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Cunnold, D. M.

Publications and source records attributed to Cunnold, D. M..

At least 19 records

Change in ozone trends at southern high latitudes

Long-term ozone variations at 60-70degS in spring are investigated using ground-based and satellite measurements. Strong positive correlation is shown between year-to-year variations of ozone and temperature in the Antarctic collar region in Septembers and Octobers. Based on this relationship, the effect of year-to-year variations in vortex dynamics has been filtered out. This process results in an ozone time series that shows increasing springtime ozone losses over the Antarctic until the mid-1990s. Since approximately 1997 the ozone losses have leveled off. The analysis confirms that this change is consistent across all instruments and is statistically significant at the 95% confidence level. This analysis quantifies the beginning of the recovery of the ozone hole, which is expected from the leveling off of stratospheric halogen loading due to the ban on CFCs and other halocarbons initiated by the Montreal Protocol.

Yang, E.-S.

Influence of isentropic transport on seasonal ozone variations in the lower stratosphere and subtropical upper troposphere

The isentropic cross-tropopause ozone transport has been estimated in both hemispheres in 1999 based on the potential vorticity mapping of Stratospheric Aerosol and Gas Experiment 11 ozone measurements and contour advection calculations using the NASA Goddard Space Flight Center Global and Modeling Assimilation Office analysis. The estimated net isentropic stratosphere-to-troposphere ozone flux is approx.118 +/- 61 x 10(exp9)kg/yr globally within the layer between 330 and 370 K in 1999; 60% of it is found in the Northern Hemisphere, and 40% is found in the Southern Hemisphere. The monthly average ozone fluxes are strongest in summer and weakest in winter in both hemispheres. The seasonal variations of ozone in the lower stratosphere (LS) and upper troposphere (UT) have been analyzed using ozonesonde observations from ozonesonde stations in the extratropics and subtropics, respectively. It is shown that observed ozone levels increase in the UT over subtropical ozonesonde stations and decrease in the LS over extratropical stations in late spring/early summer and that the ozone increases in the summertime subtropical UT are unlikely to be explained by photochemical ozone production and diabatic transport alone. We conclude that isentropic transport is a significant contributor to ozone levels in the subtropical upper troposphere, especially in summer.

Jing, P.

Comment on "Enhanced upper stratospheric ozone: Sign of recovery or solar cycle effect?"

[01] Steinbrecht et al. [2004] (hereinafter referred to as S4) have discussed the trend in upper stratospheric ozone at 35 -45-km altitude determined from their lidar measurements at Hohenpeissenberg (47.8degN, 11.0degE) from 1987 to 2003. They question the conclusion of Newchurch et al. [2003] (hereinafter referred to as N3) that after approximately 1997 the downward trend of upper stratospheric ozone at 35-45-km altitude has diminished significantly. They argue instead that recent ozone changes are associated with the recent solar maximum (i.e., the solar cycle effect on ozone). In this comment we question their procedure for identifying the solar cycle effect. Moreover, we argue that the solar cycle effect was appropriately accounted for in the N3 analysis, and we buttress our argument by demonstrating that the more extensive data set used by N3 shows that the trend in upper stratospheric ozone has diminished significantly since 1997 and that this is evidence of the first stage of ozone recovery.

Cunnold, D. M.

Isentropic Cross-Tropopause Ozone Transport in the Northern Hemisphere

This paper investigates isentropic ozone exchange between the extratropical lower stratosphere and the subtropical upper troposphere in the Northern Hemisphere. The quantification method is based on the potential vorticity (PV) mapping of Stratospheric Aerosol and Gas Experiment (SAGE)-II ozone measurements and contour advection calculations using the NASA Goddard Space Center Data Assimilation Office (DAO) analysis for the year 1990. The magnitude of the annual isentropic stratosphere-to-troposphere ozone flux is calculated to be approximately twice the flux that is directed from the troposphere into the stratosphere. The net effect is that approx.46 x 10(exp 9) kg/yr of ozone are transferred quasi horizontally from the extratropical lower stratosphere into the subtropical upper troposphere between the isentropic surfaces of 330 and 370 K. The estimated monthly ozone fluxes show that the isentropic cross-tropopause ozone transport is stronger in summer/fall than in winter/ spring, and this seasonality is more obvious at the upper three levels (i.e., 345, 355, and 365 K) than at 335 K. The distributions of the estimated monthly ozone fluxes indicate that the isentropic stratosphere-to-troposphere ozone exchange is associated with wave breaking and occurs preferentially over the eastern Atlantic Ocean and northwest Africa in winter and over the Atlantic and Pacific Oceans in summer.

Jing, P.

Evidence for slowdown in stratospheric ozone loss: First stage of ozone recovery

Global ozone trends derived from the Stratospheric Aerosol and Gas Experiment I and II (SAGE I/II) combined with the more recent Halogen Occultation Experiment (HALOE) observations provide evidence of a slowdown in stratospheric ozone losses since 1997. This evidence is quantified by the cumulative sum of residual differences from the predicted linear trend. The cumulative residuals indicate that the rate of ozone loss at 35- 45 km altitudes globally has diminished. These changes in loss rates are consistent with the slowdown of total stratospheric chlorine increases characterized by HALOE HCI measurements. These changes in the ozone loss rates in the upper stratosphere are significant and constitute the first stage of a recovery of the ozone layer.

Newchurch, M. J.

SAGE (version 5.96) Ozone Trends in the Lower Stratosphere

Ozone retrievals from Stratospheric Aerosol and Gas Experiment (SAGE) II version 5.96 (v5.96) below approx. 25 km altitude are discussed. This version of the algorithm includes improved constraints on the wavelength dependence of aerosol extinctions based on the ensemble of aerosol size distribution measurements. This results in a reduction of SAGE ozone errors in the 2 years after the Mount Pinatubo eruption. However, SAGE ozone concentrations are still approx. 10% larger than ozonesonde and Halogen Occultation Experiment (HALOE) measurements below 20 km altitude under nonvolcanic conditions (and by more than this in the tropics). The analysis by Steele and Turco suggests that the SAGE ozone overpredictions are in the wrong direction to be explained by aerosol extinction extrapolation errors. Moreover, preliminary SAGE 11 v6.0a retrievals suggest that they are partially accounted for by geometric difficulties at low altitudes in v5.96 and prior retrievals. SAGE ozone trends for the 1979-1996 and 1984-1996 periods are calculated and compared, and the sources of trend errors are discussed. These calculations are made after filtering out ozone data during periods of high, local aerosol extinctions. In the lower stratosphere, below approx. 28 km altitude, there is shown to be excellent agreement in the altitudinal structure of ozone decreases at 45 deg N between SAGE and ozonesondes with the largest decrease in both between 1979 and 1996 having occurred below 20 km altitude, amounting to 0.9 +/- 0.7% yr (2sigma) at 16 km altitude. However, in contrast to the fairly steady decreases at 45 deg N, both SAGE measurements and Lauder ozonesondes show ozone increases at 45 deg S over the period from the mid-1980s to 1996 of 0.2 +/- 0.5%/yr (2sigma) from 15 to 20 km altitude. The SAGE data suggest that this increase is a wintertime phenomenon which occurs in the 15-20 km height range. Changes in dynamics are suggested as the most likely cause of this increase. These hemispheric differences in ozone trends are supported by ozone column measurements by the Total Ozone Mapping Spectrometer (TOMS).

Cunnold, D. M.

On the Tropospheric Measurements of Ozone by the Stratospheric Aerosol and Gas Experiment II (SAGE II, version 6.1) in the Tropics

Tropospheric measurements of ozone from SAGE II (version 6.1) in the tropics have been analyzed using 12 years of data (1985-1990, 1994-1999). The seasonally averaged vertical profiles of the ozone mixing ratio in the upper troposphere have been presented for the first time from satellite measurements. These profiles show qualitative similarities with corresponding seasonal mean ozonesonde profiles at northern and southern tropical stations and are about 40-50% less than the sonde values. Despite this systematic offset, the measurements appear to be consistent with a zonal wave one pattern in the upper tropospheric column ozone and with the recently predicted summertime ozone enhancement over the Middle East. These results thus affirm the usefulness of the occultation method in studying tropospheric ozone.

Kar, J.

Upper Stratospheric Temperature Climatology Derived from SAGE II Observations: Preliminary Results

This study shows that the temperature information in the upper stratosphere can be derived from the SAGE II 385-mn observations. The preliminary results indicate that the zonal mean temperature increases with altitude below 50 km and decreases above 50 km. At 50 km, a regional maximum of 263 K is located in the tropics, and a minimum of 261 K occurs in the subtropics in both hemispheres. The derived long-term temperature changes from 1985 to 1997 reveal a statistically significant negative trend of -2 to -2.5 K/decade in the tropical upper stratosphere and about -2 K/decade in the subtropics near the stratopause. At latitudes poleward of 50, the results show a statistically significant positive trend of about 1 K/decade in the upper stratosphere. The preliminary results also show large annual temperature oscillations in the extratropics with a maximum amplitude of approx. 8 K located at about 44 km near 50 in both hemispheres during local summer. In addition, the semiannual oscillation is found to be a maximum in the tropics with a peak amplitude of approx. 3.3 K located at about 42 km during the equinox.

Wang, P.-H.

Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and they appear to be the first suggested photochemical mechanism that is capable of explaining the altitude dependence of the observed mass -independent isotopic signature.

Estupinan, E. G.

A Reference Model for Middle Atmosphere Ozone in 1992-1993

An ozone climatology for the period April 1992 to March 1993 and covering pressures from 0.1 to 100 hPa and from 80 deg N to 80 deg S is derived from satellite-based measurements by the Stratospheric Aerosol and Gas Experiment (SAGE), the Halogen Occultation Experiment (HALOE), and the Microwave Limb Sounder (MLS). At pressures less than 1 hPa, separate distributions are given for daytime and nighttime conditions. From 0.46 to 32 hPa the accuracy of the distribution is estimated to be 5%, and the precision is also approx. 5%. Estimates of atmospheric variability are provided on the basis of standard deviations of the measurements within months. Distributions of ozone monthly means and standard deviations are also given in a potential temperature, equivalent latitude coordinate system. This data set is included in the UARS reference atmosphere, and it is accessible through that web site.

Wang, H. J.

Uncertainties in Upper Stratospheric Ozone Trends from 1979 to 1996

The time series of differences in coincident measurements of ozone by Stratospheric Aerosol and Gas Experiment (SAGE) and by Solar Backscattered Ultraviolet (SBUV), SBUV/2, Umkehr and Microwave Limb Sounder (MLS) are analyzed, and the slopes in the differences are calculated. SAGE ozone measurements are also compared against those by HALOE. The purpose of these comparisons is to look for statistically significant nonzero slopes which could indicate long-term calibration problems in one or more of the measurement systems. It is found that the slopes are remarkably similar between the Northern and Southern Hemisphere midlatitudes, and, apart from a few exceptions, the slopes are also similar in the tropics. Slopes of MLS-SAGE differences and HALOE-SAGE trends from approximately 1992 to 1996 have values of approximately -0.5 +/- 0.4%/yr (95% confidence limits) in Umkehr layers 7-9 (which are centered at approx. 37, 42, and 47 km altitude). Umkehr-SAGE slopes for 1979-1996, however, are almost all positive and in the range -0.1 - 0.41%/yr for Umkehr layers 4 - 8, while SBUV-SAGE slopes for 1979-1989 are essentially zero in layers 4 - 7 and 0.3-0.4%/yr in layers 8 and 9. Averaging all these results with SBUV-SAGE 11 slopes from 1985 to 1989, the other sensors minus SAGE slopes are most likely between 0.2 and -0.2%/yr1 from approx. 20 to 40 km altitude. The results indicate slightly negative slopes in Umkehr layers 5-7 and positive slopes in the other three layers. There thus appears to be no overall drift in the SAGE ozone measurements from 1979 to 1996, but SAGE sunrise/sunset trend differences greater than 40 km altitude, combined with the more accurate SBUV-SAGE slopes for 1979-1989, suggest a most likely slope range of 0.4 to -0.4%/yr between 40 and 50 km altitude. SBUV/2 measurements from 1989 to 1994 have an upward trend with respect to SAGE measurements of approx. 0.7% /yr with some altitudinal structure; this slope exceeds the estimated 95% uncertainties on the SBUV/2 trends.

Cunnold, D. M.

A Reference Model for Middle Atmosphere Ozone in 1992/1993: Differences from That of Keating et al (1996)

Ozone distributions have been derived from recent satellite-based measurements by the Stratospheric Aerosol and Gas Experiment (SAGE), the Halogen Occultation Experiment (HALOE) and the Microwave Limb Sounder (MLS). An ozone distribution for the period April 1992 to March 1993 and covering pressures from 0.1 to 100 mb and from 80 deg N to 80 deg S is summarized. At pressures less than 1 mb, separate distributions are given for daytime and nighttime conditions. The resulting distributions extend to somewhat higher latitudes and lower altitudes than previous COSPAR reference atmosphere distributions for ozone. Differences versus the most recent COSPAR distribution by Keating et al are illustrated.

Wang, H. J.

The fate of atmospheric phosgene and the stratospheric chlorine loadings of its parent compounds: CCl4, C2Cl4, C2HCL3, CH3CCl3, and CHCl3

A study of the tropospheric and stratospheric cycles of phosgene is carried out to determine its fate and ultimate role in controlling the ozone depletion potentials of its parent compounds. Tropospheric phosgene is produced from the OH-initiated oxidation of C2Cl4, CH3CCl3, CHCl3, and C2HCl3. Simulations using a two-dimensional model indicate that these processes produce about 90 pptv/yr of tropospheric phosgene with an average concentration of about 18 pptv, in reasonable agreement with observations. We estimate a residence time of about 70 days for tropospheric phosgene, with the vast majority being removed by hydrolysis in cloudwater. Only about 0.4% of the phosgene produced in the troposphere avoids wet removal and is transported to the stratosphere, where its chlorine can be released to participate in the catalytic destruction of ozone. Stratospheric phosgene is produced from the photochemical degradation of CCl4, C2Cl4, CHCl3, and CH3CCl3 and is removed by photolysis and downward transport to the troposphere. Model calculations, in good agreement with observations, indicate that these processes produce a peak stratospheric concentration of about 25-30 pptv at an altitude of about 25 km. In contrast to tropospheric phosgene, stratospheric phosgene is found to have a lifetime against photochemical removal of the order of years. As a result, a significant portion of the phosgene that is produced in the stratosphere is ultimately returned to the troposphere, where it is rapidly removed by clouds. This phenomenon effectively decreases the amount of reactive chlorine injected into the stratosphere and available for ozone depletion from phosgene's parent compounds. A similar phenomenon due to the downward transport of stratospheric COFCl produced from CFC-11 is estimated to cause a 7% decrease in the amount of reactive chlorine injected into the stratosphere from this compound. Our results are potentially sensitive to a variety of parameters, most notably the rate of reaction of phosgene with sulfate aerosols. However, on the basis of the observed vertical distribution of COCl2, we estimate that the reaction of COCl2 with sulfate aerosol most likely has a gamma less than 5 x 10(exp -5) and, as a result, has a negligible impact on the stratospheric chlorine loadings of the phosgene parent compounds.

Kindler, T. P.

A 3-D model study of ozone eddy transport in the winter stratosphere

Calculations of the Northward eddy fluxes of stratospheric ozone in a three-dimensional chemical-dynamical model are discussed. It is shown that, although approximately 50 percent of the zonal mean flux is produced by stationary planetary wavenumbers 1 and 2, the wintertime flux due to the chemical eddies is substantially underestimated when a quasi-linear representation is used.

Hsu, N. C.

SAGE 2-Umkehr case study of ozone differences and aerosol effects from October 1984 to April 1989

A comparison of 1262 cases of coincident ozone profiles derived from 666 Umkehrs at 17 different stations and 901 SAGE 2 profiles within 1000 km and 12 hours between October 1984 and April 1989 indicates the following layer percentage differences with 2-sigma error bars: layer three 14.6 plus/minus 3.3 percent, layer four 17.6 plus/minus 1.1 percent, layer five -1.3 plus/minus 0.5 percent, layer six -5.7 plus/minus 0.7 percent, layer seven -1.0 plus/minus 0.7 percent, layer eight 4.2 plus/minus 0.7 percent, and layer nine 6.8 plus/minus 1.2 percent. Comparing SAGE 2-Umkehr differences to SAGE 1 version 5.5-Umkehr differences shows SAGE 2 higher than or equal to SAGE 1 relative to Umkehr in all layers except layer three. Adjustment for this bias would produce trends derived from SAGE 2-SAGE 1 differences and Umkehr observations in the 1980s more nearly equal to each other in layers six, seven, and eight. A possible explanation of these differences is a systematic shift in the reference altitude between SAGE 1 and SAGE 2, but there is no independent evidence of this. While the shape of the vertical profile of differences at 17 individual Umkehr stations (mostly in mid-latitudes) is generally consistent at all stations except at Poker Flat, Seoul, and Lauder, significant variation does exists among the stations. The profile of mean difference is similar to previously observed differences between Umkehr and both SAGE 2 and SBUV and also to an eigenvector analysis, but with site-dependent amplitude discrepancies. Because of the close correspondence of stratospheric aerosol optical depth at the SAGE 2-measured 0.525 micron wavelength and the extrapolated 0.32 Umkehr wavelength determined in this study, we use the 0.525 micron data to determine the aerosol effect of Umkehr profiles. The aerosol errors to the Umkehr ozone amounts in percent ozone amount per 0.01 stratospheric aerosol optical depth range from plus 2 percent in layer six to minus 3 percent in layer nine. These results agree with previous theoretical and empirical studies within their respective error bounds in layers nine, eight, and five. The result in layer six differs significantly from previous works. In view of the fact that SAGE 2 and Umkehr produce different ozone retrievals in layers eight and nine and because the intra-layer correlation of SAGE 2 ozone and aerosol in layers eight and nine in non-zero, one must exercise some caution in attributing the entire SAGE 2-Umkehr differences in the upper layers to an aerosol effect.

Newchurch, M. J.

Mesospheric ozone measurements by SAGE II

SAGE II observations of ozone at sunrise and sunset (solar zenith angle = 90 deg) at approximately the same tropical latitude and on the same day exhibit larger concentrations at sunrise than at sunset between 55 and 65 km. Because of the rapid conversion between atomic oxygen and ozone, the onion-peeling scheme used in SAGE II retrievals, which is based on an assumption of constant ozone, is invalid. A one-dimensional photochemical model is used to simulate the diurnal variation of ozone particularly within the solar zenith angle of 80 deg - 100 deg. This model indicates that the retrieved SAGE II sunrise and sunset ozone values are both overestimated. The Chapman reactions produce an adequate simulation of the ozone sunrise/sunset ratio only below 60 km, while above 60 km this ratio is highly affected by the odd oxygen loss due to odd hydrogen reactions, particularly OH. The SAGE II ozone measurements are in excellent agreement with model results to which an onion peeling procedure is applied. The SAGE II ozone observations provide information on the mesospheric chemistry not only through the ozone profile averages but also from the sunrise/sunset ratio.

Chu, D. A.

Global trends and annual releases of CCl3F and CCl2F2 estimated from ALE/GAGE and other measurements from July 1978 to June 1991

Thirteen years of Atmospheric Lifetime Experiment/Global Atmospheric Gases Experiment CCl3F and CCl2F2 measurements at five remote, surface, globally distributed sites are analyzed. Comparisons are made against shipboard measurements by the Scripps Institution of Oceanography (SIO) group and archived air samples collected at Cape Grim, Tasmania, since 1978. CCl3F in the lower troposphere was increasing at an average rate of 9.2 ppt/yr over the period July 1978 to June 1988. CCl2F2 was increasing at an average 17.3 ppt/yr in the lower troposphere over the same period. However, between July 1988 and June 1991 the increases of CCl3F and CCl2F2 in this region have averaged just 7.0 ppt/yr and 15.7 ppt/yr, respectively. The rate of increase has been decreasing 2.4 ppt/yr(exp 2) and 2.9 ppt/yr(exp 2) over this 3-year period. Based on a recent scenario of the global releases of these compounds and using the new calibration scale SIO 1993, the equilibrium lifetimes are estimated to be 44 +17/-10 and 180 +820/-81 years for CCl3F and CCl2F2, respectively. Using these lifetime estimates and a two-dimensional model, it is estimated that global releases of these two chlorofluorocarbons in 1990 were 249 +/- 28 x 10(exp 6) kg for CCl3F and 366 +/- 30 x 10(exp 6) kg for CCl2F2. It is also estimated that combined releases of these chlorofluorocarbons in 1990 were 21 +/- 5% less than those in 1986.

Cunnold, D. M.

Aerosol effect on Umkehr ozone profiles using Stratospheric Aerosol and Gas Experiment II measurements

This study examines 1211 cases of coincident ozone profiles derived from 1164 Umkehrs and 928 Stratospheric Aerosol and Gas Experiment II (SAGE II) profiles within 1000 km and 12 hours between October 1984 and April 1989 to study the stratospheric-aerosol effect on Umkehr ozone profiles. Because of the close correspondence of stratospheric aerosol optical depth at the SAGE II-measured 0.525-micrometer wavelength and the extrapolated 0.32 Umkehr wavelength determined in this study we use the 0.525-micrometer data to determine the aerosol effect on Umkehr profiles. At the 95% confidence level, we find the following errors to the Umkehr ozone amounts: in Umkehr layer 9 (-2.9 +/- 2.1), layer 8 (-2.3 +/- 1.1), layer 7 (0.1 +/- 1.1), layer 6 (2.2 +/- 1.0), layer 5 (-1.5 +/- 0.8), and layer 4 (-2.4 +/- 1.7) in percent ozone amount per 0.01 stratospheric aerosol optical depth. These results agree with previous theoretical and empirical studies within their respective error bounds in layers 9, 8, and 7. The results in layers 6, 5, and 4 differ significantly from those in previous works. Using only those eight stations with more than 47 coincidences results in mean aerosol effects that are not significantly different from the 14-station results. Because SAGE II and Umkehr produce different ozone retrievals in layer 9 and because the intralayer correlation of SAGE II ozone and aerosol in layer 9 is nonzero, one must exercise some caution in attributing the entire SAGE II-Umkehr difference in this layer to an aerosol effect.

Newchurch, M. J.