Revising the retrieval technique of a long-term stratospheric HNO3 data set: from a constrained matrix inversion to the optimal estimation algorithm

The Ground-Based Millimeter-wave Spectrometer (GBMS) was designed and built at the State University of New York at Stony Brook in the early 1990s and since then has carried out many measurement campaigns of stratospheric O3, HNO3, CO and N2O at polar and mid-latitudes. Its HNO3 data set shed light on HNO3 annual cycles over the Antarctic continent and contributed to the validation of both generations of the satellite-based JPL Microwave Limb Sounder (MLS). Following the increasing need for long-term data sets of stratospheric constituents, we resolved to establish a long-term GMBS observation site at the Arctic station of Thule (76.5 N, 68.8 W), Greenland, beginning in January 2009, in order to track the long- and short-term interactions between the changing climate and the seasonal processes tied to the ozone depletion phenomenon. Furthermore, we updated the retrieval algorithm adapting the Optimal Estimation (OE) method to GBMS spectral data in order to conform to the standard of the Network for the Detection of Atmospheric Composition Change (NDACC) microwave group, and to provide our retrievals with a set of averaging kernels that allow more straightforward comparisons with other data sets. The new OE algorithm was applied to GBMS HNO3 data sets from 1993 South Pole observations to date, in order to produce HNO3 version 2 (v2) profiles. A sample of results obtained at Antarctic latitudes in fall and winter and at mid-latitudes is shown here. In most conditions, v2 inversions show a sensitivity (i.e., sum of column elements of the averaging kernel matrix) of 100±20% from 20 to 45 km altitude, with somewhat worse (better) sensitivity in the Antarctic winter lower (upper) stratosphere. The 1 uncertainty on HNO3 v2 mixing ratio vertical profiles depends on altitude and is estimated at 15% or 0.3 ppbv, whichever is larger. Comparisons of v2 with former (v1) GBMS HNO3 vertical profiles, obtained employing the constrained matrix inversion method, show that v1 and v2 profiles are overall consistent. The main difference is at the HNO3 mixing ratio maximum in the 20–25 km altitude range, which is smaller in v2 than v1 profiles by up to 2 ppbv at mid-latitudes and during the Antarctic fall. This difference suggests a better agreement of GBMS HNO3 v2 profiles with both UARS/ and EOS Aura/MLS HNO3 data than previous v1 profiles

On the cryogenic removal of NOy from the Antarctic polar stratosphere

We review current knowledge about the annual cycle of transport of nitrogen oxides to, and removal from, the polar stratosphere, with particular attention to Antarctica where the annual winter denitrifi cation process is both regular in occurrence and severe in effect. Evidence for a large downward fl ux of NOy from the mesosphere to the stratosphere, fi rst seen briefl y in the Limb Infrared Monitor of the Stratosphere (LIMS) data from the Arctic winter of 1978-1979, has been found during the 1990s in both satellite and ground-based observations, though this still seems to be omitted from many atmospheric models. When incorporated in the Stony Brook- St. Petersburg two dimensional (2D) transport and chemistry model, more realistic treatment of the NOy fl ux, along with sulfate transport from the mesosphere, sulfate aerosol formation where temperature is favorable, and the inclusion of a simple ion-cluster reaction, leads to good agreement with observed HNO3 formation in the mid-winter middle to upper stratosphere. To further emphasize the importance of large fl uxes of thermospheric and mesospheric NOy into the polar stratosphere, we have used observations, supplemented with model calculations, to defi ne new altitude dependent correlation curves between N2O and NOy. These are more suitable than those previously used in the literature to represent conditions within the Antarctic vortex region prior to and during denitrifi cation by Polar Stratospheric Cloud (PSC) particles. Our NOy -N2O curves lead to a 40% increase in the average amount of NOy removed during the Antarctic winter with respect to estimates calculated using NOy-N2O curves from the Atmospheric Trace Molecule Spectroscopy (ATMOS)/ATLAS-3 data set

Evolution of temperature, O3, CO, and N2O profiles during the exceptional 2009 Arctic major stratospheric warming as observed by lidar and mm-wave spectroscopy at Thule (76.5°N, 68.8°W), Greenland.

The 2009 Arctic sudden stratospheric warming (SSW) was the most intense event of this kind ever observed. Unique ground-based measurements of middle atmospheric profiles for temperature, O3, CO, and N2O obtained at Thule (76.5°N, 68.8°W), Greenland, in the period January – early March are used to show the evolution of the 2009 SSW in the region of its maximum intensity. The first sign of the SSW was detected at θ~2000 K on January 19, when a rapid decrease in CO mixing ratio took place. The first evidence of a temperature increase was observed at the same level on 22 January, the earliest date on which lidar measurements reached above ~50 km. The warming propagated from the upper to the lower stratosphere in 7 days and the record maximum temperature of 289 K was observed between 1300 and 1500 K potential temperature on 22 January. A strong vortex splitting was associated with the SSW. Stratospheric backward trajectories indicate that airmasses arriving to Thule during the warming peak underwent a rapid compression and an intense adiabatic warming of up to 50 K. The rapid advection of air from the extra-tropics was also occasionally observed to produce elevated values of N2O mixing ratio. Starting from mid-February the temperature profile and the N2O mixing ratio returned to the pre-warming values in the mid and upper stratosphere, indicating the reformation of the vortex at these levels. In late winter, vertical descent from starting altitudes of ~60 km is estimated from CO profiles to be 0.25±0.05 km/day

Millimeter wave spectroscopic measurements of stratospheric and mesospheric constituents over the Italian Alps: stratospheric ozone

Measurements of rotational lines emitted by middle atmospheric trace gases have been carried out from the Alpine station of Testa Grigia (45.9°N, 7.7°E, elev. 3500 m) by means of a Ground-Based Millimeter-wave Spectrometer (GBMS). Observations of species such as O3, HNO3, CO, N2O, HCN, and HDO took place during 4 winter periods, from February 2004 to March 2007, for a total of 116 days of measurements grouped in about 18 field campaigns. By studying the pressure-broadened shape of emission lines the vertical distribution of the observed constituents is retrieved within an altitude range of ∼17-75 km, constrained by the 600 MHz pass band and the 65 kHz spectral resolution of the back-end spectrometer. This work discusses the behavior of stratospheric O3 during the entire period of operation at Testa Grigia. Mid-latitude O3 columnar content as estimated using GBMS measurements can vary by large amounts over a period of very few days, with the largest variations observed in December 2005, February 2006, and March 2006, confirming that the northern winter of 2005-2006 was characterized by a particularly intense planetary wave activity. The largest rapid variation from maximum to minimum O3 column values over Testa Grigia took place in December 2006 and reached a relative value of 72% with respect to the average column content for that period. During most GBMS observation times much of the variability is concentrated in the column below 20 km, with tropospheric weather systems and advection of tropical tropospheric air into the lower stratosphere over Testa Grigia having a large impact on the observed variations in column contents. Nonetheless, a wide variability is also found in middle stratospheric GBMS O3 measurements, as expected for mid-latitude ozone. We find that O3 mixing ratios at ∼32 km are very well correlated with the solar illumination experienced by air masses over the previous ∼15 days, showing that already at 32 km altitude ozone photochemistry dominates over transport processes. The correlation of lower stratospheric ozone concentrations with potential vorticity as an indicator of transport is instead not as clear-cut, due to very complex mixing processes that characterize stratospheric air at mid-latitudes. Correlations of O3 over Testa Grigia with stratospheric tracers such as N2O and HCN, also observed by means of the GBMS, are planned for the future, in order to better characterize lower stratospheric dynamics and therefore lower stratospheric ozone concentrations at mid-latitudes

Validation of the Aura Microwave Limb Sounder HNOmeasurements

We assess the quality of the version 2.2 (v2.2) HNO3 measurements from the Microwave Limb Sounder (MLS) on the Earth Observing System Aura satellite. The MLS HNO3 product has been greatly improved over that in the previous version (v1.5), with smoother profiles, much more realistic behavior at the lowest retrieval levels, and correction of a high bias caused by an error in one of the spectroscopy files used in v1.5 processing. The v2.2 HNO3 data are scientifically useful over the range 215 to 3.2 hPa, with single-profile precision of ∼0.7 ppbv throughout. Vertical resolution is 3–4 km in the upper troposphere and lower stratosphere, degrading to ∼5 km in the middle and upper stratosphere. The impact of various sources of systematic uncertainty has been quantified through a comprehensive set of retrieval simulations. In aggregate, systematic uncertainties are estimated to induce in the v2.2 HNO3 measurements biases that vary with altitude between ±0.5 and ±2 ppbv and multiplicative errors of ±5–15% throughout the stratosphere, rising to ∼±30% at 215 hPa. Consistent with this uncertainty analysis, comparisons with correlative data sets show that relative to HNO3 measurements from ground-based, balloon-borne, and satellite instruments operating in both the infrared and microwave regions of the spectrum, MLS v2.2 HNO3 mixing ratios are uniformly low by 10–30% throughout most of the stratosphere. Comparisons with in situ measurements made from the DC-8 and WB-57 aircraft in the upper troposphere and lowermost stratosphere indicate that the MLS HNO3 values are low in this region as well, but are useful for scientific studies (with appropriate averaging)

Spectrally resolved observations of atmospheric emitted radiance in the H2O rotation band

This paper presents the project Earth Cooling by Water Vapor Radiation, an observational programme, which aims at developing a database of spectrally resolved far infrared observations, in atmospheric dry conditions, in order to validate radiative transfer models and test the quality of water vapor continuum and line parameters. The project provides the very first set of far-infrared spectral downwelling radiance measurements, in dry atmospheric conditions, which are complemented with Raman Lidar-derived temperature and water vapor profiles

Millimeter wave spectroscopic measurements of stratospheric and mesospheric constituents over the Italian Alps: stratospheric ozone

Measurements of rotational lines emitted by middle atmospheric trace gases have been carried out from the Alpine station of Testa Grigia (45.9°N, 7.7°E, elev. 3500 m) by means of a Ground-Based Millimeter-wave Spectrometer (GBMS). Observations of species such as O3, HNO3, CO, N2O, HCN, and HDO took place during 4 winter periods, from February 2004 to March 2007, for a total of 116 days of measurements grouped in about 18 field campaigns. By studying the pressure-broadened shape of emission lines the vertical distribution of the observed constituents is retrieved within an altitude range of ?17-75 km, constrained by the 600 MHz pass band and the 65 kHz spectral resolution of the back-end spectrometer. This work discusses the behavior of stratospheric O3 during the entire period of operation at Testa Grigia. Mid-latitude O3 columnar content as estimated using GBMS measurements can vary by large amounts over a period of very few days, with the largest variations observed in December 2005, February 2006, and March 2006, confirming that the northern winter of 2005-2006 was characterized by a particularly intense planetary wave activity. The largest rapid variation from maximum to minimum O3 column values over Testa Grigia took place in December 2006 and reached a relative value of 72% with respect to the average column content for that period. During most GBMS observation times much of the variability is concentrated in the column below 20 km, with tropospheric weather systems and advection of tropical tropospheric air into the lower stratosphere over Testa Grigia having a large impact on the observed variations in column contents. Nonetheless, a wide variability is also found in middle stratospheric GBMS O3 measurements, as expected for mid-latitude ozone. We find that O3 mixing ratios at ?32 km are very well correlated with the solar illumination experienced by air masses over the previous ?15 days, showing that already at 32 km altitude ozone photochemistry dominates over transport processes. The correlation of lower stratospheric ozone concentrations with potential vorticity as an indicator of transport is instead not as clear-cut, due to very complex mixing processes that characterize stratospheric air at mid-latitudes. Correlations of O3 over Testa Grigia with stratospheric tracers such as N2O and HCN, also observed by means of the GBMS, are planned for the future, in order to better characterize lower stratospheric dynamics and therefore lower stratospheric ozone concentrations at mid-latitudes

NOMAD spectrometer on the ExoMars trace gas orbiter mission: part 2—design, manufacturing, and testing of the ultraviolet and visible channel

NOMAD is a spectrometer suite on board the ESA/Roscosmos ExoMars Trace Gas Orbiter, which launched in March 2016. NOMAD consists of two infrared channels and one ultraviolet and visible channel, allowing the instrument to perform observations quasi-constantly, by taking nadir measurements at the day- and night-side, and during solar occultations. Here, in part 2 of a linked study, we describe the design, manufacturing, and testing of the ultraviolet and visible spectrometer channel called UVIS. We focus upon the optical design and working principle where two telescopes are coupled to a single grating spectrometer using a selector mechanism