ALBERT

Description: We report on HCFC-22 data acquired by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) in the reduced spectral resolution nominal observation mode. The data cover the period from January 2005 to April 2012 and the altitude range from the upper troposphere (above cloud top altitude) to about 50 km. The profile retrieval was performed by constrained nonlinear least squares fitting of modelled spectra to the measured limb spectral radiances. The spectral ν4-band at 816.5 ± 13 cm−1 was used for the retrieval. A Tikhonov-type smoothing constraint was applied to stabilise the retrieval. In the lower stratosphere, we find a global volume mixing ratio of HCFC-22 of about 185 pptv in January 2005. The rate of linear growth in the lower latitudes lower stratosphere was about 6 to 7 pptv year−1 in the period 2005–2012. The profiles obtained were compared with ACE-FTS satellite data v3.5, as well as with MkIV balloon profiles and cryosampler balloon measurements. Between 13 and 22 km, average agreement within −3 to +5 pptv (MIPAS – ACE) with ACE-FTS v3.5 profiles is demonstrated. Agreement with MkIV solar occultation balloon-borne measurements is within 10–20 pptv below 30 km and worse above, while in situ cryosampler balloon measurements are systematically lower over their full altitude range by 15–50 pptv below 24 km and less than 10 pptv above 28 km. MIPAS HCFC-22 time series below 10 km altitude are shown to agree mostly well to corresponding time series of near-surface abundances from the NOAA/ESRL and AGAGE networks, although a more pronounced seasonal cycle is obvious in the satellite data. This is attributed to tropopause altitude fluctuations and subsidence of polar winter stratospheric air into the troposphere. A parametric model consisting of constant, linear, quasi-biennial oscillation (QBO) and several sine and cosine terms with different periods has been fitted to the temporal variation of stratospheric HCFC-22 for all 10°-latitude/1-to-2-km-altitude bins. The relative linear variation was always positive, with relative increases of 40–70 % decade−1 in the tropics and global lower stratosphere, and up to 120 % decade−1 in the upper stratosphere of the northern polar region and the southern extratropical hemisphere. Asian HCFC-22 emissions have become the major source of global upper tropospheric HCFC-22. In the upper troposphere, monsoon air, rich in HCFC-22, is instantaneously mixed into the tropics. In the middle stratosphere, between 20 and 30 km, the observed trend is inconsistent with the trend at the surface (corrected for the age of stratospheric air), hinting at circulation changes. There exists a stronger positive trend in HCFC-22 in the Southern Hemisphere and a more muted positive trend in the Northern Hemisphere, implying a potential change in the stratospheric circulation over the observation period.

Description: We use limb emission spectra of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the ENVIronmental SATellite (ENVISAT) to derive the first global distribution of peroxyacetyl nitrate (PAN) in the upper troposphere. PAN is generated in tropospheric air masses polluted by fuel combustion or biomass burning and acts as a reservoir and carrier of NOx in the cold free troposphere. Since PAN exhibits continuum-like broadband structures in the mid-infrared region, we have applied a contiguous analysis window covering the wavenumber region 775–800 cm−1 for retrieval. The interfering species CCl4, HCFC-22, H2O, ClONO2, CH3CCl3 and C2H2 were fitted along with PAN, whereas pre-fitted profiles were used to model the contribution of other contaminants like ozone. Sensitivity tests consisting in retrieval without consideration of PAN have demonstrated the existence of PAN signatures in MIPAS spectra obtained from polluted air masses. The analysed dataset consists of 10 days between 4 October and 1 December 2003. This period covers the end of the biomass burning season in South America and South and East Africa, in which generally large amounts of pollutants are produced and distributed over wide areas in the southern hemispheric free troposphere. Elevated PAN amounts of 200–700 pptv were measured in a large plume extending from Brasil over the Southern Atlantic, Central and South Africa, the South Indian Ocean as far as Australia at altitudes between 8 and 16 km. Enhanced PAN values were also found in a much more restricted area between northern subtropical Africa and India. The most significant northern midlatitude PAN signal in MIPAS data is an area extending at 8 km altitude from China into the Chinese Sea. The average mid and high latitude PAN amounts found at 8 km were around 125 pptv in the northern, but only between 75 and 50 pptv in the southern hemisphere. The PAN distribution found in the southern hemispheric tropics and subtropics is highly correlated with the jointly fitted acetylene (C2H2), which is another pollutant produced by biomass burning, and agrees reasonably well with the CO plume detected during end of September 2003 at the 275 hPa level (~10 km) by the Measurement of Pollution in the Troposphere (MOPITT) instrument on the Terra satellite. Similar southern hemispheric PAN amounts were also observed by previous airborne measurements performed in September/October 1992 and 1996 above the South Atlantic and the South Pacific, respectively.

Description: We present global distributions of carbon monoxide (CO) from the upper troposphere to the mesosphere observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat. Vertically resolved volume mixing ratio profiles have been retrieved from 4.7 μm limb emission spectra under consideration of non-local thermodynamic equilibrium. The precision of individual CO profiles is typically 5–30 ppbv (15–40%). Estimated systematic errors are in the order of 8–15%. Below 60 km, the vertical resolution is 4–7 km. The data set which covers 54 days from September 2003 to March 2004 has been derived with an improved retrieval version including (i) the retrieval of log(vmr), (ii) the consideration of illumination-dependent vibrational population gradients along the instrument's line of sight, and (iii) joint-fitted vmr horizontal gradients in latitudinal and longitudinal directions. A detailed analysis of spatially resolved CO distributions during the 2003/2004 Northern Hemisphere major warming event demonstrate the potential of MIPAS CO observations to obtain new information on transport processes during dynamical active episodes, particularly on those acting in the vertical. From the temporal evolution of zonally averaged CO abundances, we derived extraordinary polar winter descent velocities of 1200 m per day inside the recovered polar vortex in January 2004. Middle stratospheric CO abundances show a well established correlation with the chemical source CH4, particularly in the tropics. In the upper troposphere, a~moderate CO decrease from September 2003 to March 2004 was observed. Upper tropospheric CO observations provide a detailed picture of long-range transport of polluted air masses and uplift events. MIPAS observations taken on 9–11 September 2003 confirm the trapping of convective outflow of polluted CO-rich air from Southeast Asia into the Asian monsoon anticyclone, which has been described in previous studies. Upper tropospheric CO plumes, observed by MIPAS on this day, were predominantly located in the Northern Hemisphere. Most of these plumes could be related to Southeast Asian pollution by means of backward trajectory calculations. During 20–22 October, southern hemispheric biomass burning was the most likely source of the major CO plumes observed over the Southern Atlantic and Indian Ocean.

Description: This paper characterizes vertical ozone profiles retrieved with the IMK-IAA (Institute for Meteorology and Climate Research, Karlsruhe – Instituto de Astrofisica de Andalucia) science-oriented processor from spectra measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the environmental satellite Envisat. Bias determination and precision validation is performed on the basis of correlative measurements by ground-based lidars, Fourier transform infrared spectrometers, and microwave radiometers as well as balloon-borne ozonesondes, the balloon-borne version of MIPAS, and two satellite instruments (Halogen Occultation Experiment and Polar Ozone and Aerosol Measurement III). Percentage mean differences between MIPAS and the comparison instruments for stratospheric ozone are within ±10%. The precision in this altitude region is estimated at values between 5 and 10% which gives an accuracy of 15 to 20%. Below 18 km, the spread of the percentage mean differences is larger and the precision increases to values of more than 20% depending on altitude and latitude. The main reason for the degraded precision at low altitudes is attributed to undetected thin clouds which affect MIPAS retrievals, and to the influence of uncertainties in the water vapor concentration.

Description: This paper characterizes vertical ozone profiles retrieved with the IMK-IAA (Institute for Meteorology and Climate Research, Karlsruhe – Instituto de Astrofisica de Andalucia) science-oriented processor from high spectral resolution data (until March 2004) measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the environmental satellite Envisat. Bias determination and precision validation is performed on the basis of correlative measurements by ground-based lidars, Fourier transform infrared spectrometers, and microwave radiometers as well as balloon-borne ozonesondes, the balloon-borne version of MIPAS, and two satellite instruments (Halogen Occultation Experiment and Polar Ozone and Aerosol Measurement III). Percentage mean differences between MIPAS and the comparison instruments for stratospheric ozone are generally within ±10%. The precision in this altitude region is estimated at values between 5 and 10% which gives an accuracy of 15 to 20%. Below 18 km, the spread of the percentage mean differences is larger and the precision degrades to values of more than 20% depending on altitude and latitude. The main reason for the degraded precision at low altitudes is attributed to undetected thin clouds which affect MIPAS retrievals, and to the influence of uncertainties in the water vapor concentration.

Description: The Fourier transform spectrometer MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) on Envisat measures infrared emission of the Earth's atmosphere in a limb viewing mode. High spectral resolution measurements of MIPAS are sensitive to formaldehyde from the upper troposphere to the stratopause. Single profile retrievals of formaldehyde are dominated by a 60% noise error; however zonal mean values for 30 days of data during 8 September 2003 and 1 December 2003 reduces this error by a factor of 20 or more. The number of degrees of freedom for single profile retrieval ranges from 2 to 4.5 depending on latitude and number of cloud-free tangent altitudes. In the upper tropical troposphere zonal mean values of about 70 parts per trillion by volume (pptv) were found, which have been attributed to biomass burning emissions. In the stratosphere, formaldehyde values are determined by photochemical reactions. In the upper tropical stratosphere, formaldehyde zonal mean maximum values can reach 130 pptv. Diurnal variations in this region can be up to 50 pptv. Comparisons with other satellite instruments show generally good agreement in the region of upper troposphere and lower stratosphere as well as in the upper stratosphere.

Description: We present global distributions of carbon monoxide (CO) from the upper troposphere to the mesosphere observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat. Vertically resolved volume mixing ratio profiles have been retrieved from 4.7 μm limb emission spectra under consideration of non-local thermodynamic equilibrium. The precision of individual CO profiles is typically 5–30 ppbv (15–40% for altitudes greater than 40 km and lower than 15 km and 30–90% within 15–40 km). Estimated systematic errors are in the order of 8–15%. Below 60 km, the vertical resolution is 4–7 km. The data set which covers 54 days from September 2003 to March 2004 has been derived with an improved retrieval version including (i) the retrieval of log(vmr), (ii) the consideration of illumination-dependent vibrational population gradients along the instrument's line of sight, and (iii) joint-fitted vmr horizontal gradients in latitudinal and longitudinal directions. A detailed analysis of spatially resolved CO distributions during the 2003/2004 Northern Hemisphere major warming event demonstrate the potential of MIPAS CO observations to obtain new information on transport processes during dynamical active episodes, particularly on those acting in the vertical. From the temporal evolution of zonally averaged CO abundances, we derived extraordinary polar winter descent velocities of 1200 m per day inside the recovered polar vortex in January 2004. Middle stratospheric CO abundances show a well established correlation with the chemical source CH4, particularly in the tropics. In the upper troposphere, a moderate CO decrease from September 2003 to March 2004 was observed. Upper tropospheric CO observations provide a detailed picture of long-range transport of polluted air masses and uplift events. MIPAS observations taken on 9–11 September 2003 confirm the trapping of convective outflow of polluted CO-rich air from Southeast Asia into the Asian monsoon anticyclone, which has been described in previous studies. Upper tropospheric CO plumes, observed by MIPAS on this day, were predominantly located in the Northern Hemisphere. Most of these plumes could be related to Southeast Asian pollution by means of backward trajectory calculations. During 20–22 October, southern hemispheric biomass burning was the most likely source of the major CO plumes observed over the Southern Atlantic and Indian Ocean.

Description: An extensive observational data set, consisting of more than 106 SF6 vertical profiles from MIPAS measurements distributed over the whole globe has been condensed into monthly zonal means of mean age of air for the period September 2002 to January 2010, binned at 10° latitude and 1–2 km altitude. The data were analysed with respect to their temporal variation by fitting a regression model consisting of a constant and a linear increase term, 2 proxies for the QBO variation, sinusoidal terms for the seasonal and semi-annual variation and overtones for the correction of the shapes to the observed data set. The impact of subsidence of mesospheric SF6-depleted air and in-mixing into non-polar latitudes on mid-latitudinal absolute age of air and its linear increase was assessed and found to be small. The linear increase of mean age of stratospheric air was found to be positive and partly larger than the trend derived by Engel et al. (2009) for most of the Northern mid-latitudes, the middle stratosphere in the tropics, and parts of the Southern mid-latitudes, as well as for the Southern polar upper stratosphere. Multi-year decrease of age of air was found for the lowermost and the upper stratospheric tropics, for parts of Southern mid-latitudes, and for the Northern polar regions. Analysis of the amplitudes and phases of the seasonal variation shed light on the coupling of stratospheric regions to each other. In particular, the Northern mid-latitude stratosphere is well coupled to the tropics, while the Northern lowermost mid-latitudinal stratosphere is decoupled, confirming the separation of the shallow branch of the Brewer-Dobson circulation from the deep branch. We suggest an overall increased tropical upwelling, together with weakening of mixing barriers, especially in the Northern Hemisphere, as a hypothetical model to explain the observed pattern of linear multi-year increase/decrease, and amplitudes and phase shifts of the seasonal variation.

Description: Under cloud free conditions, the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) provides measurements of spectrally resolved limb radiances down to the upper troposphere. These are used to infer global distributions of mixing ratios of atmospheric constituents in the upper troposphere and the stratosphere. From 21 October to 12 November 2003, MIPAS observed enhanced amounts of upper tropospheric C2H6 (up to about 400 pptv) and ozone (up to about 80 ppbv). The absolute values of C2H6, however, may be systematically low by about 30% due to uncertainties of the spectroscopic data used. By means of trajectory calculations, the enhancements observed in the southern hemisphere are, at least partly, attributed to a biomass burning plume, which covers wide parts of the Southern hemisphere, from South America, the Atlantic Ocean, Africa, the Indian Ocean to Australia. The chemical composition of the part of the plume-like pollution belt associated with South American fires, where rainforest burning is predominant appears different from the part of the plume associated with southern African savanna burning. In particular, African savanna fires lead to a larger ozone enhancement than equatorial American fires. In this analysis, MIPAS observations of high ozone were disregarded where low CFC-11 (below 245 pptv) was observed, because this hints at a stratospheric component in the measured signal. Different type of vegetation burning (flaming versus smouldering combustion) has been identified as a candidate explanation for the different plume compositions.

Description: In the 2002 Antarctic polar vortex enhanced HOCl mixing ratios were detected by the Michelson Interferometer for Passive Atmospheric Sounding both at altitudes of around 35 km (1000 K potential temperature), where HOCl abundances are ruled by gas phase chemistry and at around 18–24 km (475–625 K), which belongs to the altitude domain where heterogeneous chlorine chemistry is relevant. At altitudes of 33 to 40 km polar vortex HOCl mixing ratios were found to be around 0.14 ppbv as long as the polar vortex was intact, centered at the pole, and thus received relatively little sunlight. This is the altitude region where in midlatitudinal and tropic atmospheres peak HOCl mixing ratios significantly above 0.2 ppbv (in terms of daily mean values) are observed. After deformation and displacement of the polar vortex in the course of a major warming, ClO-rich vortex air was more exposed to sunlight, where enhanced HOx abundances led to largely increased HOCl mixing ratios (up to 0.3 ppbv), exceeding typical midlatitudinal and tropical amounts significantly. The HOCl increase was preceded by an increase of ClO. Model runs could reproduce these measurements only when the Stimpfle et al. (1979) rate constant for the reaction ClO+HO2→HOCl+O2 was used but not with the current JPL recommendation. At an altitude of 24 km, HOCl mixing ratios of up to 0.15 ppbv were detected. This HOCl enhancement, which is already visible in 18 September data, is attributed to heterogeneous chemistry, which is in agreement with observations of polar stratospheric clouds. The measurements were compared to a model run where no polar stratospheric clouds appeared during the observation period. The fact that HOCl still was produced in the model run suggests that a significant part of HOCl was generated from ClO rather than directly via heterogeneous reaction. Excess ClO, lower ClONO2 and earlier loss of HOCl in the measurements are attributed to ongoing heterogeneous chemistry which is not reproduced by the model. On 11 October, polar vortex mean daytime mixing ratios were only 0.03 ppbv.