K. A. Walker

University of Toronto, Toronto, Ontario, Canada

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Publications (315)718.69 Total impact

  • Niall J. Ryan · Kaley A. Walker
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    ABSTRACT: A sensitivity study was performed to assess the impact that uncertainties in the spectroscopic parameters of atmospheric species have on the retrieval of gas concentrations using the 265–280 GHz region of the electromagnetic spectrum. Errors in the retrieval of O3, N2O, HNO3, and ClO from spectra measured by ground-based radiometers were investigated. The goal of the study was to identify the spectroscopic parameters of these target species, and other interfering species, available in the JPL and HITRAN 2008 catalogues, which contribute the largest error to retrieved atmospheric concentration profiles in order to provide recommendations for new laboratory measurements. The parameters investigated were the line position, line strength, broadening coefficients and their temperature dependence, and pressure shift. Uncertainties in the air broadening coefficients of gases tend to contribute the largest error to retrieved atmospheric concentration profiles. For O3 and N2O, gases with relatively strong spectral signatures, the retrieval is sensitive to uncertainties in the parameters of the main spectral line that is observed. For HNO3, the uncertainties in many closely spaced HNO3 lines can cause large errors in the retrieved profile, and for ClO, the error in the profile is dominated by uncertainties in nearby, stronger O3 lines. Fourteen spectroscopic parameters are identified, for which updated measurements would have the most impact on the accuracy of ground-based remote sensing of the target species at 265–280 GHz.
    Journal of Quantitative Spectroscopy and Radiative Transfer 08/2015; 161. DOI:10.1016/j.jqsrt.2015.03.012 · 2.29 Impact Factor
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    ABSTRACT: The ozone profile records of a large number of limb and occultation satellite instruments are widely used to address several key questions in ozone research. Further progress in some domains depends on a more detailed understanding of these data sets, especially of their long-term stability and their mutual consistency. To this end, we make a systematic assessment of fourteen limb and occultation sounders that, together, provide more than three decades of global ozone profile measurements. In particular, we consider the latest operational Level-2 records by SAGE II, SAGE III, HALOE, UARS MLS, Aura MLS, POAM II, POAM III, OSIRIS, SMR, GOMOS, MIPAS, SCIAMACHY, ACE-FTS and MAESTRO. Central to our work is a harmonized and robust analysis of the comparisons against the ground-based ozonesonde and stratospheric ozone lidar networks. It allows us to investigate, from the ground up to the stratopause, the following main aspects of data quality: long-term stability, overall bias, and short-term variability, together with their dependence on geophysical parameters and profile representation. In addition, it permits us to quantify the overall consistency between the ozone profilers. Generally, we find that between 20–40 km, the satellite ozone measurement biases are smaller than ±5 %, the short-term variabilities are better than 5–12 % and the drifts are at most ±5 % decade−1 (and ±3 % decade−1 for a few records). The agreement with ground-based data degrades somewhat towards the stratopause and especially towards the tropopause, where natural variability and low ozone abundancies impede a more precise analysis. A few records deviate from the preceding general remarks, in part of the stratosphere; we identify biases of 10 % and more (POAM II and SCIAMACHY), markedly higher single-profile variability (SMR and SCIAMACHY), and significant long-term drifts (SCIAMACHY, OSIRIS, HALOE, and possibly GOMOS and SMR as well). Furthermore, we reflect on the repercussions of our findings for the construction, analysis and interpretation of merged data records. Most notably, the discrepancies between several recent ozone profile trend assessments can be mostly explained by instrumental drift. This clearly demonstrates the need for systematic comprehensive multi-instrument comparison analyses.
    07/2015; 8(7):6661--6757. DOI:10.5194/amtd-8-6661-2015
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    ATMOS 2015, Heraklion, Greece; 06/2015
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    ABSTRACT: The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) was an infra-red (IR) limb emission spectrometer on the Envisat platform. It measured during day and night, pole-to-pole, over an altitude range from 6 to 70 km in nominal mode and up to 170 km in special modes, depending on the measurement mode, producing more than 1000 profiles day−1. We present the results of a validation study of methane version V5R_CH4_222 retrieved with the IMK/IAA MIPAS scientific level 2 processor. The level 1 spectra are provided by ESA, the version 5 was used. The time period covered corresponds to the period when MIPAS measured at reduced spectral resolution, i.e. 2005–2012. The comparison with satellite instruments includes the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), the HALogen Occultation Experiment (HALOE), the Solar Occultation For Ice Experiment (SOFIE) and the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). Furthermore, comparisons with MkIV balloon-borne solar occultation measurements and with air sampling measurements performed by the University of Frankfurt are presented. The validation activities include bias determination, in selected cases, assessment of histograms and comparison of corresponding climatologies. Above 50 km altitude, MIPAS methane mixing ratios agree within 3% with ACE-FTS and SOFIE. Between 30 and 40 km an agreement within 3% with SCIAMACHY has been found. In the middle stratosphere, there is no clear indication of a MIPAS bias since comparisons with various instruments contradict each other. In the lower stratosphere (below about 25–30 km) MIPAS CH4 is biased high with respect to satellite instruments, and the most likely estimate of this bias is 14%. However, in the comparison with CH4 data obtained from cryosampler measurements, there is no evidence of a MIPAS high bias between 20 and 25 km altitude. Precision validation is performed on collocated MIPAS-MIPAS pairs and suggests a slight underestimation of its errors by a factor of 1.2. A parametric model consisting of constant, linear, QBO and several sine and cosine terms with different periods has been fitted to the temporal variation of differences of stratospheric CH4 measurements by MIPAS and ACE-FTS for all 10° latitude/1–2 km altitude bins. Only few significant drifts can be calculated, due to the lack of data. Significant drifts with respect to ACE-FTS tend to have higher absolute values in the Northern Hemisphere, have no pronounced tendency in the sign, and do not exceed 0.2 ppmv per decade in absolute value.
    06/2015; 8(6):5565-5590. DOI:10.5194/amtd-8-5565-2015
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    ABSTRACT: The MIPAS spectrometer onboard the Envisat platform observed infrared emission from the Earth's limb between 2002 and 2012. It recorded high-resolution spectra during day and night, from pole to pole and between 6 and 70 km altitude in the nominal measurement mode or up to 170 km in special measurement modes, producing daily more than 1000 vertical profiles of various trace gases. The operational Level-2 data are processed by ESA/DLR but there exist three other, independent research Level-2 processors that are hosted by ISAC-CNR/University of Bologna, Oxford University, and KIT IMK/IAA. All four Level-2 processors rely on the same Level-1b data provided by ESA but their retrieval schemes differ. As part of ESA's Ozone Climate Change Initiative project, an intercomparison of the four MIPAS processors took place, in which vertical ozone profiles retrieved by these four processors from MIPAS nominal mode measurements were compared for 2007 and 2008. We present the results of this comparison exercise, which consisted of five parts: an information content study of the vertical averaging kernels, an intercomparison of zonal seasonal means and spreads, a determination of biases through comparison to ozonesonde and lidar measurements, a comparison to other satellite records (bias estimation and precision assessment with respect to ACE-FTS and Aura-MLS data), and a geophysical validation of the provided error bars using MIPAS–MIPAS collocations.
    Remote Sensing of Environment 06/2015; 162. DOI:10.1016/j.rse.2014.12.013 · 6.39 Impact Factor
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    ABSTRACT: We report on HCFC-22 data acquired by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) in reduced spectral resolution nominal mode in the period from January 2005 to April 2012 from version 5.02 level-1b spectral data and covering an 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 measured limb spectral radiances to modelled spectra. 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 linear growth rate in the lower latitudes lower stratosphere was about 6 to 7 pptv yr−1 in the period 2005–2012. The obtained profiles were compared with ACE-FTS satellite data v3.5, as well as with MkIV balloon profiles and in situ 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. Obtained MIPAS HCFC-22 time series below 10 km altitude are shown to agree mostly well to corresponding time series of near-surface abundances from NOAA/ESRL and AGAGE networks, although a more pronounced seasonal cycle is obvious in the satellite data, probably due 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. In the middle stratosphere between 20 and 30 km, the observed trend is not consistent with the age of stratospheric air-corrected trend at ground, but stronger positive at the Southern Hemisphere and less strong increasing in the Northern Hemisphere, hinting towards changes in the stratospheric circulation over the observation period.
    Atmospheric Chemistry and Physics 05/2015; 15(10):14783-14841. DOI:10.5194/acpd-15-14783-2015 · 4.88 Impact Factor
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    ABSTRACT: Trends in the vertical distribution of ozone are reported and compared for a number of new and recently revised datasets. The amount of ozone-depleting compounds in the stratosphere (as measured by Equivalent Effective Stratospheric Chlorine – EESC) maximised in the second half of the 1990s. We therefore examine the trends in the periods before and after that peak to see if any change in trend is discernible in the ozone record. Prior to 1998, trends in the upper stratosphere (∼45km, 4hPa) are found to be −5 to −10 % per decade at mid-latitudes and closer to −5 % per decade in the tropics. No trends are found in the mid-stratosphere (28 km, 30 hPa). Negative trends are seen in the lower stratosphere at mid-latitudes in both hemispheres and in the deep tropics. However it is hard to be categorical about the trends in the lower stratosphere for three reasons: (i) there are fewer measurements, (ii) the data quality is poorer, and (iii) the measurements in the 1990s are perturbed by aerosols from the Mt. Pinatubo eruption in 1991. These findings are similar to those reported previously even though the measurements for the two main satellite instruments (SBUV and SAGE II) and the ground-based Umkehr and ozonesonde stations have been revised. There is no sign of a continued negative trend in the upper stratosphere since 1998: instead there is a hint of an average positive trend of ∼ 2 % per decade in mid-latitudes and ∼3 % per decade in the tropics. The significance of these upward trends is investigated using different assumptions of the independence of the trend estimates found from different datasets. The averaged upward trends are significant if the trends derived from various datasets are assumed to be independent, but are generally not significant if the trends are not independent. This arises because many of the underlying mea- surement records are used in more than one merged dataset. At this point it is not possible to say which assumption is best. Including an estimate of the drift of the over- all ozone observing system decreases the significance of the trends. The significance will become clearer as (i) more years are added to the observational record, (ii) further improvements are made to the historic ozone record (e.g. through algorithm development), and (iii) the data merging techniques are refined, particularly through a more rigorous treatment of uncertainties.
    Atmospheric Chemistry and Physics 05/2015; 15(6):8565–8608. DOI:10.5194/acpd-15-8565-2015 · 4.88 Impact Factor
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    ABSTRACT: CMAM30 is a 30 year data set extending from 1979 to 2010 that is generated using a version of the Canadian Middle Atmosphere Model (CMAM) in which the winds and temperatures are relaxed to the Interim Reanalysis product from the European Centre Medium-Range for Weather Forecasts (ERA-Interim). The data set has dynamical fields that are very close to the reanalysis below 1 hPa and chemical tracers that are self-consistent with respect to the model winds and temperature. The chemical tracers are expected to be close to actual observations. The data set is here compared to two satellite records – the Atmospheric Chemistry Experiment Fourier Transform Spectometer and the Odin Optical Spectrograph and InfraRed Imaging System – for the purpose of validating the temperature, ozone, water vapour and methane fields. Data from the Aura Microwave Limb Sounder is also used for validation of the chemical processing in the polar vortex. It is found that the CMAM30 temperature is warm by up to 5 K in the stratosphere, with a low bias in the mesosphere of ~ 5–15 K. Ozone is reasonable (± 15%) except near the tropopause globally, and in the Southern Hemisphere winter polar vortex. Water vapour is consistently low by 10–20%, with corresponding high methane of 10–20%, except in the Southern Hemisphere polar vortex. Discrepancies in this region are shown to stem from the treatment of polar stratospheric cloud formation in the model.
    Atmospheric Chemistry and Physics 04/2015; 15(8):11179-11221. DOI:10.5194/acpd-15-11179-2015 · 4.88 Impact Factor
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    ABSTRACT: As part of ESA's climate change initiative high vertical resolution ozone profiles from three instruments all aboard ESA's Envisat (GOMOS, MIPAS, SCIAMACHY) in combination with ESA's third party missions (OSIRIS, SMR, ACE-FTS) are to be combined in order to create an essential climate variable data record for the last decade. A prerequisite before combining data is the examination of differences and drifts between the datasets. In this paper, we present a detailed analysis of ozone profile differences based on pairwise collocated measuerements, including the evolution of the differences with time. Such a diagnosis is helpful to identify strengths and weaknesses of each data set that may vary in time and introduce uncertainties in long-term trend estimates. Main results of this paper indicate that the 6 instruments perform well in the stratosphere particularly between 20 and 40 km with a mean relative difference of ±5% (middle latitudes) to ±10% (tropics). Larger differences and variability in the differences are found in the upper troposphere lower stratosphere region and in the mesosphere. The analysis reveals that the relative drift between the sensors is not statistically significant for most pairs of instruments.
    04/2015; 8(4):3697-3728. DOI:10.5194/amtd-8-3697-2015
  • Atmospheric Chemistry and Physics 03/2015; 15(5):2487-2488. DOI:10.5194/acp-15-2487-2015 · 5.51 Impact Factor
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    ABSTRACT: In a case study of a remarkable Major stratospheric sudden Warming (MW) during the boreal winter 2008/09, we investigate how transport and mixing triggered by this event affect the composition of the whole stratosphere in the Northern Hemisphere. We simulate this event with the Chemical Lagrangian Model of the Stratosphere (CLaMS), with optimized mixing parameters and with no mixing, i.e. with transport occurring only along the Lagrangian trajectories. The results are investigated by using the tracer–tracer correlation technique and by applying the Transformed Eulerian Mean formalism. The CLaMS simulation of N2O and O3 with optimized mixing parameters shows good agreement with the Aura Microwave Limb Sounder (MLS) data. The spatial distribution of mixing intensity in CLaMS correlates fairly well with the Eliassen–Palm flux convergence and illustrates how planetary waves drive mixing. By comparing the simulations with and without mixing, we find that after the MW poleward transport of air increases not only across the vortex edge but also across the subtropical transport barrier. Moreover, the MW event also accelerates polar descent and tropical ascent of the Brewer–Dobson circulation. The accelerated ascent in the tropics and descent at high latitudes firstly occurs in the upper stratosphere and then propagates downward to the lower stratosphere. This downward propagation takes over one month from the potential temperature level of 1000 to 400 K.
    Atmospheric Chemistry and Physics 02/2015; 15(4):4383-4426. DOI:10.5194/acpd-15-4383-2015 · 4.88 Impact Factor
  • P. E. Sheese · C. D. Boone · K. A. Walker
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    ABSTRACT: The ACE-FTS (Atmospheric Chemistry Experiment-Fourier Transform Spectrometer) instrument on board the Canadian satellite SCISAT has been observing the Earth's limb in solar occultation since its launch in 2003. Since February 2004, high resolution (0.02 cm(-1)) observations in the spectral region of 750-4400 cm(-1) have been used to derive volume mixing ratio profiles of over 30 atmospheric trace species and over 20 atmospheric isotopologues. Although the full ACE-FTS level 2 data set is available to users in the general atmospheric community, until now no quality flags have been assigned to the data. This study describes the two-stage procedure for detecting physically unrealistic outliers within the data set for each retrieved species, which is a fixed procedure across all species. Since the distributions of ACE-FTS data across regions (altitude/latitude/season/local time) tend to be asymmetric and multimodal, the screening process does not make use of the median absolute deviation. It makes use of volume mixing ratio probability density functions, assuming that the data, when sufficiently binned, are at most tri-modal and that these modes can be represented by the superposition of three normal, or log-normal, distributions. Quality flags have been assigned to the data based on retrieval statistical fitting error, the physically unrealistic outliers described in this study, and known instrumental/processing errors. The quality flags defined and discussed in this study are now available for all level 2 versions 2.5 and 3.5 data and will be made available as a standard product for future versions.
    Atmospheric Measurement Techniques 02/2015; 8(2):741-750. DOI:10.5194/amt-8-741-2015 · 3.21 Impact Factor
  • Niall J. Ryan · Kaley A. Walker
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    ABSTRACT: A preparatory performance and error characterization was carried out for a ground-based millimeter wave instrument designed for high Arctic atmospheric research. The instrument is a radiometer to measure rotational emission spectra of O3, ClO, HNO3, and N2O, between 265 and 280 GHz, using a sensitive superconductor–insulator–superconductor detector. Forward and inverse modeling tests have been performed to assess the instrument/inversion system and to determine the sources of the most significant errors in the retrieval of each trace gas. The altitude ranges over which retrievals of concentrations can be made were found to be ~13–62 km for O3, ~12.5–39 km for N2O, ~12–36 km for HNO3, and ~18–46 km for ClO. For each target species the measurement and smoothing errors calculated with an optimal estimation method (OEM) were compared to the errors calculated from inversions of 500 simulated spectra. The absolute error from these inversions agreed well the OEM results, but there were systematic differences that are attributed to nonlinearities in the forward model. The results of these nonlinearities can cause biases of the order of 5–10% of the a priori profile if they are not accounted for when averaging concentration profiles or when analyzing trends in concentration. The techniques used here can be applied to any ground-based remote sounder.
    Journal of Quantitative Spectroscopy and Radiative Transfer 01/2015; 151:26–37. DOI:10.1016/j.jqsrt.2014.09.010 · 2.29 Impact Factor
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    ABSTRACT: This paper contains a comprehensive investiga-tion of the sunset–sunrise difference (SSD, i.e., the sunset-minus-sunrise value) of the ozone mixing ratio in the lat-itude range of 10 • S–10 • N. SSD values were determined from solar occultation measurements based on data ob-tained from the Stratospheric Aerosol and Gas Experiment (SAGE) II, the Halogen Occultation Experiment (HALOE), and the Atmospheric Chemistry Experiment–Fourier trans-form spectrometer (ACE–FTS). The SSD was negative at al-titudes of 20–30 km (−0.1 ppmv at 25 km) and positive at 30–50 km (+0.2 ppmv at 40–45 km) for HALOE and ACE– FTS data. SAGE II data also showed a qualitatively simi-lar result, although the SSD in the upper stratosphere was 2 times larger than those derived from the other data sets. On the basis of an analysis of data from the Superconduct-ing Submillimeter-Wave Limb-Emission Sounder (SMILES) and a nudged chemical transport model (the specified dy-namics version of the Whole Atmosphere Community Cli-mate Model: SD–WACCM), we conclude that the SSD can be explained by diurnal variations in the ozone concentra-tion, particularly those caused by vertical transport by the at-mospheric tidal winds. All data sets showed significant sea-sonal variations in the SSD; the SSD in the upper strato-sphere is greatest from December through February, while that in the lower stratosphere reaches a maximum twice: dur-ing the periods March–April and September–October. Based on an analysis of SD–WACCM results, we found that these seasonal variations follow those associated with the tidal ver-tical winds.
    Atmospheric Chemistry and Physics 01/2015; 15(2):829-843. DOI:10.5194/acp-15-829-2015 · 4.88 Impact Factor
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    ABSTRACT: Products from the Measurements Of Pollution In The Troposphere (MOPITT) instrument are regularly validated using in situ airborne measurements. However, few of these measurements reach into the upper troposphere, thus hindering MOPITT validation in that region. Here we evaluate upper tropospheric (~500 hPa to the tropopause) MOPITT CO profiles by comparing them to satellite Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) retrievals and to measurements from the High-performance Instrumented Airborne Platform for Environmental Research Pole to Pole Observations (HIPPO) Quantum Cascade Laser Spectrometer (QCLS). Direct comparison of co-located v5 MOPITT thermal-infrared-only retrievals, v3.0 ACE-FTS retrievals, and HIPPO-QCLS measurements show a slight positive MOPITT CO bias within its 10% accuracy requirement with respect to the other two datasets. Direct comparison of co-located ACE-FTS and HIPPO-QCLS measurements results in a small number of samples, due to the large disparity in sampling pattern and density of these datasets. Thus, two additional indirect techniques for comparison of non-coincident datasets have been applied: tracer-tracer (CO-O3) correlation analysis and analysis of profiles in tropopause coordinates. These techniques suggest a negative bias of ACE-FTS with respect to HIPPO-QCLS; this could be caused by differences in resolution (horizontal, vertical) or by deficiencies in the ACE-FTS CO retrievals below ~20 km of altitude, among others. We also investigate the temporal stability of MOPITT and ACE-FTS data, which provide unique global CO records and are thus important in climate analysis. Our results indicate that the relative bias between the two datasets has remained generally stable during the 2004–2010 period.
    12/2014; 119(24). DOI:10.1002/2014JD022397
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    ABSTRACT: We present the results of an extensive validation program of the most recent version of ozone vertical pro-files retrieved with the IMK/IAA (Institute for Meteorol-ogy and Climate Research/Instituto de Astrofísica de An-dalucía) MIPAS (Michelson Interferometer for Passive At-mospheric Sounding) research level 2 processor from ver-sion 5 spectral level 1 data. The time period covered corre-sponds to the reduced spectral resolution period of the MI-PAS instrument, i.e., January 2005–April 2012. The compar-ison with satellite instruments includes all post-2005 satellite limb and occultation sensors that have measured the vertical profiles of tropospheric and stratospheric ozone: ACE-FTS, GOMOS, HALOE, HIRDLS, MLS, OSIRIS, POAM, SAGE II, SCIAMACHY, SMILES, and SMR. In addition, balloon-borne MkIV solar occultation measurements and ground-based Umkehr measurements have been included, as well as two nadir sensors: IASI and SBUV. For each reference data set, bias determination and precision assessment are per-formed. Better agreement with reference instruments than for the previous data version, V5R_O3_220 (Laeng et al., 2014), Published by Copernicus Publications on behalf of the European Geosciences Union. 3972 A. Laeng et al.: Validation of MIPAS IMK/IAA V5R_O3_224 ozone profiles is found: the known high bias around the ozone vmr (vol-ume mixing ratio) peak is significantly reduced and the verti-cal resolution at 35 km has been improved. The agreement with limb and solar occultation reference instruments that have a known small bias vs. ozonesondes is within 7 % in the lower and middle stratosphere and 5 % in the upper tro-posphere. Around the ozone vmr peak, the agreement with most of the satellite reference instruments is within 5 %; this bias is as low as 3 % for ACE-FTS, MLS, OSIRIS, POAM and SBUV.
    Atmospheric Measurement Techniques 11/2014; 7(11):3971-3987. DOI:10.5194/amt-7-3971-2014 · 3.21 Impact Factor
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    ABSTRACT: Chlorofluorocarbons (CFCs) play a key role in stratospheric ozone loss and are strong infrared absorbers that contribute to global warming. The stratospheric lifetimes of CFCs are a measure of their stratospheric loss rates that are needed to determine global warming and ozone depletion potentials. We applied the tracer–tracer correlation approach to zonal mean climatologies from satellite measurements and model data to assess the lifetimes of CFCl3 (CFC-11) and CF2Cl2 (CFC-12). We present estimates of the CFC-11/CFC-12 lifetime ratio and the absolute lifetime of CFC-12, based on a reference lifetime of 52 years for CFC-11. We analyzed climatologies from three satellite missions, the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), the HIgh Resolution Dynamics Limb Sounder (HIRDLS), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). We found a CFC-11/CFC-12 lifetime ratio of 0.47±0.08 and a CFC-12 lifetime of 112(96–133) years for ACE-FTS, a ratio of 0.46±0.07 and a lifetime of 113(97–134) years for HIRDLS, and a ratio of 0.46±0.08 and a lifetime of 114(98–136) years for MIPAS. The error-weighted, combined CFC-11/CFC-12 lifetime ratio is 0.46±0.04 and the CFC-12 lifetime estimate is 113(103–124) years. These results agree with the recent Stratosphere-troposphere Processes And their Role in Climate (SPARC) reassessment, which recommends lifetimes of 52(43–67) years and 102(88–122) years, respectively. Having smaller uncertainties than the results from other recent studies, our estimates can help to better constrain CFC-11 and CFC-12 lifetime recommendations in future scientific studies and assessments. Furthermore, the satellite observations were used to validate first simulation results from a new coupled model system, which integrates a Lagrangian chemistry transport model into a climate model. For the coupled model we found a CFC-11/CFC-12 lifetime ratio of 0.48±0.07 and a CFC-12 lifetime of 110(95–129) years, based on a 10-year perpetual run. Closely reproducing the satellite observations, the new model system will likely become a useful tool to assess the impact of advective transport, mixing, and photochemistry as well as climatological variability on the stratospheric lifetimes of long-lived tracers.
    Atmospheric Chemistry and Physics 11/2014; 14(11):16865-16906. DOI:10.5194/acpd-14-16865-2014 · 4.88 Impact Factor
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    ABSTRACT: The abundance of chlorine in the Earth's atmosphere increased considerably during the 1970s to 1990s, following large emissions of anthropogenic long-lived chlorine-containing source gases, notably the chlorofluorocarbons. The chemical inertness of chlorofluorocarbons allows their transport and mixing throughout the troposphere on a global scale, before they reach the stratosphere where they release chlorine atoms that cause ozone depletion. The large ozone loss over Antarctica was the key observation that stimulated the definition and signing in 1987 of the Montreal Protocol, an international treaty establishing a schedule to reduce the production of the major chlorine- and bromine-containing halocarbons. Owing to its implementation, the near-surface total chlorine concentration showed a maximum in 1993, followed by a decrease of half a per cent to one per cent per year, in line with expectations. Remote-sensing data have revealed a peak in stratospheric chlorine after 1996, then a decrease of close to one per cent per year, in agreement with the surface observations of the chlorine source gases and model calculations. Here we present ground-based and satellite data that show a recent and significant increase, at the 2σ level, in hydrogen chloride (HCl), the main stratospheric chlorine reservoir, starting around 2007 in the lower stratosphere of the Northern Hemisphere, in contrast with the ongoing monotonic decrease of near-surface source gases. Using model simulations, we attribute this trend anomaly to a slowdown in the Northern Hemisphere atmospheric circulation, occurring over several consecutive years, transporting more aged air to the lower stratosphere, and characterized by a larger relative conversion of source gases to HCl. This short-term dynamical variability will also affect other stratospheric tracers and needs to be accounted for when studying the evolution of the stratospheric ozone layer.
    Nature 11/2014; 515(7525):104-107. DOI:10.1038/nature13857 · 42.35 Impact Factor

Publication Stats

3k Citations
718.69 Total Impact Points

Institutions

  • 2005–2015
    • University of Toronto
      • Department of Physics
      Toronto, Ontario, Canada
  • 1058–2011
    • University of Waterloo
      • Department of Chemistry
      Waterloo, Ontario, Canada
  • 2004
    • Trent University
      • Environmental and Resource Studies
      Питерборо, Ontario, Canada