Stratospheric ozone chemistry in the Antarctic: what determines the lowest ozone values reached and their recovery?

Balloon-borne observations of ozone from the South Pole Station have been reported to reach ozone mixing ratios below the detection limit of about 10 ppbv at the 70 hPa level by late September. After reaching a minimum, ozone mixing ratios increase to above 1 ppmv on the 70 hPa level by late December. While the basic mechanisms causing the ozone hole have been known for more than 20 yr, the detailed chemical processes determining how low the local concentration can fall, and how it recovers from the minimum have not been explored so far. Both of these aspects are investigated here by analysing results from the Chemical Lagrangian Model of the Stratosphere (CLaMS). As ozone falls below about 0.5 ppmv, a balance is maintained by gas phase production of both HCl and HOCl followed by heterogeneous reaction between these two compounds in these simulations. Thereafter, a very rapid, irreversible chlorine deactivation into HCl can occur, either when ozone drops to values low enough for gas phase HCl production to exceed chlorine activation processes or when temperatures increase above the polar stratospheric cloud (PSC) threshold. As a consequence, the timing and mixing ratio of the minimum ozone depends sensitively on model parameters, including the ozone initialisation. The subsequent ozone increase between October and December is linked mainly to photochemical ozone production, caused by oxygen photolysis and by the oxidation of carbon monoxide and methane

What causes the irregular cycle of the atmospheric tape recorder signal in HCN?

Variations in the mixing ratio of long-lived trace gases entering the stratosphere in the tropics are carried upward with the rising air with the signal being observable throughout the tropical lower stratosphere. This phenomenon, referred to as "atmospheric tape recorder" has previously been observed for water vapor, CO2, and CO which exhibit an annual cycle. Recently, based on Microwave Limb Sounder (MLS) and the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) satellite measurements, the tape recorder signal has been observed for hydrogen cyanide (HCN) but with an approximately two-year period. Here we report on a model simulation of the HCN tape recorder for the time period 2002-2008 using the Chemical Lagrangian Model of the Stratosphere (CLaMS). The model can reproduce the observed pattern of the HCN tape recorder signal if time-resolved emissions from fires in Indonesia are used as lower boundary condition. This finding indicates that inter-annual variations in biomass burning in Indonesia, which are strongly influenced by El Nino events, control the HCN tape recorder signal. A longer time series of tropical HCN data will probably exhibit an irregular cycle rather than a regular biannual cycle. Citation: Pommrich, R., R. Muller, J.-U. Grooss, G. Gunther, P. Konopka, M. Riese, A. Heil, M. Schultz, H.-C. Pumphrey, and K. A. Walker (2010), What causes the irregular cycle of the atmospheric tape recorder signal in HCN?, Geophys. Res. Lett., 37, L16805, doi:10.1029/2010GL044056

Horizontal transport affecting trace gas seasonality in the Tropical Tropopause Layer (TTL)

We analyze horizontal transport from midlatitudes into the tropics (in-mixing) and its impact on seasonal variations of ozone, carbon monoxide and water vapor in the Tropical Tropopause Layer (TTL). For this purpose, we use three-dimensional backward trajectories, driven by ECMWF ERA-Interim winds, and a conceptual one-dimensional model of the chemical composition of the TTL. We find that the fraction of in-mixed midlatitude air shows an annual cycle with maximum during NH summer, resulting from the superposition of two inversely phased annual cycles for in-mixing from the NH and SH, respectively. In-mixing is driven by the monsoonal upper-level anticyclonic circulations. This circulation pattern is dominated by the Southeast Asian summer monsoon and, correspondingly, in-mixing shows an annual cycle. The impact of in-mixing on TTL mixing ratios depends on the in-mixed fraction of midlatitude air and on the meridional gradient of the particular species. For CO the meridional gradient and consequently the effect of in-mixing is weak. For water vapor, in-mixing effects are negligible. For ozone, the meridional gradient is large and the contribution of in-mixing to the ozone maximum during NH summer is about 50%. This in-mixing contribution is not sensitive to the tropical ascent velocity, which is about 40% too fast in ERA-Interim. As photochemically produced ozone in the TTL shows no distinct summer maximum, the ozone annual anomaly in the upper TTL turns out to be mainly forced by in-mixing of ozone-rich extratropical air during NH summer

Annual cycle of ozone at and above the tropical tropopause: observations versus simulations with the Chemical Model of the Stratosphere (CLaMS)

Multi-annual simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) were conducted to study the seasonality of O-3 within the stratospheric part of the tropical tropopause layer (TTL), i.e. above theta = 360K potential temperature level. In agreement with satellite (HALOE) and in-situ observations (SHADOZ), CLaMS simulations show a pronounced annual cycle in O-3, at and above theta = 380 K, with the highest mixing ratios in the late boreal summer. Within the model, this cycle is driven by the seasonality of both upwelling and in-mixing. The latter process occurs through enhanced horizontal transport from the extratropics into the TTL that is mainly driven by the meridional, isentropic winds. The strongest in-mixing occurs during the late boreal summer from the Northern Hemisphere in the potential temperature range between 370 and 420 K. Complementary, the strongest upwelling occurs in winter reducing O-3 to the lowest values in early spring. Both CLaMS simulations and Aura MLS O-3 observations consistently show that enhanced in-mixing in summer is mainly driven by the Asian monsoon anticyclone

Carbon monoxide as a tracer for tropical troposphere to stratosphere transport in the Chemical Lagrangian Model of the Stratosphere (CLaMS)

Abstract. Variations in the mixing ratio of trace gases of tropospheric origin entering the stratosphere in the tropics are of interest for assessing both troposphere to stratosphere transport fluxes in the tropics and the impact on the composition of the tropical lower stratosphere of quasi-horizontal in-mixing into the tropical tropopause layer from the mid-latitude stratosphere. Here, we present a simplified chemistry scheme for the Chemical Lagrangian Model of the Stratosphere (CLaMS) for the simulation, at comparatively low numerical cost, of CO, ozone, and long-lived trace substances (CH4, N2O, CCl3F, and CO2) in the lower tropical stratosphere. The boundary conditions at the ground are represented for the long-lived trace substances CH4, N2O, CCl3F, and CO2 based on ground-based measurements. The boundary condition for CO in the free troposphere is deduced from MOPITT measurements. We find that the zonally averaged tropical CO anomaly patterns simulated by this model version of CLaMS are in good agreement with observations. The introduction of a new scheme in the ECMWF integrated forecast system (Tompkins et al., 2007) for the ice supersaturation after September 2006, results in a somewhat less good agreement between observed and simulated CO patterns in the tropical lower stratosphere after this date. </jats:p

Tropical troposphere to stratosphere transport of carbon monoxide and long-lived trace species in the Chemical Lagrangian Model of the Stratosphere (CLaMS)

Variations in the mixing ratio of trace gases of tropospheric origin entering the stratosphere in the tropics are of interest for assessing both troposphere to stratosphere transport fluxes in the tropics and the impact of these transport fluxes on the composition of the tropical lower stratosphere. Anomaly patterns of carbon monoxide (CO) and long-lived tracers in the lower tropical stratosphere allow conclusions about the rate and the variability of tropical upwelling to be drawn. Here, we present a simplified chemistry scheme for the Chemical Lagrangian Model of the Stratosphere (CLaMS) for the simulation, at comparatively low numerical cost, of CO, ozone, and long-lived trace substances (CH4, N2O, CCl3F (CFC-11), CCl2F2 (CFC-12), and CO2) in the lower tropical stratosphere. For the long-lived trace substances, the boundary conditions at the surface are prescribed based on ground-based measurements in the lowest model level. The boundary condition for CO in the free troposphere is deduced from MOPITT measurements (at ≈ 700–200 hPa). Due to the lack of a specific representation of mixing and convective uplift in the troposphere in this model version, enhanced CO values, in particular those resulting from convective outflow are underestimated. However, in the tropical tropopause layer and the lower tropical stratosphere, there is relatively good agreement of simulated CO with in-situ measurements (with the exception of the TROCCINOX campaign, where CO in the simulation is biased low ≈ 10–20 ppbv). Further, the model results are of sufficient quality to describe large scale anomaly patterns of CO in the lower stratosphere. In particular, the zonally averaged tropical CO anomaly patterns (the so called "tape recorder" patterns) simulated by this model version of CLaMS are in good agreement with observations. The simulations show a too rapid upwelling compared to observations as a consequence of the overestimated vertical velocities in the ERA-interim reanalysis data set. Moreover, the simulated tropical anomaly patterns of N2O are in good agreement with observations. In the simulations, anomaly patterns for CH4 and CFC-11 were found to be consistent with those of N2O; for all long-lived tracers, positive anomalies are simulated because of the enhanced tropical upwelling in the easterly phase of the quasi-biennial oscillation