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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Calculations of Arctic ozone chemistry using objectively analyzed data in a 3-D CTM

A three-dimensional chemical transport model (CTM) (Kaminski, 1992) has been used to study the evolution of the Arctic ozone during the winter of 1992. The continuity equation has been solved using a spectral method with Rhomboidal 15 (R15) truncation and leap-frog time stepping. Six-hourly meteorological fields from the Canadian Meteorological Center global objective analysis routines run at T79 were degraded to the model resolution. In addition, they were interpolated to the model time grid and were used to drive the model from the surface to 10 mb. In the model, processing of Cl(x) occurred over Arctic latitudes but some of the initial products were still present by mid-January. Also, the large amounts of ClO formed in the model in early January were converted to ClNO3. The results suggest that the model resolution may be insufficient to resolve the details of the Arctic transport during this time period. In particular, the wind field does not move the ClO(x) 'cloud' to the south over Europe as seen in the MLS measurements.

Kaminski, J. W.↗
NASA NTRS1994

Effects of the Mount Pinatubo eruption on the radiative and chemical processes in the troposphere and stratosphere

The Lawrence Livermore National Laboratory two-dimensional zonally-averaged chemical-radiative-transport model of the global atmosphere was used to study the effects of the 15 June 1991 eruption of the Mt. Pinatubo volcano on stratospheric processes. SAGE 2 time-dependent aerosol surface area density and optical extinction data were used as input into the model. By 22 December 1991, a maximum equatorial change of -1.8 percent in column ozone was derived from heterogeneous chemical processes that convert NO(x) into HNO3 on sulfuric acid aerosols. Radiative feedbacks from increased aerosol optical thickness independently changes column ozone by approximately -3.5 percent for the same period. This occurs from increasing the net heating of the lower stratosphere, which indirectly increases chemical reaction rates via their temperature dependence and from changes in actinic fluxes, which directly modify photodissociation rates. Including both heterogeneous and radiative effects changes column ozone by -5.5 percent. The model-derived change overestimates the decrease in column ozone relative to the TOMS instrument on the Nimbus 7 satellite. Maximum local ozone decreases of 12 percent were derived in the equatorial region, at 25 km. Model-derived column NO2 peaked (-14 percent) at 30 deg S in October 1991. The timing of the NO2 peak is consistent with observation, but the model underestimates the magnitude of the decrease. Local concentrations of NO(x) (NO + NO2), ClO(x) (Cl + ClO), and HO(x) (OH + HO2), in the lower stratosphere between 30 deg S and 30 deg N, were calculated to have changed by -40 percent, +100 to +160 percent, and +120 to +140 percent respectively.

Kinnison, Douglas E.↗
NASA NTRS1993

Airborne Arctic Stratospheric Expedition 2: An overview

The sudden onset of ozone depletion in the antarctic vortex set a precedent for both the time scale and the severity of global change. The Airborne Antarctic Ozone Experiment (AAOE), stages from Punta Arenas, Chile, in 1987, established that CFCs, halons, and methyl bromide, the dominant sources of chlorine and bromide radicals in the stratosphere, control the rate of ozone destruction over the Antarctic; that the vortex is depleted in reactive nitrogen and water vapor; and that diabatic cooling during the antarctic winter leads to subsidence within the vortex core, importing air from higher altitudes and lower latitudes. This last conclusion is based on observed dramatic distortion in the tracer fields, most notably N2O. In 1989, the first Airborne Arctic Stratospheric Expedition (AASE-1), staged from Stavanger, Norway, and using the same aircraft employed for AAOE (the NASA ER-2 and the NASA DC-8), discovered that while NO(x) and to some degree NO(y) were perturbed within the arctic vortex, there was little evidence for desiccation. Under these (in contrast to the antarctic) marginally perturbed conditions, however, ClO was found to be dramatically enhanced such that a large fraction of the available (inorganic) chlorine resided in the form of ClO and its dimer ClOOCl. This leaves two abiding issues for the northern hemisphere and the mission of the second Airborne Arctic Stratospheric Expedition (AASE-2): (1) Will significant ozone erosion occur within the arctic vortex in the next ten years as chlorine loading in the stratosphere exceeds four parts per billion by volume? (2) Which mechanisms are responsible for the observed ozone erosion poleward of 30 deg N in the winter/spring northern hemisphere reported in satellite observations?

Anderson, James G.↗
NASA NTRS1993

Use of Fourier transforms for asynoptic mapping: Applications to the Upper Atmosphere Research Satellite microwave limb sounder

Fourier analysis has been applied to data obtained from limb viewing instruments on the Upper Atmosphere Research Satellite. A coordinate system rotation facilitates the efficient computation of Fourier transforms in the temporal and longitudinal domains. Fields such as ozone (O3), chlorine monoxide (ClO), temperature, and water vapor have been transformed by this process. The transforms have been inverted to provide maps of these quantities at selected times, providing a method of accurate time interpolation. Maps obtained by this process show evidence of both horizontal and vertical transport of important trace species such as O3 and ClO. An examination of the polar regions indicates that large-scale planetary variations are likely to play a significant role in transporting midstratospheric O3 into the polar regions. There is also evidence that downward transport occurs, providing a means of moving O3 into the polar vortex at lower altitudes. The transforms themselves show the structure and propagation characteristics of wave variations.

Elson, Lee S.↗
NASA NTRS1994

The chemical and radiative effects of the Mount Pinatubo eruption

To clarify the mechanisms leading to effects on stratospheric ozone, time-dependent stratospheric aerosol and gas experiment II (SAGE II) and cryogenic limb array elaton spectrometer (CLAES) aerosol optical extinction data and SAGE II surface area density are used as parameters in a two-dimensional (2-D) zonally averaged chemical radiative transport model. The model was integrated with time from before the eruption through December 1993. The modeled impact on global ozone results from increased rates of heterogeneous reactions on sulfate aerosols and from the increased radiative heating and scattering caused by these aerosols. When the aerosol heating is allowed to modify the temperature distribution, the maximum change calculated in equatorial column ozone is -1.6%. The calculated equatorial temperature change and peak local ozone change in October 1991 are +6K and -4%, respectively. When aerosol heating perturbs the circulation in the model, the maximum change in equatorial column ozone is -6%. Increased heterogeneous processing on sulfate aerosols is calculated to have changed equatorial column ozone in late 1991 by -1.5%. Global column ozone in the model in 1992 and 1993 changed by -2.8% and -2.4%, respectively. The relationship of ozone-controlling processes in the lower stratosphere is altered as well; HO(x) becomes the most important catalytic cycle, followed by ClO(x) and NO(x). This is driven by significant changes in trace gas concentrations. In October 1991, lower stratospheric, equatorial NO(x) decreased by 40%, ClO(x) increased by 60%, and HO(x) increased by 25%. When the effect of heterogeneous chemical processing on sulfate aerosols is combined with aerosol heating, modifying either circulation or temperature, dramatically different ozone fingerprints with time and latitude are predicted. Model-derived changes in the equatorial region in column ozone best represented the observed data when perturbed circulation was combined with heterogeneous chemical effects. However, at high latitudes, the increased ozone production from the strengthening of the mean circulation tends to cancel the heterogeneous reduction of ozone. This is not in good agreement with observed data, especially in 1992 and 1993. When the circulation is held fixed and the temperature allowed to change, and heterogeneous chemical effects are included, the equatorial ozone decrease predicted was too small for 1991. However, the mid- to high-latitude decrease in 1992 and 1993 is in better agreement with observed data.

Kinneson, Douglas E.↗
NASA NTRS1996

Bromine-Chlorine Coupling in the Antarctic Ozone Hole

The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioninig in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5 - 25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70 deg. S, NO(sub y) = 2 ppbv, with Polar Stratospheric Clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC- perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO an Cl2O2 back to HCI. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (alpha-factor) ranges from 33 to 55, decreasing with increase of bromine.

Danilin, Michael Y.↗
NASA NTRS1993

Airborne Arctic Stratospheric Expedition 2: Air Parcel Trajectories

An overview of Airborne Arctic Stratospheric Expedition 2 is given. Effects of Pinatubo aerosol on stratospheric ozone at mid-latitudes, in situ measurements of ClO and ClO/HCl ratio, balloon-borne measurements of ClO, NO, and O3 in a volcanic cloud, and new observations of the NO(y)/N2O correlation in the lower stratosphere are discussed. Among other topics addressed are the following: in situ tracer correlations of methane, nitrous oxide, and ozone as observed aboard the DC-8, in situ measurements of changes in stratospheric aerosol and the N2O-aerosol relationship inside and outside of the polar vortex, measurements of halogenated organic compounds near the tropical tropopause, and airborne brightness measurements of the polar winter troposphere.

Source record↗
NASA NTRS1996

Arctic Ozone Depletion Observed by UARS MLS During the 1994-95 Winter

During the unusually cold 1994-95 Arctic winter, the Microwave Limb Sounder observed enhanced chlorine monoxide (ClO) in late Dec and throughout Feb and early Mar. Late Dec ClO was higher than during any of the previous 3 years, consistent with the colder early winter. Between late Dec 1994 and early Feb 1995, 465 K (about 50 hPa) vortex-averaged ozone (03) decreased by about 15%, with local decreases of about 30%; additional local decreases of about 5% were seen between early Feb and early Mar. Transport calculations indicate that vortex-averaged chemical loss between late Dec and early Feb was about 20% at 465 K, with about 1/4 of that masked by downward transport of O3. This Arctic chemical O3 loss is not readily detectable in MLS column O3 data.

Manney, G. L.↗
NASA NTRS1996

A Comparison of Measurements from ATMOS and Instruments Aboard the ER-2 Aircraft: Halogenated Gases

We compare volume mixing ratio profiles of N2O, CFC-11, CFC-12, CCl4, SF6, and HCl in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov. 1994. Good agreement is found between ATMOS and in situ correlations of [CFC-11], [CFC-12], and [SF6] with [N2O]. ATMOS measurements of [CCl4] are 15% high compared to ER-2 data, but agree within the systematic uncertainties. ATMOS observations of [HCl] vs [N2O] are within approximately 10% of ER-2 data for [HCl] > 1 ppbv, but exceed in situ measurements by larger fractional amounts for smaller [HCl]. ATMOS measurements of [ClONO2] agree well with values inferred from in situ observations of [ClO], [NO], and [O3]. The sum of [HCl] and [ClONO2] observed by ATMOS, supplemented by a minor contribution from [ClO] estimated with a photochemical model, is consistent with the levels of inorganic chlorine inferred from in situ measurements of chlorine source gases.

Chang, A. Y.↗
NASA NTRS1999

The Budget and Partitioning of Stratospheric Chlorine During the 1997 Arctic Summer

Volume mixing ratio profiles of HCl, HOCl, ClNO3, CH3Cl, CFC-12, and CFC-11, CCl4, HCFC-22, and CFC-113 were measured simultaneously from 9 to 38 km by the Jet Propulsion Laboratory MkIV Fourier Transform Infrared solar absorption spectrometer during two balloon flights from Fairbanks, Alaska (64.8 N), on May 8 and July 8, 1997. The altitude variation of total organic chlorine (CCl(sub y)), total inorganic chlorine (Cl(sub y)), and the nearly constant value (3.7 +/- 0.2 ppbv) of their sum (Cl(sub TOT)) demonstrates that the stratospheric chlorine species available to react with O3 are supplied by the decomposition of organic chlorinated compounds whose abundances are well quantified. Measured profiles of HCl and ClNO3 agree well with profiles found by photochemical model (differences < 10% for altitudes below 35 km) constrained by various other constituents measured by MkIV. The production of HCl by ClO + OH plays a relatively small role in the partitioning of HCl and ClNO3 for the sampled air masses. However, better agreement with the measured profiles of HCl and ClNO3 is obtained when this source of HCl is included in the model. Both the measured and calculated [ClNO3]/[HCl] ratios exhibit the expected near linear variation with [O3](sup 2)/[CH4] over a broad range of altitudes. MkIV measurements of HCl, ClNO3, and CCl(sub y) agree well with ER-2 in situ observations of these quantities for directly comparable air masses. These results demonstrate good understanding of the budget of stratospheric chlorine and that the partitioning of inorganic chlorine is accurately described by photochemical models that employ JPL97 reaction rates and production of HCl from ClO + OH for the environmental conditions encountered: relatively warm temperatures, long periods of solar illumination, and relatively low aerosol surface areas.

Sen, B.↗
NASA NTRS2000

Trajectory Hunting: A Case Study of Rapid Chlorine Activation in December 1992 as Seen by UARS

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the Atmospheric and Environmental Research, Inc. (AER) photochemical box model. As a case study, we investigate rapid chlorine activation in the Arctic lower stratosphere on December 29, 1992 associated with a polar stratospheric cloud (PSC) event. Eleven air parcels that have been sampled several times along 5-day trajectories at the 465 K (approx. 46 hPa), 520 K (approx. 31 hPa), and 585 K (approx. 22 hPa) levels were investigated. For the first time, the latest versions of the Cryogenic Limb Array Etalon Spectrometer (CLAES, version 9) and Microwave Limb Sounder (MLS, version 5) data sets are analyzed, and their consistency is assessed. A detailed sensitivity study with the AER photochemical box model along these trajectories leads to the conclusion that for the December 24-29, 1992 episode (1) the individual CLAES version 9 ClONO2 and MLS version 5 ClO measurements are self-consistent within their uncertainties; and (2) most of the time, UARS measurements of ClO, ClONO2, HNO3, and aerosol extinction at 780 cm (exp -1) agree within the range of their uncertainties with the model calculations. It appears that the HNO3 and aerosol extinction measurements for four parcels at 520 K look more supportive for the nitric acid trihydrate (NAT) scheme. However, the uncertainties in the individual UARS measurements and U.K. Meteorological Office temperature do not allow a definite discrimination between the NAT and supercooled ternary solution (STS) PSC schemes for this chlorine activation episode in December 1992.

Danilin, M. Y.↗
NASA NTRS1998

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.↗
NASA NTRS1999

The Budget and Partitioning of Stratospheric Chlorine During the 1997 Arctic Summer

Volume mixing ratio profiles of HCl, HOCl, ClNO3, CH3Cl, CFC-12, CFC-11, CCl4, HCFC-22, and CFC-113 were measured simultaneously from 9 to 38 km by the Jet Propulsion Laboratory MkIV Fourier Transform Infrared solar absorption spectrometer during two balloon flights from Fairbanks, Alaska (64.8 N), on May 8 and July 8, 1997. The altitude variation of total organic chlorine (CCly) total inorganic chlorine (Cly), and the nearly constant value (3.7 +/- 0.2 ppbv) of their sum (Cl(sub TOT)) demonstrates that the stratospheric chlorine species available to react with O3 are supplied by the decomposition of organic chlorinated compounds whose abundances are well quantified. Measured profiles of HCl and ClNO3 agree well with profiles found by photochemical model (differences < 10% for altitudes below 35 km) constrained by various other constituents measured by MkIV. The production of HCl by ClO + OH plays a relatively small role in the partitioning of HCl and ClNO3 for the sampled air masses. However, better agreement with the measured profiles of HCl and ClNO3 is obtained when this source of HCl is included in the model. Both the measured and calculated [ClNO3]/[HCl] ratios exhibit the expected near linear variation with [O3]2/[CH4] over a broad range of altitudes. MkIV measurements of HCl, ClNO3, and CC1y agree well with ER-2 in situ observations of these quantities for directly comparable air masses. These results demonstrate good understanding of the budget of stratospheric chlorine and that the partitioning of inorganic chlorine is accurately described by photochemical models that employ JPL97 reaction rates and production of HCl from ClO + OH for the environmental conditions encountered: relatively warm temperatures, long periods of solar illumination, and relatively low aerosol surface areas.

Sen, B.↗
NASA NTRS2000

An Examination of the Inorganic Chlorine Budget in the Lower Stratosphere

We use the first simultaneous in situ measurements of ClONO2, ClO, and HCl acquired using the NASA ER-2 aircraft during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission to test whether these three compounds quantitatively account for total inorganic chlorine (Cly) in the lower stratosphere in 1997. We find (ClO + ClONO2 + HCl)/Cly = 0.92 +/- 0.10, where Cly is inferred from in situ measurements of organic chlorine source gases. These observations are consistent with our current understanding of the budget and partitioning of Cly in the lower stratosphere. We find no evidence in support of missing inorganic chlorine species that compose a significant fraction of Cly. We apply the analysis to earlier ER-2 observations dating from 1991 to investigate possible causes of previously observed discrepancies in the inorganic chlorine budget. Using space shuttle, satellite, balloon, and aircraft measurements in combination with ER-2 data, we find that the discrepancy is unlikely to have been caused by missing chlorine species or an error in the photolysis rate of chlorine nitrate. We also find that HCl/Cly is not significantly controlled by aerosol surface area density in the lower stratosphere.

Bonne, G. P.↗
NASA NTRS2001

Mechanisms for Midlatitude Ozone Loss: Heterogeneous Chemistry in the Lowermost Stratosphere?

The question of midlatitude ozone erosion by chlorine free radical catalysis is examined. We present and analyze simultaneous, high-resolution observations of ClO, H2O, tropopause height, particle reactive surface area, and ice saturation occurrence frequency obtained from the NASA ER-2 aircraft. The objective is to test the hypothesis that the existence of cirrus clouds or cold aerosols in the first few kilometers above the tropopause at midlatitudes is responsible for increasing the ratio of chlorine free radicals to total inorganic chlorine, thus amplifying the rate of catalytic ozone destruction. The observations reveal a sharp decrease in ice saturation frequency at the tropopause, a marked degree of undersaturation just above the tropopause, a corresponding sharp gradient in the product of cold aerosol reactive surface area and reaction probability, gamma-S(sub a), and, finally, the consistent absence of enhanced concentrations of ClO immediately above the tropopause. These results suggest that midlatitude ozone loss is not controlled in situ by the mechanism of cirrus cloud and/or cold aerosol enhancement of chlorine radicals in the vicinity of the tropopause.

Smith, Jessica B.↗
NASA NTRS2000

Trajectory Hunting: A Case Study of Rapid Chlorine Activation in December 1992 as Seen by UARS

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the Atmospheric and Environmental Research, Inc. (AER) photochemical box model. As a case study, we investigate rapid chlorine activation in the Arctic lower stratosphere on December 29, 1992 associated with a polar stratospheric cloud (PSC) event. Eleven air parcels that have been sampled several times along five-day trajectories at the 465 K (approx. 46 hPa), 520 K (approx. 31 hPa), and 585 K (approx. 22 hPa) levels were investigated. For the first time, the latest versions of the Cryogenic Limb Array Etalon Spectrometer (CLAES, version 9) and Microwave Limb Sounder (MLS, version 5) data sets are analyzed, and their consistency is assessed. A detailed sensitivity study with the AER photochemical box model along these trajectories leads to the conclusion that for the December 24-29, 1992 episode: (1) the individual CLAES ClONO2 and MLS ClO measurements are self-consistent within their uncertainties; and (2) most of the time, UARS measurements of ClO, ClONO2, HNO3, and aerosol extinction at 780 cm(exp -1) agree within the range of their uncertainties with the model calculations. It appears that the HNO3 and aerosol extinction measurements for four parcels at 520 K look more supportive for the nitric acid trihydrate (NAT) scheme, However, the uncertainties in the individual UARS measurements and UK Meteorological Office temperature do not allow a definite discrimination between the NAT and supercooled ternary solution (STS) PSC schemes for this chlorine activation episode in December 1992.

Danilin, M. Y.↗
NASA NTRS2002

Variations and climatology of CI0 in the polar lower stratosphere from UARS Microwave Limb Sounder measurements

The Microwave Limb Sounder (MLS) on board the Upper Atmosphere Research Satellite (UARS) measured the global distribution of stratospheric ClO over annual cycles for much of the 1990s, albeit with reduced sampling frequency in the latter half of the decade. Here we present an overview of the interannual and interhemispheric variations in the distribution of ClO derived from UARS MLS measurements, with a particular emphasis on enhancements in the winter polar lower stratosphere.

Microwave Limb Sounder (MLS)↗
NASA NTRS1994

Interhemispheric Differences in Dentifrication and Related Processes Affecting Polar Ozone

The severe depletion of stratospheric ozone over Antarctica in late winter and early spring is caused by enhanced CLO abundances arising from heterogeneous reactions on polar stratospheric clouds (PSCs). CLO abundances comparable to those over Antarctica have also been observed throughout the Arctic Vortex, but the accompanying loss of Arctic ozone has been much less severe.

ozone depletion↗