scholarly journals Chlorine partitioning near the polar vortex boundary observed with ground-based FTIR and satellites at Syowa Station, Antarctica in 2007 and 2011

2019 ◽  
Author(s):  
Hideaki Nakajima ◽  
Isao Murata ◽  
Yoshihiro Nagahama ◽  
Hideharu Akiyoshi ◽  
Kosuke Saeki ◽  
...  

Abstract. We retrieved lower stratospheric vertical profiles of O3, HNO3, and HCl from solar spectra taken with a ground-based Fourier-Transform infrared spectrometer (FTIR) installed at Syowa Station, Antarctica (69.0° S, 39.6° E) from March to December 2007 and September to November 2011. This was the first continuous measurements of chlorine species throughout the ozone hole period from the ground in Antarctica. We analyzed temporal variation of these species combined with ClO, HCl, and HNO3 data taken with the Aura/MLS (Microwave Limb Sounder) satellite sensor, and ClONO2 data taken with the Envisat/MIPAS (The Michelson Interferometer for Passive Atmospheric Sounding) satellite sensor at 18 and 22 km over Syowa Station. HCl and ClONO2 decrease occurred at both 18 and 22 km, and soon ClONO2 was almost depleted in early winter. When the sun returned to Antarctica in spring, enhancement of ClO and gradual O3 destruction were observed. During the ClO enhanced period, negative correlation between ClO and ClONO2 was observed in the time-series of the data at Syowa Station. This negative correlation was associated with the distance between Syowa Station and the inner edge of the polar vortex. We used MIROC3.2 Chemistry-Climate Model (CCM) results to see the comprehensive behavior of chlorine and related species inside the polar vortex and the edge region in more detail. From CCM model results, rapid conversion of chlorine reservoir species (HCl and ClONO2) into Cl2, gradual conversion of Cl2 into Cl2O2, increase of ClO when sunlight became available, and conversion of ClO into HCl, was successfully reproduced. HCl decrease in the winter polar vortex core continued to occur due to the transport of ClONO2 from the subpolar region to higher latitudes, providing a flux of ClONO2 from more sunlit latitudes into the polar vortex. Temporal variation of chlorine species over Syowa Station was affected by both heterogeneous chemistry related to Polar Stratospheric Cloud (PSC) occurrence deep inside the polar vortex, and transport of an NOx-rich airmass from lower latitudinal polar vortex boundary region which can produce additional ClONO2 by reaction of ClO with NO2. The deactivation pathways from active chlorine into reservoir species (HCl and/or ClONO2) were found to be highly dependent on the availability of ambient O3. At an altitude where most ozone was depleted in Antarctica (18 km), most ClO was converted to HCl. However, at an altitude where there were some O3 available (22 km), additional increase of ClONO2 from initial value can occur, similar to the case in the Arctic.

2020 ◽  
Vol 20 (2) ◽  
pp. 1043-1074
Author(s):  
Hideaki Nakajima ◽  
Isao Murata ◽  
Yoshihiro Nagahama ◽  
Hideharu Akiyoshi ◽  
Kosuke Saeki ◽  
...  

Abstract. We retrieved lower stratospheric vertical profiles of O3, HNO3, and HCl from solar spectra taken with a ground-based Fourier transform infrared spectrometer (FTIR) installed at Syowa Station, Antarctica (69.0∘ S, 39.6∘ E), from March to December 2007 and September to November 2011. This was the first continuous measurement of chlorine species throughout the ozone hole period from the ground in Antarctica. We analyzed temporal variation of these species combined with ClO, HCl, and HNO3 data taken with the Aura MLS (Microwave Limb Sounder) satellite sensor and ClONO2 data taken with the Envisat MIPAS (the Michelson Interferometer for Passive Atmospheric Sounding) satellite sensor at 18 and 22 km over Syowa Station. An HCl and ClONO2 decrease occurred from the end of May at both 18 and 22 km, and eventually, in early winter, both HCl and ClONO2 were almost depleted. When the sun returned to Antarctica in spring, enhancement of ClO and gradual O3 destruction were observed. During the ClO-enhanced period, a negative correlation between ClO and ClONO2 was observed in the time series of the data at Syowa Station. This negative correlation was associated with the relative distance between Syowa Station and the edge of the polar vortex. We used MIROC3.2 chemistry–climate model (CCM) results to investigate the behavior of whole chlorine and related species inside the polar vortex and the boundary region in more detail. From CCM model results, the rapid conversion of chlorine reservoir species (HCl and ClONO2) into Cl2, gradual conversion of Cl2 into Cl2O2, increase in HOCl in the winter period, increase in ClO when sunlight became available, and conversion of ClO into HCl were successfully reproduced. The HCl decrease in the winter polar vortex core continued to occur due to both transport of ClONO2 from the subpolar region to higher latitudes, providing a flux of ClONO2 from more sunlit latitudes into the polar vortex, and the heterogeneous reaction of HCl with HOCl. The temporal variation of chlorine species over Syowa Station was affected by both heterogeneous chemistries related to polar stratospheric cloud (PSC) occurrence inside the polar vortex and transport of a NOx-rich air mass from the polar vortex boundary region, which can produce additional ClONO2 by reaction of ClO with NO2. The deactivation pathways from active chlorine into reservoir species (HCl and/or ClONO2) were confirmed to be highly dependent on the availability of ambient O3. At 18 km, where most ozone was depleted, most ClO was converted to HCl. At 22 km where some O3 was available, an additional increase in ClONO2 from the prewinter value occurred, similar to the Arctic.


2020 ◽  
Author(s):  
Hideaki Nakajima ◽  
Isao Murata ◽  
Yoshihiro Nagahama ◽  
Hideharu Akiyoshi ◽  
Takeshi Kinase ◽  
...  

<p>We retrieved lower stratospheric vertical profiles of O<sub>3</sub>, HNO<sub>3</sub>, and HCl from solar spectra taken with a ground-based Fourier-Transform infrared spectrometer (FTIR) installed at Syowa Station, Antarctica (69.0°S, 39.6°E) from March to December 2007 and September to November 2011.  This was the first continuous measurements of chlorine species throughout the ozone hole period from the ground in Antarctica.  We analyzed temporal variation of these species combined with ClO, HCl, and HNO<sub>3</sub> data taken with the Aura/MLS (Microwave Limb Sounder) satellite sensor, and ClONO<sub>2</sub> data taken with the Envisat/MIPAS (The Michelson Interferometer for Passive Atmospheric Sounding) satellite sensor at 18 and 22 km over Syowa Station.  HCl and ClONO<sub>2</sub> decrease occurred from the end of May at both 18 and 22 km, and eventually in early winter, both HCl and ClONO<sub>2</sub> were almost depleted.  When the sun returned to Antarctica in spring, enhancement of ClO and gradual O<sub>3</sub> destruction were observed.  During the ClO enhanced period, negative correlation between ClO and ClONO<sub>2</sub> was observed in the time-series of the data at Syowa Station.  This negative correlation was associated with the relative distance between Syowa Station and the edge of the polar vortex.  We used MIROC3.2 Chemistry-Climate Model (CCM) results to investigate the behavior of whole chlorine and related species inside the polar vortex and the boundary region in more detail.  From CCM model results, rapid conversion of chlorine reservoir species (HCl and ClONO<sub>2</sub>) into Cl<sub>2</sub>, gradual conversion of Cl<sub>2</sub> into Cl<sub>2</sub>O<sub>2</sub>, increase of HOCl in winter period, increase of ClO when sunlight became available, and conversion of ClO into HCl, was successfully reproduced.  HCl decrease in the winter polar vortex core continued to occur due to both transport of ClONO<sub>2</sub> from the subpolar region to higher latitudes, providing a flux of ClONO<sub>2</sub> from more sunlit latitudes into the polar vortex, and the heterogeneous reaction of HCl with HOCl.  Temporal variation of chlorine species over Syowa Station was affected by both heterogeneous chemistries related to Polar Stratospheric Cloud (PSC) occurrence inside the polar vortex, and transport of a NOx-rich airmass from the polar vortex boundary region which can produce additional ClONO<sub>2</sub> by reaction of ClO with NO<sub>2</sub>.  The deactivation pathways from active chlorine into reservoir species (HCl and/or ClONO<sub>2</sub>) were confirmed to be highly dependent on the availability of ambient O<sub>3</sub>.  At 18 km where most ozone was depleted, most ClO was converted to HCl.  At 22km where some O<sub>3</sub> was available, additional increase of ClONO<sub>2</sub> from pre-winter value occurred, similar as in the Arctic.</p>


2018 ◽  
Author(s):  
Hideaki Nakajima ◽  
Isao Murata ◽  
Yoshihiro Nagahama ◽  
Hideharu Akiyoshi ◽  
Kosuke Saeki ◽  
...  

Abstract. To understand and project future ozone recovery, understanding of mechanisms related to polar ozone destruction is crucial. For polar stratospheric ozone destruction, chlorine species play an important role, but detailed temporal evolution of chlorine species in the Antarctic winter is not well understood. We retrieved lower stratospheric vertical profiles of O3, HNO3, and HCl from solar spectra taken with a ground-based Fourier-Transform infrared spectrometer (FTIR) installed at Syowa Station, Antarctica (69.0º S, 39.6º E) from March to December 2007 and September to November 2011. We analyzed temporal variation of these species combined with ClO, HCl, and HNO3 data taken with the Aura/MLS (Microwave Limb Sounder) satellite sensor, and ClONO2 data taken with the Envisat/MIPAS (The Michelson Interferometer for Passive Atmospheric Sounding) satellite sensor at 18 and 22 km over Syowa Station. When the stratospheric temperature over Syowa Station fell below polar stratospheric cloud (PSC) saturation temperature in early winter, PSCs started to form and heterogeneous reaction on PSCs convert chlorine reservoirs into reactive chemical species. HCl and ClONO2 decrease occurred at both 18 and 22 km, and soon ClONO2 was almost depleted in early winter. When the sun returned to Antarctica in spring, enhancement of ClO and gradual O3 destruction were observed. During the ClO enhanced period, negative correlation between ClO and ClONO2 was observed in the time-series of the data at Syowa Station. This negative correlation was associated with the distance between Syowa Station and the inner edge of the polar vortex. Temporal variation of chlorine species over Syowa Station was affected by both heterogeneous chemistry related to PSC occurrence deep inside the polar vortex, and transport of an NONOx-rich airmass from lower latitudinal polar vortex boundary region which can produce additional ClONO2 by reaction between ClO and NO2. We used MIROC3.2 Chemistry-Climate Model (CCM) results to see the comprehensive behavior of chlorine and related species inside the polar vortex and the edge region in more detail. Rapid conversion of chlorine reservoir species (HCl and ClONO2) into Cl2, gradual conversion of Cl2 into Cl2O2, increase of ClO when sunlight became available, and conversion of ClO into HCl, was successfully reproduced by the CCM. HCl decrease in the winter polar vortex core continued to occur due to the transport of ClONO2 from the subpolar region (55–65º S) to higher latitudes (65–75º S), providing a flux of ClONO2 from more sunlit latitudes into the polar vortex. The deactivation pathways from active ClO into reservoir species (HCl and/or ClONO2) were found to be highly dependent on the availability of ambient O3 and NOx. At an altitude where most ozone was depleted in Antarctica, most ClO was converted to HCl. However, when there were some O3 and NOx available, super-recovery of ClONO2 can occur, similar to the case in the Arctic.


2012 ◽  
Vol 12 (14) ◽  
pp. 6581-6592 ◽  
Author(s):  
G. Wetzel ◽  
H. Oelhaf ◽  
O. Kirner ◽  
F. Friedl-Vallon ◽  
R. Ruhnke ◽  
...  

Abstract. The winter 2009/2010 was characterized by a strong Arctic vortex with extremely cold mid-winter temperatures in the lower stratosphere associated with an intense activation of reactive chlorine compounds (ClOx) from reservoir species. Stratospheric limb emission spectra were recorded during a flight of the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 24 January 2010 inside the Arctic vortex. Several fast limb sequences of spectra (in time steps of about 10 min) were measured from nighttime photochemical equilibrium to local noon allowing the retrieval of chlorine- and nitrogen-containing species which change rapidly their concentration around the terminator between night and day. Mixing ratios of species like ClO, NO2, and N2O5 show significant changes around sunrise, which are temporally delayed due to polar stratospheric clouds reducing the direct radiative flux from the sun. ClO variations were derived for the first time from MIPAS-B spectra. Daytime ClO values of up to 1.6 ppbv are visible in a broad chlorine activated layer below 26 km correlated with low values (below 0.1 ppbv) of the chlorine reservoir species ClONO2. Observations are compared and discussed with calculations performed with the 3-dimensional Chemistry Climate Model EMAC (ECHAM5/MESSy Atmospheric Chemistry). Mixing ratios of the species ClO, NO2, and N2O5 are well reproduced by the model during night and noon. However, the onset of ClO production and NO2 loss around the terminator in the model is not consistent with the measurements. The MIPAS-B observations along with Tropospheric Ultraviolet-Visible (TUV) radiation model calculations suggest that polar stratospheric clouds lead to a delayed start followed by a faster increase of the photodissoziation of ClOOCl and NO2 near the morning terminator since stratospheric clouds alter the direct and the diffuse flux of solar radiation. These effects are not considered in the EMAC model simulations which assume a cloudless atmosphere.


2017 ◽  
Author(s):  
Gerald Wetzel ◽  
Hermann Oelhaf ◽  
Michael Höpfner ◽  
Felix Friedl-Vallon ◽  
Andreas Ebersoldt ◽  
...  

Abstract. The first stratospheric measurements of the diurnal variation of the inorganic bromine (Bry) reservoir species BrONO2 around sunrise and sunset are reported. Arctic flights of the balloon-borne Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) were carried out from Kiruna (68°N, Sweden) in January 2010 and March 2011 inside the stratospheric polar vortices where diurnal variations of BrONO2 around sunrise have been observed. High nighttime BrONO2 volume mixing ratios of up to 21 parts per trillion by volume (pptv) were detected in the late winter 2011 in the absence of polar stratospheric clouds (PSCs). In contrast, the amount of measured BrONO2 was significantly lower in January 2010 due to low available NO2 amounts (for the build-up of BrONO2), heterogeneous destruction of BrONO2 on PSC particles, and the gas-phase interaction of BrO (the source to form BrONO2) with ClO. A further balloon flight took place at mid-latitudes from Timmins (49°N, Canada) in September 2014. Mean BrONO2 mixing ratios of 22 pptv were observed after sunset in the altitude region between 21 and 29 km. Measurements are compared and discussed with the results of a multi-year simulation performed with the chemistry climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC). The calculated temporal variation of BrONO2 is in principal agreement with the balloon-borne observations. Using the nighttime simulated ratio between BrONO2 and Bry, the amount of Bry observed by MIPAS-B was estimated to about 21–25 pptv in the lower stratosphere.


2015 ◽  
Vol 15 (14) ◽  
pp. 8065-8076 ◽  
Author(s):  
G. Wetzel ◽  
H. Oelhaf ◽  
M. Birk ◽  
A. de Lange ◽  
A. Engel ◽  
...  

Abstract. The Arctic winter 2010/2011 was characterized by a persistent vortex with extremely low temperatures in the lower stratosphere above northern Scandinavia leading to a strong activation of chlorine compounds (ClOx) like Cl, Cl2, ClO, ClOOCl, OClO, and HOCl, which rapidly destroyed ozone when sunlight returned after winter solstice. The MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding) and TELIS (TErahertz and submillimeter LImb Sounder) balloon measurements obtained in northern Sweden on 31 March 2011 inside the polar vortex have provided vertical profiles of inorganic and organic chlorine species as well as diurnal variations of ClO around sunrise over the whole altitude range in which chlorine has been undergoing activation and deactivation. This flight was performed at the end of the winter during the last phase of ClOx deactivation. The complete inorganic and organic chlorine partitioning and budget for 31 March 2011, assumed to be representative for the late-winter Arctic stratosphere, has been derived by combining MIPAS-B and TELIS simultaneously observed molecules. A total chlorine amount of 3.41 ± 0.30 parts per billion by volume is inferred from the measurements (above 24 km). This value is in line with previous stratospheric observations carried out outside the tropics confirming the slightly decreasing chlorine amount in the stratosphere. Observations are compared and discussed with the output of a multi-year simulation performed with the chemistry climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry). The simulated stratospheric total chlorine amount is in accordance with the MIPAS-B/TELIS observations, taking into account the fact that some chlorine source gases and very short-lived species are not included in the model.


2015 ◽  
Vol 15 (4) ◽  
pp. 5391-5422
Author(s):  
G. Wetzel ◽  
H. Oelhaf ◽  
M. Birk ◽  
A. de Lange ◽  
A. Engel ◽  
...  

Abstract. The Arctic winter 2010/11 was characterized by a persisting vortex with extremely cold temperatures in the lower stratosphere above northern Scandinavia leading to a strong activation of chlorine compounds (ClOx) like Cl, Cl2, ClO, ClOOCl, OClO, and HOCl which rapidly destroyed ozone when sunlight returned after winter solstice. MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) and TELIS (Terahertz and submillimeter Limb Sounder) balloon measurements obtained in northern Sweden on 31 March 2011 inside the polar vortex have provided vertical profiles of inorganic and organic chlorine species as well as diurnal variations of ClO around sunrise over the whole altitude range in which chlorine is undergoing activation and deactivation. This flight was performed at the end of the winter during the last phase of ClOx deactivation. The complete inorganic and organic chlorine partitioning and budget in the stratosphere has been derived by combining MIPAS-B and TELIS simultaneously observed molecules. A total chlorine amount of 3.41 ± 0.30 ppbv is inferred from the measurements. This value is in line with previously carried out stratospheric observations confirming the slightly decreasing chlorine trend in the stratosphere. Observations are compared and discussed with the output of a multi-year simulation performed with the Chemistry Climate Model EMAC (ECHAM5/MESSy Atmospheric Chemistry). The simulated stratospheric total chlorine amount is in accordance with the MIPAS-B/TELIS observation taking into account the fact that some chlorine source gases and very short lived species are not included in the model.


2017 ◽  
Vol 17 (23) ◽  
pp. 14631-14643
Author(s):  
Gerald Wetzel ◽  
Hermann Oelhaf ◽  
Michael Höpfner ◽  
Felix Friedl-Vallon ◽  
Andreas Ebersoldt ◽  
...  

Abstract. The first stratospheric measurements of the diurnal variation in the inorganic bromine (Bry) reservoir species BrONO2 around sunrise and sunset are reported. Arctic flights of the balloon-borne Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) were carried out from Kiruna (68° N, Sweden) in January 2010 and March 2011 inside the stratospheric polar vortices where diurnal variations of BrONO2 around sunrise have been observed. High nighttime BrONO2 volume mixing ratios of up to 21 pptv (parts per trillion by volume) were detected in late winter 2011 in the absence of polar stratospheric clouds (PSCs). In contrast, the amount of measured BrONO2 was significantly lower in January 2010 due to low available NO2 amounts (for the build-up of BrONO2), the heterogeneous destruction of BrONO2 on PSC particles, and the gas-phase interaction of BrO (the source to form BrONO2) with ClO. A further balloon flight took place at midlatitudes from Timmins (49° N, Canada) in September 2014. Mean BrONO2 mixing ratios of 22 pptv were observed after sunset in the altitude region between 21 and 29 km. Measurements are compared and discussed with the results of a multi-year simulation performed with the chemistry climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC). The calculated temporal variation in BrONO2 largely reproduces the balloon-borne observations. Using the nighttime simulated ratio between BrONO2 and Bry, the amount of Bry observed by MIPAS-B was estimated to be about 21–25 pptv in the lower stratosphere.


Atmosphere ◽  
2021 ◽  
Vol 12 (5) ◽  
pp. 625
Author(s):  
Ansgar Schanz ◽  
Klemens Hocke ◽  
Niklaus Kämpfer ◽  
Simon Chabrillat ◽  
Antje Inness ◽  
...  

In this study, we compare the diurnal variation in stratospheric ozone of the MACC (Monitoring Atmospheric Composition and Climate) reanalysis, ECMWF Reanalysis Interim (ERA-Interim), and the free-running WACCM (Whole Atmosphere Community Climate Model). The diurnal variation of stratospheric ozone results from photochemical and dynamical processes depending on altitude, latitude, and season. MACC reanalysis and WACCM use similar chemistry modules and calculate a similar diurnal cycle in ozone when it is caused by a photochemical variation. The results of the two model systems are confirmed by observations of the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) experiment and three selected sites of the Network for Detection of Atmospheric Composition Change (NDACC) at Mauna Loa, Hawaii (tropics), Bern, Switzerland (midlatitudes), and Ny-Ålesund, Svalbard (high latitudes). On the other hand, the ozone product of ERA-Interim shows considerably less diurnal variation due to photochemical variations. The global maxima of diurnal variation occur at high latitudes in summer, e.g., near the Arctic NDACC site at Ny-Ålesund, Svalbard. The local OZORAM radiometer observes this effect in good agreement with MACC reanalysis and WACCM. The sensed diurnal variation at Ny-Ålesund is up to 8% (0.4 ppmv) due to photochemical variations in summer and negligible during the dynamically dominated winter. However, when dynamics play a major role for the diurnal ozone variation as in the lower stratosphere (100–20 hPa), the reanalysis models ERA-Interim and MACC which assimilate data from radiosondes and satellites outperform the free-running WACCM. Such a domain is the Antarctic polar winter where a surprising novel feature of diurnal variation is indicated by MACC reanalysis and ERA-Interim at the edge of the polar vortex. This effect accounts for up to 8% (0.4 ppmv) in both model systems. In summary, MACC reanalysis provides a global description of the diurnal variation of stratospheric ozone caused by dynamics and photochemical variations. This is of high interest for ozone trend analysis and other research which is based on merged satellite data or measurements at different local time.


Author(s):  
Yousuke Yamashita ◽  
Hideharu Akiyoshi ◽  
Masaaki Takahashi

Arctic ozone amount in winter to spring shows large year-to-year variation. This study investigates Arctic spring ozone in relation to the phase of quasi-biennial oscillation (QBO)/the 11-year solar cycle, using satellite observations, reanalysis data, and outputs of a chemistry climate model (CCM) during the period of 1979–2011. For this duration, we found that the composite mean of the Northern Hemisphere high-latitude total ozone in the QBO-westerly (QBO-W)/solar minimum (Smin) phase is slightly smaller than those averaged for the QBO-W/Smax and QBO-E/Smax years in March. An analysis of a passive ozone tracer in the CCM simulation indicates that this negative anomaly is primarily caused by transport. The negative anomaly is consistent with a weakening of the residual mean downward motion in the polar lower stratosphere. The contribution of chemical processes estimated using the column amount difference between ozone and the passive ozone tracer is between 10–20% of the total anomaly in March. The lower ozone levels in the Arctic spring during the QBO-W/Smin years are associated with a stronger Arctic polar vortex from late winter to early spring, which is linked to the reduced occurrence of sudden stratospheric warming in the winter during the QBO-W/Smin years.


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