scholarly journals A re-evaluation of the ClO/Cl<sub>2</sub>O<sub>2</sub> equilibrium constant based on stratospheric in-situ observations

2004 ◽  
Vol 4 (5) ◽  
pp. 5075-5102
Author(s):  
M. von Hobe ◽  
J.-U. Grooß ◽  
R. Müller ◽  
S. Hrechanyy ◽  
U. Winkler ◽  
...  
Keyword(s):  
Temperature Dependence ◽  
Equilibrium Constant ◽  
Thermal Equilibrium ◽  
Loss Rate ◽  
Equilibrium Constants ◽  
The Arctic ◽  
Strong Temperature Dependence ◽  
Atmospheric Models ◽  
Ozone Loss

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.

scholarly journals A re-evaluation of the ClO/Cl<sub>2</sub>O<sub>2</sub> equilibrium constant based on stratospheric in-situ observations

2005 ◽  
Vol 5 (3) ◽  
pp. 693-702 ◽  
Author(s):  
M. von Hobe ◽  
J.-U. Grooß ◽  
R. Müller ◽  
S. Hrechanyy ◽  
U. Winkler ◽  
...  
Keyword(s):  
Temperature Dependence ◽  
Equilibrium Constant ◽  
Thermal Equilibrium ◽  
Loss Rate ◽  
Equilibrium Constants ◽  
The Arctic ◽  
Strong Temperature Dependence ◽  
Atmospheric Models ◽  
Ozone Loss

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.

Temperature Dependence of Ozone Loss Rate

2013 ◽  
Vol 133 (9) ◽  
pp. 465-470
Author(s):  
Kazuki Omiya ◽  
Ilko Mitkov Rusinov ◽  
Susumu Suzuki ◽  
Haruo Itoh
Keyword(s):  
Temperature Dependence ◽  
Loss Rate ◽  
Ozone Loss

scholarly journals The impact of mid-latitude intrusions into the polar vortex on ozone loss estimates

2003 ◽  
Vol 3 (2) ◽  
pp. 395-402 ◽  
Author(s):  
J.-U. Grooß ◽  
R. Müller
Keyword(s):  
Large Scale ◽  
Loss Rate ◽  
Polar Vortex ◽  
Control Measures ◽  
Lagrangian Model ◽  
The Arctic ◽  
Match Method ◽  
Ozone Loss ◽  
The Impact ◽  
Loss Rates

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.

scholarly journals Why unprecedented ozone loss in the Arctic in 2011? Is it related to climate change?

2013 ◽  
Vol 13 (10) ◽  
pp. 5299-5308 ◽  
Author(s):  
J.-P. Pommereau ◽  
F. Goutail ◽  
F. Lefèvre ◽  
A. Pazmino ◽  
C. Adams ◽  
...  
Keyword(s):  
Climate Change ◽  
Total Ozone ◽  
Loss Rate ◽  
The Arctic ◽  
Vortex Strength ◽  
High Loss ◽  
Ozone Loss ◽  
The Antarctic ◽  
High Loss Rate ◽  
Daily Total

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.

scholarly journals The impact of mid-latitude intrusions into the polar vortex on ozone loss estimates

2002 ◽  
Vol 2 (6) ◽  
pp. 2489-2506
Author(s):  
J.-U. Grooß ◽  
R. Müller
Keyword(s):  
Loss Rate ◽  
Polar Vortex ◽  
Lagrangian Model ◽  
The Arctic ◽  
Mixing Ratio ◽  
Match Method ◽  
Air Masses ◽  
Model Simulations ◽  
Ozone Loss ◽  
The Impact

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.

Applications of In Situ Ellipsometry in RTP Temperature Measurement and Process Control

1991 ◽  
Vol 224 ◽  
Author(s):  
Hisham Z. Massoud ◽  
Ronald K. Sampson ◽  
Kevin A. Conrad ◽  
Yao-Zhi Hu ◽  
Eugene A. Irene
Keyword(s):  
Temperature Dependence ◽  
Thermal Processing ◽  
Rapid Thermal Processing ◽  
Index Of Refraction ◽  
Strong Temperature Dependence ◽  
Heating And Cooling ◽  
Wafer Processing ◽  
And Control ◽  
Measurement And Control

AbstractThe applications of in situ automated ellipsometry in the measurement and control of temperature in rapid-thermal processing (RTP) equipment are investigated. This technique relies on the accurate measurement of the index of refraction of a wafer using ellipsometry and the strong temperature dependence of the index of refraction to determine the wafer temperature. In principle, this technique is not limited to silicon wafer processing and could be applied to any surface whose index of refraction has a strong and well known temperature dependence. This technique is non-invasive, non-contact, fast, accurate, compatible with ultraclean processing, and lends itself to monitoring the dynamic heating and cooling cycles encountered in rapid-thermal processing.

scholarly journals Nitric acid trihydrate (NAT) formation at low NAT supersaturations

2004 ◽  
Vol 4 (6) ◽  
pp. 8579-8607 ◽  
Author(s):  
C. Voigt ◽  
H. Schlager ◽  
B. P. Luo ◽  
A. Dörnbrack ◽  
A. Roiger ◽  
...  
Keyword(s):  
Nitric Acid ◽  
High Altitude ◽  
Equilibrium Temperature ◽  
In Situ Measurements ◽  
The Arctic ◽  
Ozone Loss ◽  
Polar Stratospheric Cloud ◽  
Research Aircraft ◽  
Polar Ozone

Abstract. A polar stratospheric cloud (PSC) was observed on 6 February 2003 in the Arctic stratosphere by in-situ measurements onboard the high-altitude research aircraft Geophysica. Low number densities (~10−4 cm−3) of nitric acid (HNO3) containing particles – probably NAT – with diameters up to 6 µm were measured at altitudes between 18 and 20 km. These particles have the potential to grow further and to remove HNO3 from the stratosphere, thereby enhancing polar ozone loss. Interestingly, the NAT particles formed in less than a day at temperatures T>TNAT−3.5 K, just slightly below the NAT equilibrium temperature TNAT. This unique measurement of PSC formation at extremely low NAT saturation ratios (SNAT≤11) constrains current NAT nucleation theories. In particular, NAT formation on ice can for certain be excluded. Conversely, we suggest that meteoritic particles may be favorable candidates for triggering nucleation of NAT at the observed low number densities.

scholarly journals Ozone loss derived from balloon-borne tracer measurements and the SLIMCAT CTM

2004 ◽  
Vol 4 (6) ◽  
pp. 7089-7120 ◽  
Author(s):  
A. D. Robinson ◽  
G. A. Millard ◽  
F. Danis ◽  
M. Guirlet ◽  
N. R. P. Harris ◽  
...  
Keyword(s):  
Vertical Distribution ◽  
Reasonable Agreement ◽  
The Arctic ◽  
Data Sets ◽  
Gas Chromatograph ◽  
Ozone Loss ◽  
Empirical Estimates ◽  
Vertical Distributions ◽  
Good Agreement

Abstract. Balloon-borne measurements of CFC-11 (on flights of the DIRAC in situ gas chromatograph and the DESCARTES grab sampler), ClO and O3 were made during the 1999/2000 winter as part of the SOLVE-THESEO 2000 campaign. Here we present the CFC-11 data from nine flights and compare them first with data from other instruments which flew during the campaign and then with the vertical distributions calculated by the SLIMCAT 3-D CTM. We calculate ozone loss inside the Arctic vortex between late January and early March using the relation between CFC-11 and O3 measured on the flights, the peak ozone loss (1200 ppbv) occurs in the 440–470 K region in early March in reasonable agreement with other published empirical estimates. There is also a good agreement between ozone losses derived from three independent balloon tracer data sets used here. The magnitude and vertical distribution of the loss derived from the measurements is in good agreement with the loss calculated from SLIMCAT over Kiruna for the same days.

scholarly journals Characteristics of tropospheric ozone depletion events in the Arctic spring: analysis of the ARCTAS, ARCPAC, and ARCIONS measurements and satellite BrO observations

2012 ◽  
Vol 12 (20) ◽  
pp. 9909-9922 ◽  
Author(s):  
J.-H. Koo ◽  
Y. Wang ◽  
T. P. Kurosu ◽  
K. Chance ◽  
A. Rozanov ◽  
...  
Keyword(s):  
Correlation Analysis ◽  
Ozone Depletion ◽  
Tropospheric Ozone ◽  
The Arctic ◽  
Satellite Measurements ◽  
Air Mass ◽  
Ozone Loss ◽  
Time Lagged ◽  
Lagged Correlation

Abstract. Arctic ozone depletion events (ODEs) are caused by halogen catalyzed ozone loss. In situ chemistry, advection of ozone-poor air mass, and vertical mixing in the lower troposphere are important factors affecting ODEs. To better characterize the ODEs, we analyze the combined set of surface, ozonesonde, and aircraft in situ measurements of ozone and bromine compounds during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC), and the Arctic Intensive Ozonesonde Network Study (ARCIONS) experiments (April 2008). Tropospheric BrO columns retrieved from satellite measurements and back trajectory calculations are also used to investigate the characteristics of observed ODEs. In situ observations from these field experiments are inadequate to validate tropospheric BrO columns derived from satellite measurements. In view of this difficulty, we construct an ensemble of tropospheric column BrO estimates from two satellite (OMI and GOME-2) measurements and with three independent methods of calculating stratospheric BrO columns. Furthermore, we select analysis methods that do not depend on the absolute magnitude of column BrO, such as time-lagged correlation analysis of ozone and tropospheric column BrO, to understand characteristics of ODEs. Time-lagged correlation analysis between in situ (surface and ozonesonde) measurements of ozone and satellite derived tropospheric BrO columns indicates that the ODEs are due to either local halogen-driven ozone loss or short-range (∼1 day) transport from nearby regions with ozone depletion. The effect of in situ ozone loss is also evident in the diurnal variation difference between low (10th and 25th percentiles) and higher percentiles of surface ozone concentrations at Alert, Canada. Aircraft observations indicate low-ozone air mass transported from adjacent high-BrO regions. Correlation analyses of ozone with potential temperature and time-lagged tropospheric BrO column show that the vertical extent of local ozone loss is surprisingly deep (1–2 km) at Resolute and Churchill, Canada. The unstable boundary layer during ODEs at Churchill could potentially provide a source of free-tropospheric BrO through convective transport and explain the significant negative correlation between free-tropospheric ozone and tropospheric BrO column at this site.

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