Christopher E. Sioris

Stratospheric effects of energetic particle precipitation in 2003-2004

Upper stratospheric enhancements in NOx (NO and NO2) were observed at high northern latitudes from March through at least July of 2004. Multi-satellite data analysis is used to examine the temporal evolution of the enhancements, to place them in historical context, and to investigate their origin. The enhancements were a factor of 4 higher than nominal at some locations, and are unprecedented in the northern hemisphere since at least 1985. They were accompanied by reductions in O-3 of more than 60% in some cases. The analysis suggests that energetic particle precipitation led to substantial NOx production in the upper atmosphere beginning with the remarkable solar storms in late October 2003 and possibly persisting through January. Downward transport of the excess NOx, facilitated by unique meteorological conditions in 2004 that led to an unusually strong upper stratospheric vortex from late January through March, caused the enhancements.

Sensitivity of ozone to bromine in the lower stratosphere

Measurements of BrO suggest that inorganic bromine (Br_y) at and above the tropopause is 4 to 8 ppt greater than assumed in models used in past ozone trend assessment studies. This additional bromine is likely carried to the stratosphere by short-lived biogenic compounds and their decomposition products, including tropospheric BrO. Including this additional bromine in an ozone trend simulation increases the computed ozone depletion over the past ∼25 years, leading to better agreement between measured and modeled ozone trends. This additional Br_y (assumed constant over time) causes more ozone depletion because associated BrO provides a reaction partner for ClO, which increases due to anthropogenic sources. Enhanced Br_y causes photochemical loss of ozone below ∼14 km to change from being controlled by HO_x catalytic cycles (primarily HO_2+O_3) to a situation where loss by the BrO+HO_2 cycle is also important.

Ozone profile and tropospheric ozone retrievals from the Global Ozone Monitoring Experiment: Algorithm description and validation

Received 18 May 2005; revised 4 August 2005; accepted 1 September 2005; published 29 October 2005. [1] Ozone profiles are derived from back scattered radiance spectra in the ultraviolet (289–339 nm) measured by the Global Ozone Monitoring Experiment (GOME) using the optimal estimation technique. Tropospheric Column Ozone (TCO) is directly derived using the known tropopause to divide the stratosphere and troposphere. To optimize the retrieval and improve the fitting precision needed for tropospheric ozone, we perform extensive wavelength and radiometric calibrations and improve forward model inputs. The a priori influence of retrieved TCO is � 15% in the tropics and increases to � 50% at high latitudes. The dominant error terms are the smoothing errors, instrumental randomnoise errors, and systematic temperature errors. We compare our GOME retrievals with Earth-Probe Total Ozone Mapping Spectrometer (TOMS) Total column Ozone (TO), Dobson/Brewer (DB) TO, and ozonesonde TCO at 33 World Ozone and Ultraviolet Radiation Data Centre (WOUDC) stations between 71� S and 75� N during 1996–1999. The mean biases with TOMS and DB TO are within 6 DU (2%, 1 DU = 2.69 � 10 16 molecules cm � 2 ) at most of the stations. The retrieved Tropospheric Column Ozone (TCO) captures most of the temporal variability in ozonesonde TCO; the mean biases are mostly within 3 DU (15%) and the standard deviations (1s) are within 3–8 DU (13–27%). We also compare our retrieved ozone profiles above � 15 km against Stratospheric Aerosol and Gas Experiment II measurements from 1996 to 1999. The mean biases and standard deviations are usually within 15%.

Air quality over the Canadian oil sands : a first assessment using satellite observations

Results from the first assessment of air quality over the Canadian oil sands–one of the largest industrial undertakings in human history–using satellite remote sensing observations of two pollutants, nitrogen dioxide (NO2) and sulfur dioxide (SO2), are presented. High-resolution maps were created that revealed distinct enhancements in both species over an area (roughly 30 km × 50 km) of intensive surface mining at scales of a few kilometers. The magnitude of these enhancements, quantified in terms of total mass, are comparable to the largest seen in Canada from individual sources. The rate of increase in NO2between 2005 and 2010 was assessed at 10.4 ± 3.5%/year and resulted from increases both in local values as well as the spatial extent of the enhancement. This is broadly consistent with both surface-measurement trends and increases in annual bitumen production. An increase in SO2 was also found, but given larger uncertainties, it is not statistically significant.

Polar vortex evolution during the 2002 Antarctic major warming as observed by the Odin satellite

In September 2002 the Antarctic polar vortex split in two under the influence of a sudden warming. During this event, the Odin satellite was able to measure both ozone (O3) and chlorine monoxide (ClO), a key constituent responsible for the so-called “ozone hole”, together with nitrous oxide (N2O), a dynamical tracer, and nitric acid (HNO3) and nitrogen dioxide (NO2), tracers of denitrification. The submillimeter radiometer (SMR) microwave instrument and the Optical Spectrograph and Infrared Imager System (OSIRIS) UV-visible light spectrometer (VIS) and IR instrument on board Odin have sounded the polar vortex during three different periods: before (19–20 September), during (24–25 September), and after (1–2 and 4–5 October) the vortex split. Odin observations coupled with the Reactive Processes Ruling the Ozone Budget in the Stratosphere (REPROBUS) chemical transport model at and above 500 K isentropic surfaces (heights above 18 km) reveal that on 19–20 September the Antarctic vortex was dynamically stable and chemically nominal: denitrified, with a nearly complete chlorine activation, and a 70% O3 loss at 500 K. On 25–26 September the unusual morphology of the vortex is monitored by the N2O observations. The measured ClO decay is consistent with other observations performed in 2002 and in the past. The vortex split episode is followed by a nearly complete deactivation of the ClO radicals on 1–2 October, leading to the end of the chemical O3 loss, while HNO3 and NO2 fields start increasing. This acceleration of the chlorine deactivation results from the warming of the Antarctic vortex in 2002, putting an early end to the polar stratospheric cloud season. The model simulation suggests that the vortex elongation toward regions of strong solar irradiance also favored the rapid reformation of ClONO2. The observed dynamical and chemical evolution of the 2002 polar vortex is qualitatively well reproduced by REPROBUS. Quantitative differences are mainly attributable to the too weak amounts of HNO3 in the model, which do not produce enough NO2 in presence of sunlight to deactivate chlorine as fast as observed by Odin.

Retrieval of stratospheric O3 and NO2 profiles from Odin Optical Spectrograph and Infrared Imager System (OSIRIS) limb-scattered sunlight measurements

Scientific studies of the major environmental questions of global warming and ozone depletion require global data sets of atmospheric constituents with relevant temporal and spatial resolution. In this paper global number density profiles of O3 and NO2 are retrieved from Odin/OSIRIS limb-scattered sunlight measurements, using the Maximum A Posteriori estimator. Differential Optical Absorption Spectroscopy is applied to OSIRIS radiances as an intermediate step, using the wavelength windows 571-617 nm for O3 and 435-451 nm for NO2. The method is computationally efficient for processing OSIRIS data on an operational basis. Results show that a 2-3 km height resolution is generally achievable between about 12 km and 45 km for O3 with an estimated accuracy of 13\% at the peak and between about 15 km and 40 km for NO2 with an estimated accuracy of 10\% at the peak. First validations of the retrieved data indicate a good agreement both with other retrieval techniques applied to OSIRIS measurements and with the results of other instruments. Once the validation has reached a confident level, the retrieved data will be used to study important stratospheric processes relevant to global environmental problems. The unique NO2 data set will be of particular interest for studies of nitrogen chemistry in the middle atmosphere.

Undersampling correction for array detector-based satellite spectrometers

Array detector-based instruments are now fundamental to measurements of ozone and other atmospheric trace gases from space in the ultraviolet, visible, and infrared. The present generation of such instruments suffers, to a greater or lesser degree, from undersampling of the spectra, leading to difficulties in the analysis of atmospheric radiances. We provide extended analysis of the undersampling suffered by modern satellite spectrometers, which include the Global Ozone Monitoring Experiment, Scanning Imaging Absorption Spectrometer for Atmospheric Chartography, Ozone Monitoring Instrument, and Ozone Mapping and Profiler Suite. The analysis includes basic undersampling, the effects of binning into separate detector pixels, and the application of high-resolution Fraunhofer spectral data to correct for undersampling in many useful cases.

Stratospheric profiles of nitrogen dioxide observed by Optical Spectrograph and Infrared Imager System on the Odin satellite

[1] Vertical profiles of nitrogen dioxide in the 19–40 km altitude range are successfully retrieved over the globe from Optical Spectrograph and Infrared Imager System (OSIRIS) limb scatter observations in late 2001 and early 2002. The inclusion of multiple scattering in the radiative transfer model used in the inversion algorithm allows for the retrieval of NO2 down to 19 km. The slant column densities, which represent the observations in the inversion, are obtained by fitting the fine structure in normalized radiance spectra over the 435–449 nm range, where NO2 electronic absorption is readily observable because of long light paths through stratospheric layers rich in this constituent. Details of the spectral fitting and inversion algorithm are discussed, including the discovery of a pseudo-absorber associated with pixelated detectors and a new method to verify altitude registration. Comparisons are made with spatially and temporally coincident profile measurements of this photochemically active trace gas. Better than 20% agreement is obtained with all correlative measurements over the common retrieval altitude range, confirming the validity of OSIRIS NO2 profiles. Systematic biases in the number densities are not observed at any altitude. A ‘‘snapshot’’ meridional cross section between 40� N and 70� S is shown from observations during a fraction of an orbit. INDEX TERMS: 0340 Atmospheric Composition and Structure: Middle atmosphere—composition and chemistry; 0360 Atmospheric Composition and Structure: Transmission and scattering of radiation; 0394 Atmospheric Composition and Structure: Instruments and techniques; 3334 Meteorology and Atmospheric Dynamics: Middle atmosphere dynamics (0341, 0342); KEYWORDS: optical, Sun-synchronous, polar-orbiting, Fraunhofer, Ring effect, iterative onion peel

Latitudinal and vertical distribution of bromine monoxide in the lower stratosphere from Scanning Imaging Absorption Spectrometer for Atmospheric Chartography limb scattering measurements

[1] Vertical profiles of stratospheric bromine monoxide (BrO) in the 15–30 km range are retrieved from SCIAMACHY limb scatter data over the globe. First validation comparisons with the balloon-borne SAOZ-BrO and LPMA/DOAS instruments indicate retrieval biases of � 20% or less. Propagated spectral fitting uncertainties lead to a precision approaching � 25% on a 2 km grid at 25 km. This worsens at higher altitudes because of reduced signal and at lower altitudes because of the reduced penetrability of the atmosphere. In terms of volume mixing ratio (VMR), the single profile precision increases from � 4 pptv at 17 km to � 8 pptv at 27 km. Repeatability, an alternative indicator of precision, is 2–3 pptv for SCIAMACHY retrievals and independent of altitude. The BrO stratospheric number density peak generally lies 5 ± 2 km above the tropopause. In the tropics, the stratospheric BrO VMR generally increases with increasing altitude. The observed stratospheric BrO global distribution is generally consistent with previous balloon measurements but does not agree well with results of a model that uses Bry inferred only from the observed breakdown of long-lived bromoalkanes (i.e., methyl bromide and halons). We find best agreement with the observed vertical and latitudinal distribution of BrO for model results that include an 8.4 ± 2 pptv contribution to stratospheric Bry, most of which is expected from the breakdown of VSL (very short lived) bromocarbons, in addition to the � 16 pptv contribution from longer-lived sources. This suggests that stratospheric Bry exceeds 20 pptv. Profiles of Bry profiles derived from the balloon measurements of BrO also suggest Bry is in excess of 20 pptv, but the uncertainty and variability of these results do not allow us to definitively rule out this concentration. We find typical BrO VMRs of � 4 pptv at 15 km in the tropical tropopause layer, suggesting that a significant portion of the bromine from VSL bromoalkane sources may be carried across the tropopause in the form of inorganic decomposition products. We discuss a variety of VSL bromocarbons species that may be contributing to the elevated concentrations of stratospheric BrO.

Impact of rotational Raman scattering in the O2A band

Radiative transfer calculations with scattering and absorption by aerosols and molecules are used to estimate the magnitude of the Ring effect in the O2A band. Rotational Raman scattering significantly alters the A band line depths and shapes for a satellite nadir-viewing case at high solar zenith angles in the absence of thick clouds. In the limb view, at low spectral resolution, the only impact of rotational Raman scattering is that it significantly reduces the radiance in the shoulder of the R branch. The latter effect is also observed for zenith viewing geometry from the ground.