Midlatitude ClO during the maximum atmospheric chlorine burden : in situ balloon measurements and model simulations

Chlorine monoxide (ClO) plays a key role in stratospheric ozone loss processes at midlatitudes. We present two balloonborne in situ measurements of ClO conducted in northern hemisphere midlatitudes during the period of the maximum of total inorganic chlorine loading in the atmosphere. Both ClO measurements were conducted on board the TRIPLE balloon payload, launched in November 1996 in Le´on, Spain, and in May 1999 in Aire sur l’Adour, France. For both flights a ClO daylight and night time vertical profile could be derived over an altitude range of approximately 15–31 km. ClO mixing ratios are compared to model simulations performed with the photochemical box model version of the Chemical Lagrangian Model of the Stratosphere (CLaMS). Simulations along 24-h backward trajectories were performed to study the diurnal variation of ClO in the midlatitude lower stratosphere. Model simulations for the flight launched in Aire sur l’Adour 1999 show a good agreement with the ClO measurements. For the flight launched in Le´on 1996, a similar good agreement is found, except at around ~ 650 K potential temperature (~26km altitude). However, a tendency is found that for solar zenith angles greater than 86°–87° the simulated ClO mixing ratios substantially overestimate measured ClO by approximately a factor of 2.5 or more for both flights. Therefore we conclude that no indication can be deduced from the presented ClO measurements that substantial uncertainties exist in midlatitude chlorine chemistry of the stratosphere. An exception is the situation at solar zenith angles greater than 86°–87° where model simulations substantial overestimate ClO observations

Measurements of quantum yields of bromine atoms in the photolysis of bromoform from 266 to 324 nm

The quantum yield for the formation of bromine atoms in the photolysis of bromoform, CHBr_3, has been measured between 266 and 324 nm. For 303 to 306 nm the quantum yields are unity within the experimental uncertainty of the measurements. At longer wavelengths, where the bromoform cross sections decrease rapidly, an apparent trend to slightly lower quantum yields is probably the result of systematic and random errors or incorrect CHBr_3 absorption cross sections. Support for a unit quantum yield for all wavelengths longer than 300 nm comes from the recent theoretical calculations of Peterson and Francisco. At 266 nm the bromine atom quantum yield is 0.76 (±0.03), indicating that at least one additional dissociation channel becomes important at shorter wavelengths. For modeling of the troposphere, it is recommended that a quantum yield of unity be used for wavelengths of 300 nm and longer

Measurements of quantum yields of bromine atoms in the photolysis of bromoform from 266 to 324 nm

The quantum yield for the formation of bromine atoms in the photolysis of bromoform, CHBr_3, has been measured between 266 and 324 nm. For 303 to 306 nm the quantum yields are unity within the experimental uncertainty of the measurements. At longer wavelengths, where the bromoform cross sections decrease rapidly, an apparent trend to slightly lower quantum yields is probably the result of systematic and random errors or incorrect CHBr_3 absorption cross sections. Support for a unit quantum yield for all wavelengths longer than 300 nm comes from the recent theoretical calculations of Peterson and Francisco. At 266 nm the bromine atom quantum yield is 0.76 (±0.03), indicating that at least one additional dissociation channel becomes important at shorter wavelengths. For modeling of the troposphere, it is recommended that a quantum yield of unity be used for wavelengths of 300 nm and longer

Observation of Stratospheric Ozone Depletion associated with Delta II Rocket Emissions

Ozone, chlorine monoxide, methane, and submicron particulate concentrations were measured in the stratospheric plume wake of a Delta II rocket powered by a combination of solid (NH4ClO4/Al) and liquid (LOX/kerosene) propulsion systems. We apply a simple kinetics model describing the main features of gas-phase chlorine reactions in solid propellant exhaust plumes to derive the abundance of total reactive chlorine in the plume and estimate the associated cumulative ozone loss. Measured ozone loss during two plume encounters (12 and 39 minutes after launch) exceeded the estimate by about a factor of about two. Insofar as only the most significant gas-phase chlorine reactions are included in the calculation, these results suggest that additional plume wake chemical processes or emissions other than reactive chlorine from the Delta II propulsion system affect ozone levels in the plume

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

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

situ measurements of bromine oxide at two high-latitude boundary layer sites: Implications of variability

[1] Bromine oxide (BrO) was measured in situ during the Arctic Tropospheric Ozone Chemistry (ARCTOC) '96 campaign in Ny Å lesund, Spitsbergen (April-May 1996), and during the Alert 2000 Polar Sunrise Experiment in Alert, Nunavut, Canada (April-May 2000). Measurements were made in near-surface air during low-ozone events in early May at both sites. The average of the in situ concentrations of BrO at Ny Å lesund is consistent with the path average of near-simultaneous long-path differential optical absorption spectroscopy measurements, but there is considerable scatter in a point-by-point comparison. The differences between these observations are consistent with a strong surface influence on reactive bromine. We see similar variability of the in situ measurements at Alert, which reflects the real variability of both surface sources and sinks. The fluctuations of BrO abundances are used to assess the expected loss rates and associated lifetimes of ozone during depletion events. We show that ozone loss will be underpredicted by any temporal or spatial average of BrO

Enhanced ClO from 10 to 12 km Near the Winter Polar Tropopause During SOLVE/THESEO-2000

Abundances of chlorine oxide have been measured in situ near the tropopause from the NASA DC-8 aircraft during the SOLVE/THESEO-2000 campaign. Significant abundances, averaging 15-20 parts per trillion, were observed throughout the lowermost stratosphere at high latitudes during winter. Mixing ratios of ClO generally increased with increasing ozone (the latter an indicator of stratospheric air) as has been observed at other latitudes and seasons. However, the ratio of ClO to inorganic chlorine ([ClO]/[Cl(sub y)]) was found to be largest in air characterized by low abundances of ozone (approximately l00-250). It was within this range of ozone values that cirrus clouds were also observed occasionally throughout the measurement period, although distinct enhancements of ClO were not commonly observed directly within cirrus clouds. Elevated abundances of ClO were also apparently observed in polar darkness. However, we attribute these measurements to OClO, a species that can also be detected by the DC-8 instrument under the conditions encountered during SOLVE/THESEO-2000. Using a photochemical box model constrained by daytime abundances of ClO, we infer that BrO mixing ratios in this region were approximately 2-4 ppt, consistent with previous measurements from balloon-borne remote sensors