Temperature Dependence of Ozone Loss Rate

2013 ◽  
Vol 133 (9) ◽  
pp. 465-470
Author(s):  
Kazuki Omiya ◽  
Ilko Mitkov Rusinov ◽  
Susumu Suzuki ◽  
Haruo Itoh
2005 ◽  
Vol 5 (3) ◽  
pp. 693-702 ◽  
Author(s):  
M. von Hobe ◽  
J.-U. Grooß ◽  
R. Müller ◽  
S. Hrechanyy ◽  
U. Winkler ◽  
...  

Abstract. In-situ measurements of ClO and its dimer carried out during the SOLVE II/VINTERSOL-EUPLEX and ENVISAT Validation campaigns in the Arctic winter 2003 suggest that the thermal equilibrium between the dimer formation and dissociation is shifted significantly towards the monomer compared to the current JPL 2002 recommendation. Detailed analysis of observations made in thermal equilibrium allowed to re-evaluate the magnitude and temperature dependence of the equilibrium constant. A fit of the JPL format for equilibrium constants yields KEQ=3.61x10-27exp(8167/T), but to reconcile the observations made at low temperatures with the existing laboratory studies at room temperature, a modified equation, KEQ=5.47x10-25(T/300)-2.29exp(6969/T), is required. This format can be rationalised by a strong temperature dependence of the reaction enthalpy possibly induced by Cl2O2 isomerism effects. At stratospheric temperatures, both equations are practically equivalent. Using the equilibrium constant reported here rather than the JPL 2002 recommendation in atmospheric models does not have a large impact on simulated ozone loss. Solely at large zenith angles after sunrise, a small decrease of the ozone loss rate due to the ClO dimer cycle and an increase due to the ClO-BrO cycle (attributed to the enhanced equilibrium ClO concentrations) is observed, the net effect being a slightly stronger ozone loss rate.


2004 ◽  
Vol 4 (5) ◽  
pp. 5075-5102
Author(s):  
M. von Hobe ◽  
J.-U. Grooß ◽  
R. Müller ◽  
S. Hrechanyy ◽  
U. Winkler ◽  
...  

Abstract. In-situ measurements of ClO and its dimer carried out during the SOLVE II/VINTERSOL-EUPLEX and ENVISAT Validation campaigns in the Arctic winter 2003 suggest that the thermal equilibrium between the dimer formation and dissociation is shifted significantly towards the monomer compared to the current JPL 2002 recommendation. Detailed analysis of observations made in thermal equilibrium was used to re-evaluate the magnitude and temperature dependence of the equilibrium constant. A fit of the JPL format for equilibrium constants yields KEQ=4.06×10−23exp(6201/T), but to reconcile the observations made at low temperatures with the existing laboratory studies at room temperature, a modified equation, KEQ=2.31×10−13(T/300)−34.9exp( −1118/T), is required. This format can be rationalised by a strong temperature dependence of the reaction enthalpy possibly induced by Cl2O2 isomerism effects. At stratospheric temperatures, both equations are practically equivalent. Using the equilibrium constant reported here rather than the JPL 2002 recommendation in atmospheric models does not have a large impact on simulated ozone loss. Solely at large zenith angles after sunrise, a small decrease of the ozone loss rate due to the ClO dimer cycle and an increase due to the ClO-BrO cycle (attributed to the enhanced equilibrium ClO concentrations) is observed, the net effect being a slightly stronger ozone loss rate. The effects of Cl2O2 isomerism are not studied in detail, but the presence of isomers other than ClOOCl would be expected to lead to reduced ozone loss.


2003 ◽  
Vol 3 (2) ◽  
pp. 395-402 ◽  
Author(s):  
J.-U. Grooß ◽  
R. Müller

Abstract. Current stratospheric chemical model simulations underestimate substantially the large ozone loss rates that are derived for the Arctic from ozone sondes for January of some years. Until now, no explanation for this discrepancy has been found. Here, we examine the influence of intrusions of mid-latitude air into the polar vortex on these ozone loss estimates. This study focuses on the winter 1991/92, because during this winter the discrepancy between simulated and experimentally derived ozone loss rates is reported to be the largest. Also during the considered period the vortex was disturbed by a strong warming event with large-scale intrusions of mid-latitude air into the polar vortex, which is quite unusual for this time of the year. The study is based on simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS). Two methods for determination the ozone loss are investigated, the so-called vortex average approach and the Match method. The simulations for January 1992 show that the intrusions induce a reduction of vortex average ozone mixing ratio corresponding to a systematic offset of the ozone loss rate of about 12 ppb per day. This should be corrected for in the vortex average method. The simulations further suggest, that these intrusions do not cause a significant bias for the Match method due to effective quality control measures in the Match technique.


2013 ◽  
Vol 13 (10) ◽  
pp. 5299-5308 ◽  
Author(s):  
J.-P. Pommereau ◽  
F. Goutail ◽  
F. Lefèvre ◽  
A. Pazmino ◽  
C. Adams ◽  
...  

Abstract. An unprecedented ozone loss occurred in the Arctic in spring 2011. The details of the event are revisited from the twice-daily total ozone and NO2 column measurements of the eight SAOZ/NDACC (Système d'Analyse par Observation Zénithale/Network for Detection of Atmospheric Composition Changes) stations in the Arctic. It is shown that the total ozone depletion in the polar vortex reached 38% (approx. 170 DU) by the end of March, which is larger than the 30% of the previous record in 1996. Aside from the long extension of the cold stratospheric NAT PSC period, the amplitude of the event is shown to be resulting from a record daily total ozone loss rate of 0.7% d−1 after mid-February, never seen before in the Arctic but similar to that observed in the Antarctic over the last 20 yr. This high loss rate is attributed to the absence of NOx in the vortex until the final warming, in contrast to all previous winters where, as shown by the early increase of NO2 diurnal increase, partial renoxification occurs by import of NOx or HNO3 from the outside after minor warming episodes, leading to partial chlorine deactivation. The cause of the absence of renoxification and thus of high loss rate, is attributed to a vortex strength similar to that of the Antarctic but never seen before in the Arctic. The total ozone reduction on 20 March was identical to that of the 2002 Antarctic winter, which ended around 20 September, and a 15-day extension of the cold period would have been enough to reach the mean yearly amplitude of the Antarctic ozone hole. However there is no sign of trend since 1994, either in PSC (polar stratospheric cloud) volume (volume of air cold enough to allow formation of PSCs), early winter denitrification, late vortex renoxification, and vortex strength or in total ozone loss. The unprecedented large Arctic ozone loss in 2011 appears to result from an extreme meteorological event and there is no indication of possible strengthening related to climate change.


2002 ◽  
Vol 2 (6) ◽  
pp. 2489-2506
Author(s):  
J.-U. Grooß ◽  
R. Müller

Abstract. Current stratospheric chemical model simulations underestimate substantially the large ozone loss rates that are derived for the Arctic from ozone sondes for January of some years. Until now, no explanation for this discrepancy has been found. Here, we examine the influence of intrusions of mid-latitude air into the polar vortex on these ozone loss estimates. This study focuses on the winter 1991/92. It is based on simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS). The simulations for January 1992 show that the intrusions induce a reduction of vortex average ozone mixing ratio corresponding to a systematic offset of the ozone loss rate of about 12 ppb per day. Further, the results of the Match method are influenced by the intrusions, since the intruded air masses are deformed and reach dimensions below the Match radius. From our calculations we deduce a systematic offset of the Match ozone loss rate by about 10 ppb/day, which may explain about 28% of the published discrepancy between Match and box model simulations for the winter 1991/92.


2004 ◽  
Vol 26 (5) ◽  
pp. 487-497 ◽  
Author(s):  
Haruo Itoh ◽  
Tooru Suzuki ◽  
Susumu Suzuki ◽  
Ilko M. Rusinov

2005 ◽  
Vol 5 (9) ◽  
pp. 2571-2592 ◽  
Author(s):  
G. A. Morris ◽  
B. R. Bojkov ◽  
L. R. Lait ◽  
M. R. Schoeberl

Abstract. We apply the NASA Goddard Trajectory Model to data from a series of ozonesondes to derive ozone loss rates in the lower stratosphere for the AASE-2/EASOE mission (January-March 1992) and for the SOLVE/THESEO 2000 mission (January-March 2000) in an approach similar to Match. Ozone loss rates are computed by comparing the ozone concentrations provided by ozonesondes launched at the beginning and end of the trajectories connecting the launches. We investigate the sensitivity of the Match results to the various parameters used to reject potential matches in the original Match technique. While these filters effectively eliminate from consideration 80% of the matched sonde pairs and >99% of matched observations in our study, we conclude that only a filter based on potential vorticity changes along the calculated back trajectories seems warranted. Our study also demonstrates that the ozone loss rates estimated in Match can vary by up to a factor of two depending upon the precise trajectory paths calculated for each trajectory. As a result, the statistical uncertainties published with previous Match results might need to be augmented by an additional systematic error. The sensitivity to the trajectory path is particularly pronounced in the month of January, for which the largest ozone loss rate discrepancies between photochemical models and Match are found. For most of the two study periods, our ozone loss rates agree with those previously published. Notable exceptions are found for January 1992 at 475K and late February/early March 2000 at 450K, both periods during which we generally find smaller loss rates than the previous Match studies. Integrated ozone loss rates estimated by Match in both of those years compare well with those found in numerous other studies and in a potential vorticity/potential temperature approach shown previously and in this paper. Finally, we suggest an alternate approach to Match using trajectory mapping. This approach uses information from all matched observations without filtering and uses a two-parameter fit to the data to produce robust ozone loss rate estimates. As compared to loss rates from our version of Match, the trajectory mapping approach produces generally smaller loss rates, frequently not statistically significantly different from zero, calling into question the efficacy of the Match approach.


2014 ◽  
Vol 14 (1) ◽  
pp. 217-229 ◽  
Author(s):  
M. C. Parrondo ◽  
M. Gil ◽  
M. Yela ◽  
B. J. Johnson ◽  
H. A. Ochoa

Abstract. Thirteen years of ozone soundings at the Antarctic Belgrano II station (78° S, 34.6° W) have been analysed to establish a climatology of stratospheric ozone and temperature over the area. The station is inside the polar vortex during the period of development of chemical ozone depletion. Weekly periodic profiles provide a suitable database for seasonal characterization of the evolution of stratospheric ozone, especially valuable during wintertime, when satellites and ground-based instruments based on solar radiation are not available. The work is focused on ozone loss rate variability (August–October) and its recovery (November–December) at different layers identified according to the severity of ozone loss. The time window selected for the calculations covers the phase of a quasi-linear ozone reduction, around day 220 (mid-August) to day 273 (end of September). Decrease of the total ozone column over Belgrano during spring is highly dependent on the meteorological conditions. Largest depletions (up to 59%) are reached in coldest years, while warm winters exhibit significantly lower ozone loss (20%). It has been found that about 11% of the total O3 loss, in the layer where maximum depletion occurs, takes place before sunlight has arrived, as a result of transport to Belgrano of air from a somewhat lower latitude, near the edge of the polar vortex, providing evidence of mixing inside the vortex. Spatial homogeneity of the vortex has been examined by comparing Belgrano results with those previously obtained for South Pole station (SPS) for the same altitude range and for 9 yr of overlapping data. Results show more than 25% higher ozone loss rate at SPS than at Belgrano. The behaviour can be explained taking into account (i) the transport to both stations of air from a somewhat lower latitude, near the edge of the polar vortex, where sunlight reappears sooner, resulting in earlier depletion of ozone, and (ii) the accumulated hours of sunlight, which become much greater at the South Pole after the spring equinox. According to the variability of the ozone hole recovery, a clear connection between the timing of the breakup of the vortex and the monthly ozone content was found. Minimum ozone concentration of 57 DU in the 12–24 km layer remained in November, when the vortex is more persistent, while in years when the final stratospheric warming took place "very early", mean integrated ozone rose by up to 160–180 DU.


2013 ◽  
Vol 13 (1) ◽  
pp. 311-343 ◽  
Author(s):  
J.-P. Pommereau ◽  
F. Goutail ◽  
F. Lefèvre ◽  
A. Pazmino ◽  
C. Adams ◽  
...  

Abstract. An unprecedented ozone loss occurred in the Arctic in spring 2011. The details of the event are re-visited from the twice-daily total ozone and NO2 columns measurements of the eight SAOZ/NDACC (Système d'Analyse par Observation Zénitale/Network for Detection of Atmospheric Composition Changes) stations in the Arctic. It is shown that the total ozone depletion in the polar vortex reached 38% (approx. 170 DU) by the end of March that is larger than the 30% of the previous record in 1996. Asides from the long extension of the cold stratospheric NAT PSC period, the amplitude of the event is shown to be resulting from a record daily total ozone loss rate of 0.7% day−1 after mid-February, never seen before in the Arctic but similar to that observed in the Antarctic over the last 20 yr. This high loss rate is attributed to the absence of NOx in the vortex until the final warming, in contrast to all previous winters where, as shown by the early increase of NO2 diurnal increase, partial renoxification is occurring by import of NOx or HNO3 from the outside after minor warming episodes, leading to partial chlorine deactivation. The cause of the absence of renoxification and thus of high loss rate, is attributed to a vortex strength similar to that of the Antarctic but never seen before in the Arctic. The total ozone reduction on 20 March was identical to that of the 2002 Antarctic winter, which ended around 20 September, and a 15-day extension of the cold period would have been enough to reach the mean yearly amplitude of the Antarctic ozone hole. However there is no sign of trend since 1994, neither in PSC volume, early winter denitrification, late vortex renoxification, and vortex strength nor in total ozone loss. The unprecedented large Arctic ozone loss in 2011 appears to resulting from an extreme meteorological event and there is no indication of possible strengthening related to climate change.


2013 ◽  
Vol 13 (6) ◽  
pp. 15663-15695
Author(s):  
M. C. Parrondo ◽  
M. Gil ◽  
M. Yela ◽  
B. J. Johnson ◽  
H. A. Ochoa

Abstract. 13 yr of ozonesoundings at the Antarctic Belgrano II station (78° S, 34.6° W) have been analyzed to establish a climatology of stratospheric ozone and temperature over the area. The station is inside the polar vortex during the period of development of chemical ozone depletion. Weekly periodic profiles provide a suitable database for seasonal characterization of the evolution of stratospheric ozone, especially valuable during winter time when satellites and ground-based instruments based on solar radiation are lacking. The work is focused on ozone loss rate variability (August–October) and its recovery (November–December) at different layers identified according to the severity of ozone loss. The time window selected for the calculations covers the phase of a quasi-linear ozone reduction, about day 220 (mid August) to day 273 (end of September). Decrease of the total ozone column over Belgrano during spring is highly dependent on the meteorological conditions. Largest depletions (up to 59%) are reached in coldest years while warms winters exhibit significantly lower ozone loss (20%). It has been found that about 11% of the total O3 loss in the layer where maximum depletion occurs takes place before the sun has arrived as a result of transport of lower latitude air masses, providing evidence of mixing inside the vortex. Spatial homogeneity of the vortex has been examined by comparing Belgrano results with those previously obtained for South Pole Station (SPS) for the same altitude range and for 9 yr of overlapping data. Unexpected results show more than 25% larger ozone loss rate at SPS than at Belgrano. It has been found that the accumulated hours of sunlight are the dominant factor driving the ozone loss rate. According to the variability of the ozone-hole recovery, a clear connection between the timing of the breakup of the vortex and the monthly ozone content was found. Minimum ozone concentration of 57 DU in the 12–24 km layer remained in November for the longest vortex, while years when the final stratospheric warming took "very early", mean integrated ozone rises up to 160–180 DU.


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