in cooled low temperature cells, with irradiation from an Osram high pressure mercury arc, filtered to remove radiation below 325 nm. Spectral analysis was by means of a Cary Model 2200 UV spectrometer. The principal objectives were: (1) to determine the lifetime of the dimer as a function of temperature; (2) to observe spectral changes in the mixtures which could be attributed to dimer or related products; and (3) to observe chemical or photochemical reactions of the dimer.
Demore, W. B.↗
Small scale structure and mixing at the edge of the Antarctic vortex
Small scale correlations and patterns in the chemical tracers measured from the NASA ER-2 aircraft in the 1987 AAOE campaign can be used to investigate the structure of the edge of the polar vortex and the chemically perturbed region within it. Examples of several types of transport processes can be found in the data. Since ClO and O3 have similar vertical gradients and opposite horizontal gradients near the chemically perturbed region, the correlation between ClO and O3 can be used to study the extent of horizontal transport at the edge of the chemically perturbed region. Horizontal transport dominates the correlation for a latitude band up to 4 degrees on each side of the boundary. This implies a transition zone containing a substantial fraction of the mass of the total polar vortex. Similar horizontal transport can be seen in other tracers as well. It has not been possible to distinguish reversible transport from irreversible mixing. One manifestation of the horizontal transport is that the edge of the chemically perturbed region is often layered rather than a vertical curtain. This can be seen from the frequent reversed vertical gradients of NO2, caused by air with high NO2 overlapping layers with lower mixing ratios. Water and NO2 are positively correlated within the chemically perturbed region. This is the opposite sign to the correlation in the unperturbed stratosphere. The extent of the positive correlation is too great to be attributed solely to horizontal mixing. Instead, it is hypothesized that dehydration and descent are closely connected on a small scale, possibly due to radiative cooling of the clouds that also cause ice to fall to lower altitudes.
Murphy, D. M.↗
Southern Hemisphere In Situ Observations of OH, HO2, CIO and BrO from the ER-2 Aircraft for the 1994 ASHOE Mission
A summary of the first order scientific conclusions that emerged from the research done under this grant are as follows: (1) For the first time, the concentration of the key hydrogen and halogen radicals OH, H02, ClO and BrO were determined on a global scale extending from the arctic circle to the antarctic circle, over the altitude domain of the ER-2. That domain extends from 15-20 km altitude, covering a critical part of the lower stratosphere; (2) Simultaneous, in situ measurements of the concentrations of OH, H02, ClO, BrO, NO and NO2 demonstrate the predominance of odd-hydrogen and halogen free radical catalysis in determining the rate of removal of ozone in the lower stratosphere over the complete ASHOE mission. This extends to the global scale the "first look" data obtained during the NASA Stratospheric Photochemistry and Dynamics Experiment (SPADE), executed out of Ames Research Center in June 1993. This represents a major rearrangement of our understanding with respect to the hierarchy of dominant catalytic cycles controlling ozone loss in the lower stratosphere. For the past twenty years, it has been assumed that nitrogen radicals dominate the destruction rate of ozone in the lower stratosphere; (3) Throughout the altitude and latitude range covered by ASHOE, it was determined that a single catalytic cycle, HO2 + O3 yields OH + 2O2, accounted for one half of the total O3 removal in this region of the atmosphere. Halogen radical catalytic cycles were found to account for one third of the ozone loss, and nitrogen radicals were found to account for 20% of the loss; (4) Simultaneous observations of the full complement of radicals, tracers, ozone, and water vapor during ASHOE demonstrated quantitatively the coupling that exists between the rate limiting radicals and other reactive species in the photochemical reaction network. Specifically, the concentrations of ClO and HO2 are inversely correlated with the concentration of NOx. This carries the implication that the NOx effluent from the proposed High Speed Civil Transport may be less destructive to stratospheric ozone than had previously been thought. ASHOE brought this conclusion forward for the first time on a global basis; and (5) The density of BrO was measured on a global scale during ASHOE in the lower stratosphere. It was found that bromine is responsible for 55-65% of the local rate of catalytic destruction of ozone by reactions involving bromine and chlorine. Normalizing calculated loss rates to total available inorganic bromine and chlorine explicitly demonstrates that bromine is 60-80 times more efficient than chlorine in removing ozone in the lower stratosphere. An inferred value of total inorganic bromine is in excellent agreement with measurements of their source species, organic bromine compounds in the troposphere.
Anderson, James G.↗
Direct EPP Affects on the Middle Atmosphere
Energetic precipitating particles (EPPs) can cause significant direct constituent changes in the mesosphere and stratosphere (middle atmosphere) during certain periods. Both protons and electrons can influence the polar middle atmosphere through ionization and dissociation processes. EPPs can enhance HOx (H, OH, HO2) through the formation of positive ions followed by complex ion chemistry and NOx (N, NO, NO2) through the dissociation of molecular nitrogen. The HOx increases result in direct ozone destruction in the mesosphere and upper stratosphere via several catalytic loss cycles. Such middle atmospheric HOx-caused ozone loss is rather short-lived due to the relatively short lifetime (hours) of the HOx constituents. The NOx family has a considerably longer lifetime than the HOx family and can also lead to catalytic ozone destruction. EPP-caused enhancements of the NOx family can affect ozone directly, if produced in the stratosphere. Ozone decreases from the EPPs lead to a reduction in atmospheric heating and, subsequent atmospheric cooling. Conversely, EPPs can cause direct atmospheric heating through Joule heating. Measured HOx constituents OH and HO2 showed increases due to solar protons. Observed NOx constituents NO and NO2 were enhanced due to both solar protons and precipitating electrons. Other hydrogen- and nitrogen-ocntaining constituents were also measured to be directly influenced by EPPs, including N2O, HNO3, HO2NO2, N2OS, H2O2, ClONO2, HCl, and HOCl. Observed constituents ClO and CO were directly affected by EPPs as well. Many measurements indicated significant direct ozone decreases. A significant number of satellites housed instruments, which observed direct EPP-caused atmospheric effects, including Nimbus 4 (BUV), Nimbus 7 (SBUV), several NOAA platforms (SBUV/2), SME, UARS (HALOE, CLAES), SCISAT-1 (ACE-FTS), Odin (OSIRIS), Envisat-l (GOMOS, MIPAS, SCIAMACHY), and Aura (MLS). Measurements by rockets and ground-based radar also indicated EPP direct impacts. Atmospheric models have been used with some success in predicting the direct EPP impacts on the mesosphere and stratosphere. A review of the observed direct effects of EPP on the middle atmosphere will be given in this presentation.
Jackman, Charles H.↗