ClO Mixing Ratios Research Articles

OClO and BrO observations in the volcanic plume of Mt. Etna – implications on the chemistry of chlorine and bromine species in volcanic plumes

Abstract. Spatial and temporal profiles of chlorine dioxide (OClO), bromine monoxide (BrO) and sulfur dioxide (SO2) of the volcanic plume at Mt. Etna, Italy, were investigated in September 2012 using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS). OClO was detected in 119 individual measurements covering plume ages up to 6 min. BrO could be detected in 452 spectra up to 23 min downwind. The retrieved slant column densities (SCDs) reached maximum values of 2.0 × 1014 molecules cm-2 (OClO) and 1.1 × 1015 molecules cm-2 (BrO). Mean mixing ratios of BrO and OClO were estimated assuming a circular plume cross section. Furthermore, ClO mixing ratios were derived directly from the BrO and OClO-SCDs. Average abundances of BrO = 1.35 ppb, OClO = 300 ppt and ClO = 139 ppt were found in the young plume (plume age τ < 4 min) with peak values of 2.7 ppb (BrO), 600 ppt (OClO) and 235 ppt (ClO) respectively. The chemical evolution of BrO and OClO in the plume was investigated in great detail by analysing the OClO/SO2 and BrO/SO2 ratios as a function of plume age τ. A marked increase of both ratios was observed in the young plume (τ < 142 s) and a levelling off at larger plume ages showing mean SO2 ratios of 3.17 × 10-5 (OClO/SO2) and 1.65 × 10-4 (BrO/SO2). OClO was less abundant in the plume compared to BrO with a mean OClO/BrO ratio of 0.16 at plume ages exceeding 3 min. A measurement performed in the early morning at low solar radiances revealed BrO/SO2 and OClO/SO2 ratios increasing with time. This observation substantiates the importance of photochemistry regarding the formation of BrO and OClO in volcanic plumes. These findings support the current understanding of the underlying chemistry, namely, that BrO is formed in an autocatalytic, heterogeneous reaction mechanism (in literature often referred to as "bromine explosion") and that OClO is formed in the reaction of OClO with BrO. These new findings, especially the very detailed observation of the BrO and OClO formation in the young plume, were used to infer the prevailing Cl-atom concentrations in the plume. Relatively small values ranging from [Cl] = 2.5 × 106 cm-3 (assuming 80 ppb background O3) to [Cl] = 2.0 × 108 cm-3 (at 1 ppb O3) were calculated at plume ages of about 2 min. Based on these Cl abundances, a potential – chlorine-induced – depletion of tropospheric methane (CH4) in the plume was investigated. CH4 lifetimes between 14 h (at 1 ppb O3) and 47 days (at 80 ppb O3) were derived. While these lifetimes are considerably shorter than the atmospheric lifetime of CH4, the impact of gaseous chlorine on the CH4 budget in the plume environment should nevertheless be relatively small due to plume dispersion (decreasing Cl concentrations) and ongoing mixing of the plume with the surrounding atmosphere (replenishing O3 and CH4). In addition, all spectra were analysed for signatures of IO, OIO and BrO. None of these species could be detected. Upper limits for IO/SO2, OIO/SO2 and OBrO/SO2 are 1.8 × 10-6, 2.0 × 10-5 and 1.1 × 10-5 respectively.

Constraints for the photolysis rate and the equilibrium constant of ClO‐dimer from airborne and balloon‐borne measurements of chlorine compounds

AbstractWe analyze measurements of ClO across the terminator taken by the Airborne Submillimeter Radiometer (ASUR) in the activated vortices of the Arctic winters of 1995/1996, 1996/1997, and 1999/2000 to evaluate the plausibility of various determinations of the ClO‐dimer photolysis cross section and the rate constant controlling the thermal equilibrium between ClO‐dimer and ClO. We use measured ClO during sunlit conditions to estimate total active chlorine (ClOx). As the measurements suggest nearly full chlorine activation in winter 1999/2000, we compare ClOx estimates based on various photolysis frequencies of ClO‐dimer with total available inorganic chlorine (Cly), estimated from an N2O‐Cly correlation established by a balloon‐borne MkIV interferometer measurement. Only ClO‐dimer cross sections leading to the fastest photolysis frequencies in the literature (including the latest evaluation by the Jet Propulsion Laboratory) give ClOx mixing ratios that overlap with the estimated range of available Cly. Slower photolysis rates lead to ClOx values that are higher than available Cly. We use the ClOx calculated from sunlit ClO measurements to estimate ClO in darkness based on different equilibrium constants, and compare it with ASUR ClO measurements before sunrise at high solar zenith angles. Calculations with equilibrium constants published in recent evaluations of the Jet Propulsion Laboratory give good agreement with observed ClO mixing ratios. Equilibrium constants leading to a higher ClO/ClOx ratio in darkness yield ClO values that tend to exceed observed abundances. Perturbing the rates for the ClO + BrO reaction in a manner that increases OClO formation and decreases BrCl formation leads to lower ClO values calculated for twilight conditions after sunset, resulting in better agreement with ASUR measurements.

Evidence for heterogeneous chlorine activation in the tropical UTLS

Abstract. Airborne in-situ observations of ClO in the tropics were made during the TROCCINOX (Aracatuba, Brazil, February 2005) and SCOUT-O3 (Darwin, Australia, November/December 2005) field campaigns. While during most flights significant amounts of ClO (≈10–20 parts per trillion, ppt) were present only in aged stratospheric air, instances of enhanced ClO mixing ratios of up to 40 ppt – significantly exceeding those expected from gas phase chemistry – were observed in air masses of a more tropospheric character. Most of these observations are associated with low temperatures or with the presence of cirrus clouds (often both), suggesting that cirrus ice particles and/or liquid aerosol at low temperatures may promote significant heterogeneous chlorine activation in the tropical upper troposphere lower stratosphere (UTLS). In two case studies, particularly high levels of ClO observed were reproduced by chemistry simulations only under the assumption that significant denoxification had occurred in the observed air. However, to reproduce the ClO observations in these simulations, O3 mixing ratios higher than observed had to be assumed, and at least for one of these flights, a significant denoxification is in contrast to the observed NO levels, suggesting that the coupling of chlorine and nitrogen compounds in the tropical UTLS may not be completely understood.

Validation of the Aura Microwave Limb Sounder ClO measurements

We assess the quality of the version 2.2 (v2.2) ClO measurements from the Microwave Limb Sounder (MLS) on the Earth Observing System Aura satellite. The MLS v2.2 ClO data are scientifically useful over the range 100 to 1 hPa, with a single‐profile precision of ∼0.1 ppbv throughout most of the vertical domain. Vertical resolution is ∼3–4 km. Comparisons with climatology and correlative measurements from a variety of different platforms indicate that both the amplitude and the altitude of the peak in the ClO profile in the upper stratosphere are well determined by MLS. The latitudinal and seasonal variations in the ClO distribution in the lower stratosphere are also well determined, but a substantial negative bias is present in both daytime and nighttime mixing ratios at retrieval levels below (i.e., pressures larger than) 22 hPa. Outside of the winter polar vortices, this negative bias can be eliminated by subtracting gridded or zonal mean nighttime values from the individual daytime measurements. In studies for which knowledge of lower stratospheric ClO mixing ratios inside the winter polar vortices to better than a few tenths of a ppbv is needed, however, day − night differences are not recommended and the negative bias must be corrected for by subtracting the estimated value of the bias from the individual measurements at each affected retrieval level.

Polar stratospheric chlorine kinetics from a self‐match flight during SOLVE‐II/EUPLEX

In‐situ measurements of ClO made onboard the Geophysica aircraft on 30 January 2003 in the Arctic afford a novel approach to constrain the kinetic parameters governing polar stratospheric chlorine chemistry using atmospheric observations. The self‐match flight pattern, i.e. sampling individual air masses twice at different zenith angles, was utilized by simulating the evolution of ClO mixing ratios between two ‘matching’ points using a photochemical model and optimizing the model parameters to fit the observations within a retrieval framework. Our results suggest a ClO/ClOOCl thermal equilibrium constant Keq a factor of 5 smaller and a ratio J/kf a factor of 2 larger than the values based on the JPL recommendations. This concurs with other studies based on observed ClOx partitioning and corroborates that our understanding of stratospheric chlorine chemistry is incomplete, particularly in the light of the most recent laboratory experiments pointing to a J/kf ratio almost an order of magnitude below the JPL recommendation.

Experimental evidence of perturbed odd hydrogen and chlorine chemistry after the October 2003 solar proton events

Time series of stratospheric ClO and HOCl have been measured with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board the Environmental Satellite (ENVISAT) during the solar storm episode in October/November 2003. A remarkable enhancement of ClO mean values (averaged over latitudes poleward from 70°N) was found, reaching values of more than 0.2 ppbv and even 0.4 ppbv when only nighttime measurements are considered. HOCl was found to increase by up to more than 0.3 ppbv at altitudes above 32 km. This gives indirect proof of enhanced odd hydrogen abundances as a consequence of the solar proton events between 27 and 31 October 2003. Simultaneous increase of both ClO and HOCl hints at HCl destruction either through OH or directly via ion cluster chemistry. When HOCl and ClO mixing ratios decreased, most probably due to then lowered odd hydrogen abundances, large amounts of ClONO2 (polar cap averages enhanced by up to 0.4 ppbv) in early November indicate that ClO then was buffered in this reservoir. Daytime Antarctic ClO enhancements reach 0.2 ppbv and are largest above approximately 40 km. The largest response of Antarctic nighttime ClO is seen at 35 km altitude, where the enhancement reaches 0.3 ppbv. HOCl enhancement in the southern stratosphere was weaker by approximately a factor of two compared with the northern counterpart. The most prominent HOCl increase in the southern stratosphere was observed in subpolar regions between 60°S and 70°S.

Vertical profiles of activated ClO and ozone loss in the Arctic vortex in January and March 2000: In situ observations and model simulations

In situ observations of ClO mixing ratios obtained from a balloonborne instrument launched in Kiruna on 27 January 2000 and on 1 March 2000 are presented. ClO mixing ratios and quasi‐simultaneously observed ozone loss are compared to model simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS). ClO mixing ratios are simulated initializing the model simulations for early winter conditions. Sensitivity studies are performed to explore the impact of the surface area of the background aerosol, of denitrification, and of the recently reported kinetics of the ClO self‐reaction [Bloss et al., 2001] on simulated ClO. For 27 January 2000, model simulations agree with rate constants reported by Bloss et al. [2001], whereas for 1 March 2000 simulations employing rate constants reported by Bloss et al. [2001] and by Sander et al. [2000] reproduce the ClO measurements. The impact of uncertainties arising from accumulated errors along the calculated backward trajectories and uncertainties within temperatures derived from the UK Met Office are also studied. For both flights, simulated ClO show a good overall agreement with measured ClO within uncertainties arising from accumulated errors along air parcel histories. We find a layer of low ClO mixing ratios < 100 pptv between 600 and 620 K for the flight on 27 January 2000 and between 525 and 550 K on 1 March 2000. For this layer, measured ClO is substantially lower than simulated ClO. Potential causes are discussed, but the discrepancy remains unexplained at present. Furthermore, for 1 March 2000, an overall agreement is found between model simulations and measurements by the HALOE instrument of HCl and NOx (=NO + NO2) for all altitudes considered. We conclude that denitrification occurred up to a potential temperature of ≈550 K (≈24 km altitude) on 1 March 2000. Finally, model simulations show that between late January and 1 March, a significant ozone loss of about 0.8–1.8 ppmv is derived between 425 and 490 K of potential temperature in agreement with measured ozone loss and correlated with the enhanced ClO. For 1 March 2000, 77 ± 10 DU is obtained as an estimate of the loss in column ozone.

Measurements of stratospheric ClO over Antarctica in 1996–2000 and implications for ClO dimer chemistry

Measurements of ClO over Antarctica during the 1996 to 2000 ozone holes are compared with predictions of the SLIMCAT model. The model captures all of the major features of the measurements, including the rapid rise in August, the drop in mid or late September due to the arrival of warmer, ClOx poor air overhead, and the deactivation of ClOx into the reservoir species, HCl and ClONO2 in the ozone poor air. The model uses the standard JPL rates for the photolysis of the ClO dimer (j) and for the forward reaction forming the dimer (kf). The predicted ClO mixing ratios and columns are in excellent agreement with the measurements. A comparison of the model and data for all 5 years leads to a value of the ratio (j/kf) consistent with the standard value, namely 1.06 ± 0.30(j/kf)JPL.

Indications of heterogeneous chlorine activation on moderately cold aerosol based on chlorine observations in the Arctic stratosphere

During two balloon flights in the Arctic winter in February 1994 two distinctly different vertical profiles of ClO were measured. On 1 February enhanced values of ClO were observed between about 420 and 620 K inside the polar vortex in an air mass that had experienced moderately cold temperatures about 10 h prior to our measurements. In contrast, on 9 February an unstructured vertical profile was observed outside of the vortex with lower mixing ratios of ClO. Based on calculations with a photochemical box trajectory model we show that the observed enhancement in ClO can be explained by heterogeneous processing of chlorine reservoir species on supercooled liquid aerosols. When NAT formation is forced in the model or when lee wave processing is assumed, the mixing ratios of ClO inside the vortex are overpredicted. Under conditions where air masses are only cooled to low temperatures for a short period of time this may be a very important chlorine activation mechanism.

A test of our understanding of the ozone chemistry in the Arctic polar vortex based on in situ measurements of ClO, BrO, and O3 in the 1994/1995 winter

We present an analysis of in situ measurements of ClO, BrO, O3, and long‐lived tracers obtained on a balloon flight in the Arctic polar vortex launched from Kiruna, Sweden, 68°N, on February 3, 1995. Using the method of tracer correlations, we deduce that the air masses sampled at an altitude of 21 km (480 K potential temperature), where a layer of enhanced ClO mixing ratios of up to 1150 parts per trillion by volume was observed, experienced a cumulative chemical ozone loss of 1.0±0.3 ppmv between late November 1994 and early February 1995. This estimate of chemical ozone loss can be confirmed using independent data sets and independent methods. Calculations using a trajectory box model show that the simulations underestimate the cumulative ozone loss by approximately a factor of 2, although observed ClO and BrO mixing ratios are well reproduced by the model. Employing additional simulations of ozone loss rates for idealized conditions, we conclude that the known chlorine and bromine catalytic cycles destroying odd oxygen with the known rate constants and absorption cross sections do not quantitatively account for the early winter ozone losses infered for air masses observed at 21 km.

The vertical distribution of ClO at Ny‐Ålesund during March 1997

Results of the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA) are compared with vertical ClO profiles measured by the ground‐based Millimeter Wave Radiometer MIRA2 inside the vortex during March 1997 at Ny‐Ålesund. The influence of the OH + ClO and HO2 + ClO reaction branching ratio and of the absorption cross section of Cl2O2 on the calculated mixing ratios of ClO and ozone has been investigated. In the upper stratosphere the ClO mixing ratio is reduced by 90% by using a minor channel of the OH + ClO reaction with a branching ratio of 0.07. A temperature dependent minor channel of the HO2 + ClO reaction reduces the upper stratospheric ClO mixing ratio by 22%. Different absorption spectra of Cl2O2 alter the ClO mixing ratios up to 12% at noon at 20 km. This causes differences of 15% in the ozone loss during winter.

Stratosphere over Dumont d'Urville, Antarctica, in winter 1992

We present an analysis of the temporal evolution of stratospheric constituents above the station of Dumont d'Urville in Antarctica (67°S, 140°E) from August 14 to September 20, 1992. Data sets include temperature profiles and H2O, ClO, O3, NO2, ClONO2, HNO3, N2O, and CH4 mixing ratios and aerosol extinction coefficients from 46 to 1 hPa measured by the Microwave Limb Sounder (MLS) and the Cryogenic Limb Array Etalon Spectrometer (CLAES) instruments aboard the Upper Atmosphere Research Satellite (UARS). At the station, aerosol extinction coefficients and O3 profiles are obtained by a lidar together with O3 profiles provided by sondes. Integrated O3 and NO2 column amounts are given by a Système d'Analyse par Observation Zénithale (SAOZ) spectrometer located at the station. Column O3 is also provided by the Total Ozone Mapping Spectrometer (TOMS) instrument aboard the NIMBUS 7 satellite, complemented with potential vorticity derived from the U.K. Meteorological Office assimilated data set and temperature fields provided by the European Centre for Medium‐Range Weather Forecasts. Time evolution of these measurements is interpreted by comparison with results from the SLIMCAT three‐dimensional chemical transport model. We show that the site is near the vortex edge on average and is alternately inside the vortex or just outside in the region referred to as the “collar” region. There are no observations of polar stratospheric clouds (PSCs) over the station above 46 hPa (∼18 km). In fact, PSCs mainly appear over the Palmer Peninsula area at 46 hPa. The rates of change of chemical species are evaluated at 46 hPa when the station is conservatively inside the vortex collar region. The ozone loss rate is 0.04 ppmv d−1 (∼1.3% d−1), which is consistent with other analyses of southern vortex ozone loss rates; chlorine monoxide tends to decrease by 0.03 ppbv d−1, while chlorine nitrate increases by 0.025 ppbv d−1. These negative ClO and positive ClONO2 trends are only observed in the collar region of the vortex where O3 amounts are far from near zero, and little denitrification is observed. Loss and production rates as measured by UARS are more pronounced than the ones deduced from the SLIMCAT model, probably because of the moderate model horizontal resolution (3.75° × 3.75°), which is not high enough to resolve the vortex crossings above Dumont d'Urville and which leads to a larger extent of denitrified air than indicated by the UARS data. The analysis also shows activated ClO inside the vortex at 46 hPa, a dehydrated vortex at 46 hPa, and rehydrated above, with no trace of denitrification in the lower stratosphere. Good agreement between coincident measurements of O3 profiles by UARS/MLS, lidar, and sondes is also observed. Finally, the agreement between UARS and SLIMCAT data sets is much better in the middle stratosphere (4.6 hPa) than in the lower stratosphere (46 hPa).

Heterogeneous chlorine chemistry in the tropopause region

Satellite observations of cloud optical depths and occurrence frequencies are used as input to a two‐dimensional numerical model of the chemistry and dynamics of the atmosphere to study the effects of heterogeneous reactions on cloud surfaces upon chemical composition and ozone depletion in the tropopause region. Efficient reactions of ClONO2 with HCl and H2O, and of HOCl with HCl, are likely to take place on the surfaces of cirrus clouds [Borrmann et al., 1996] and perturb chlorine chemistry, much as they do on polar stratospheric clouds present at higher altitudes and colder temperatures. Because of the very low predicted background abundances of ClO near the tropopause, such reactions could enhance the local ClO mixing ratios by up to 30‐fold at midlatitudes. Substantial perturbations are also predicted for related chemical species (e.g., HCl, HOCl, ClONO2, NO2, HO2) in the midlatitude and tropical tropopause regions due to these heterogeneous reactions. If cirrus clouds occur with sufficient frequency and spatial extent, they could influence not only the chemical composition but also the ozone depletion in the region near the tropopause. Because of variations in observed cloud occurrence frequency and in photochemical and dynamical timescales, the presence of cirrus clouds likely has its largest effect on ozone near the midlatitude tropopause of the northern hemisphere in summer.

On the occurrence of ClO in cirrus clouds and volcanic aerosol in the tropopause region

Airborne observations during descents of the ER‐2 through layers of volcanic aerosol (Mount Pinatubo eruption of 1991) and a cirrus cloud are utilized to study the the abundance of ClO and its relation to aerosol surface area in the midlatitude tropopause region. During a cirrus event near the tropopause ClO mixing ratios up to 2.7 pptv were detected and near the tropopause ClO levels from a few to 70 pptv were found. These measurements are associated with large experimental uncertainties but demonstrate the possible presence of ClO inside cirrus clouds and near the tropopause. Model calculations show that possible enhancements of ClO by heterogeneous chemistry on cirrus cloud particles could considerably increase the ozone loss rates and could have implications for the ozone budget in this region. It is not possible to decide from the limited data base whether the observed ClO levels are due to transport or heterogeneous chemistry.

ClONO2 vertical profile and estimated mixing ratios of ClO and HOCl in winter Arctic stratosphere from Michelson interferometer for passive atmospheric sounding limb emission spectra

Nighttime limb emission spectra recorded by the balloon‐borne Michelson interferometer for passive atmospheric sounding (MIPAS) on February 11, 1995, near Kiruna were used to infer a vertical profile of ClONO2 as well as estimates of ClO and HOCl volume mixing ratios. The highest ClONO2 mixing ratio (2.6 parts per billion by volume (ppbv)) was found at 22.69 km altitude and is explained by an early recovery of this chlorine reservoir in the upper part of the formerly chlorine‐activated height range. Inferred nighttime ClO mixing ratios appear to be rather high for the lower stratosphere (0.38 ppbv at 16.43 km altitude) and indicate chlorine activation at this altitude region. The HOCl mixing ratio is estimated as 0.03 ppbv at 28.04 km altitude, while for lower altitudes the HOCl concentrations are clearly below the detection limit of MIPAS. The measurements are compared with three‐dimensional chemical transport model calculations. Results agree reasonably well but show differences in detail.

A wintertime in situ profile of BrO between 17 and 27 km in the Arctic vortex

The vertical profile of bromine oxide (BrO) was measured in situ from a balloon launched near Kiruna, Sweden (68°N, 21°E) at sunrise on February 3, 1995. BrO mixing ratios of 10±2 parts per trillion by volume (pptv) were observed at high solar zenith angles (90–92°) between 20 and 23 km in a layer that coincided with significantly enhanced abundances of ClO. Above 23 km, where ClO mixing ratios typical of midlatitudes were observed, BrO mixing ratios ranged from 5 to 11 pptv, increasing nearly monotonically with increasing altitude and decreasing solar zenith angle. The measurements indicate that 30 to 60% of the total bromine (assuming 18 pptv total bromine) is in the form of BrO between 23 and 27 km at these latitudes in winter. These results are consistent with lower altitude measurements of BrO from the NASA ER‐2 at similar latitudes and season. Observations of higher fractions of BrO (50 to 95% of total bromine) in the chemically perturbed region at sunrise imply the rapid release of bromine from a photolabile reservoir species, such as BrCl.

Vertical profile of night-time stratospheric OClO

The first night-time observation of the vertical profile of OClO wasperformed by the AMON balloon-borne spectrometer during the SESAME arcticcampaign, launched from Kiruna in northern Scandinavia. The flight, which tookplace inside the polar vortex on February 10, 1995, reveals mixing ratios of45±10 pptv at 20 km. These results are in excellent agreement with theREPROBUS 3D model simulations, which indicate that the observed OClOcorresponds to daytime ClO and BrO mixing ratios of 1.2 ppbv and 10 pptv,respectively.

Partitioning Between Chlorine Reservoir Species Deduced from Observations in the Arctic Winter Stratosphere

Simultaneous observations of several chlorine source gases, as well asHCl and ClO, have been performed in the Arctic stratosphere on 1 and 9February 1994, using balloon-borne instrumentation as a contribution toSESAME (Second European Stratospheric Arctic and Mid latitude Experiment).The observed mixing ratios of HCl and N2O show a clearanticorrelation. No severe loss of HCl was observed inside the vortex duringour measurement. These measurements showed that during this period at 20 kmand above, HCl was either in excess, or at least as abundant, asClONO2 and comprised between 50 and 70% of theavailable chlorine, Cly. On 1 February, measurements were madeinside the polar vortex. The air mass sampled on this day showed a clearsignature of diabatic descent, and also enhanced levels of ClO with amaximum of 230 pptv at 22.5 km. A 10 day backward trajectory analysis showedthat these air masses had passed a large region of low temperatures a fewhours prior to the measurement. Temperatures along the back trajectory atthe 475 K and 550 K levels (20.1 and 23.7 km respectively) were cold enoughfor heterogeneous chlorine activation to occur, in agreement with theobserved elevated ClO mixing ratios.

Stratospheric ClO profiles from McMurdo Station, Antarctica, spring 1992

We describe ground‐based measurements of ClO made at McMurdo Station, Antarctica, during September and October 1992. Vertical profiles were retrieved from molecular rotational emission spectra at 278 GHz. Peak mixing ratios of 1.6±0.3 ppbv were seen in mid‐September at approximately 18 km altitude, suggestive of somewhat larger quantities than were measured at the same site and season in 1987. As the core of the polar vortex moved away from McMurdo by early October, the ClO mixing ratio at this altitude dropped to less than 0.2 ppbv, coincident with increasing temperature, ozone, and NO2. The diurnal variation of ClO was also observed. The lower stratospheric layer from 15 to 27 km was found to reach approximately midday abundance by 2–3 hours after sunrise. The column abundance in this layer began to decrease by the period 4–2 hours before sunset and had declined to approximately one quarter of its midday value by 2–0 hours before sunset. In contrast, the ClO column in the upper stratosphere, from 28 to 50 km, built up slowly until midday and remained large while sunlight persisted.

Time and temperature dependences of fractional HCl abundances from airborne data in the Southern Hemisphere during 1994

Measurements of HCl and CH4 taken by the aircraft laser infrared absorption spectrometer (ALIAS) on the ER-2 high-altitude research aircraft during the Southern Hemisphere winter of 1994 have been used to examine the abundance of HCl as a fraction of total inorganic chlorine. The fractional abundance of HCl shows a threshold behaviour as a function of temperature history; on a 10 day timescale, the abundance dropped sharply in those air parcels experiencing a temperature < 195 K, but little or no change was seen in parcels which stayed warmer than this temperature. The behaviour mirrors well the temperature behaviour calculated for the transformation of HCl into reactive forms (Cl2, HOCl) from laboratory studies of sulfate aerosols and polar stratospheric clouds. During the course of the winter, the fractional abundance of HCl outside the vortex decreased from its values in late May by about a third, while inside it dropped to near zero by early August. Some recovery was evident in October. Examples of the peel-off of low-HCl air equatorward of the wind maximum were evident in early June. Meteorological trajectories are used to show, in a case study of a flight in early August, that air parcels which experienced temperatures of < 195 K, and as a result had low fractional HCl abundances, did so largely poleward of the maximum in the polar night jet stream. Encountering temperatures of < 195 K during the previous 10 days was a necessary and sufficient condition for the transformation of HCl into reactive forms by heterogeneous reactions. The trajectories further showed that air arriving from sub-tropical latitudes had higher fractional HCl abundances than the air in the middle latitudes, and much higher fractions than the air at high latitudes. The resulting picture is one in which the fractional abundance of HCl in air at mid latitudes was the result of mixing of air from sub-tropical latitudes with air mainly from polward of the jet stream core which has experienced temperatures < 195 K. The sensitivity of the fractional abundance of HCl to the assumption that no HCl enters the stratosphere via the tropical tropopause is examined in the light of an observed profile near the equator with a volume fraction of 0.4 ppb HCl, zero ClO and tropospheric mixing ratios of CFCs at the tropical tropopause.