Stratospheric chemical ionization mass spectrometry: nitric acid detection by different ion molecule reaction schemes

Detailed height profiles of stratospheric nitric acid mixing ratios have been derived with a baloon borne chemical ionization mass spectrometer by applying several ion molecule reaction schemes, each associated to a specific and selective ion source. These ions (CO₃⁻, Cl_n⁻, CF₃O⁻, and CF₃O⁻H₂O) give rise to specific product ions (mainly CO₃⁻HNO₃, NO₃⁻HCl, NO₃⁻HF, and CF₃O⁻HNO₃) upon reaction with ambient nitric acid molecules. This paper reports on the instrumental details as well as on the results obtained during two balloon flights with the instrument. Within the accuracy of the measurements, the nitric acid height profiles obtained with the three different ion sources are in good agreement with one another as well as with literature data.     

The ν5 and 2ν9 bands of the N isotopic species of nitric acid (H15NO3): Line positions and intensities

Nitric acid (HNO₃) plays an important role in the Earth’s atmosphere as a reservoir molecule of NO_x species. It has a strong infrared signature at 11 μm which is one of the most commonly used for the infrared retrieval of this species in the atmosphere since this spectral region coincides with an atmospheric window. It is therefore essential to have high quality spectral parameters in this spectral region. For the H¹⁴NO₃ (main) isotopic species, the 11 μm bands were already the subject of numerous extensive studies which involve not only the ν₅ and 2ν₉ cold bands but also the first hot bands. The present work is the first high resolution Fourier transform analysis of the 11 μm bands for H¹⁵NO₃, which is the second most abundant isotopomer of nitric acid [a ≅ 0.00365(7)]. In this way, the analysis of the ν₅ and 2ν₉ cold bands centered at 871.0955 and 893.4518 cm⁻¹ was performed, and as for H¹⁴NO₃, these bands are significantly perturbed since rather strong resonances couple the 5¹ and 9² rotational levels. The theoretical model that we used to compute the line positions and line intensities is directly issued from the one which we used recently for H¹⁴NO₃ [A. Perrin, J. Orphal, J.-M. Flaud, S. Klee, G. Mellau, H. Mäder, D. Walbrodt, M. Winnewisser, J. Mol. Spectrosc. 228 (2004) 375-391]. Actually, for the H¹⁵NO₃ line positions, the Hamiltonian matrix accounts for the rather strong Fermi and the weaker Coriolis interactions linking the 5¹⇔9² rotational levels. Using this model which accounts correctly for the strong mixing of the 5¹ and 9² upper state energy levels, the ν₅ and 2ν₉ line intensities for H¹⁵NO₃ were satisfactorily computed using the ν₅ and 2ν₉ transition moment operators achieved previously for the ¹⁴N (main) isotopic species. In this way, the transfer of intensities from the ν₅ fundamental (and presumably strong) band to the 2ν₉ overtone (and presumably weak) band could be explained for H¹⁵NO₃ as it was done previously for the ¹⁴N (main) isotopic species. Finally, the position of the H¹⁵NO₃ν₅ + ν₉ − ν₉ hot band was identified at 875.245 cm⁻¹.     

An airborne diode laser spectrometer for the simultaneous measurement of H2O and HNO3 content of stratospheric cirrus clouds

We describe a tunable diode laser spectrometer for the in situ simultaneous detection of the nitric acid and the water vapour by means of high resolution absorption spectroscopy on rovibronic lines, using a single laser emitting in the mid-infrared (5.8 μm) and a multipass cell. The instrument was designed to be installed on a high altitude aircraft, as a part of a composite payload for atmospheric aerosol studies. The instrument design criteria are discussed and the expected performances are compared with results of laboratory and field operation. Due to the high chemical activity of HNO₃, that makes difficult to use a reference cell, a fast sweep detection of direct absorption was used for the measurement. An absorption sensitivity of about 2×10⁻⁴ was achieved with an integration time of 2.5 s, corresponding to a concentration of about 4 ppb of HNO₃ in the cell and 0.1 ppb in the external aerosol. The data acquisition and processing techniques, based on the full molecular lineshape fitting are also shown and discussed, including some examples of the data acquired during the scientific flights.     

The ν1, ν2, and ν3 bands of carbonyl chlorofluoride (COFCl) at 5.3, 9.1, and 13.1 μm: position and intensity parameters and their use for atmospheric studies

A list of line positions and, for the first time, of line intensities was generated for the ν₁, ν₂, and ν₃ fundamental bands of the ¹²C¹⁶OF³⁵Cl and ¹²C¹⁶OF³⁷Cl isotopologs of carbonyl chlorofluoride, located at 5.3, 9.1, and 13.1 μm, respectively. In addition, for the most abundant isotopolog (¹²C¹⁶OF³⁵Cl) this linelist includes also the contributions from the first two associated hot bands. The parameters included in this database were generated by combining the results of previous experimental analyses and ab initio calculations [Perrin A, Flaud JM, Bürger H, Pawelke G, Sander S, Willner H. First high resolution analysis of the six fundamental bands ν₁, ν₂, ν₃, ν₄, ν₅ and ν₆ of COF³⁵Cl in the 340 to 2000 cm⁻¹ region. J Mol Spectrosc 2001;209:122-232; Demaison J, Perrin A, Bürger H. Ab initio anharmonic force field and equilibrium structure of carbonyl chlorofluoride. J Mol Spectrosc 2003;221:47-56]. For the purpose of the present work, a partial re-investigation of the ν₁ of COF³⁵Cl was performed, together with the first identification of the ν₂ band of COF³⁷Cl.These parameters were generated in order to improve the quality of remote sensing of the atmosphere in the mid-IR. Analyses of atmospheric solar occultation spectra measured by the JPL MkIV interferometer show that the new linelist not only improves the quality of retrievals of COFCl, but also of several other gases whose absorptions overlap those of COFCl.     

A new software suite for NO2 vertical profile retrieval from ground-based zenith-sky spectrometers

Here we present an operational method to improve accuracy and information content of ground-based measurements of stratospheric NO₂. The motive is to improve the investigation of trends in NO₂, and is important because the current trend in NO₂ appears to contradict the trend in its source, suggesting that the stratospheric circulation has changed. To do so, a new software package for retrieving NO₂ vertical profiles from slant columns measured by zenith-sky spectrometers has been created. It uses a Rodgers optimal linear inverse method coupled with a radiative transfer model for calculations of transfer functions between profiles and columns, and a chemical box model for taking into account the NO₂ variations during twilight and during the day. Each model has parameters that vary according to season and location. Forerunners of each model have been previously validated. The scheme maps random errors in the measurements and systematic errors in the models and their parameters on to the retrieved profiles. Initialisation for models is derived from well-established climatologies. The software has been tested by comparing retrieved profiles to simultaneous balloon-borne profiles at mid-latitudes in spring.     

Adsorption and photochemistry of multilayer bromoform on ice

The adsorption and photochemistry of bromoform multilayers on and in amorphous solid water (ASW) are studied using reflection absorption infrared spectroscopy (RAIRS), temperature-programmed desorption (TPD), and time-of-flight (TOF) techniques. Regardless of the initial exposure, bromoform resides on top of the ASW layer. No migration of bromoform molecules into the ASW film is observed for adsorption on top of the water layer. UV irradiation at a wavelength of 266 nm results in significant desorption of photochemical fragments, reaction of photochemical products on the surface and light-induced molecular reorganization of the remaining CHBr₃, which is apparent from a comparison of pre- and post-irradiation TPD experiments. The ice-mediated C-C (C₂H₂Br₂) and C-O (CHBrO) photoproducts desorb from both the ASW surface and the Pt surface. The photoproduct C₂H₂Br₄ is formed exclusively from multilayers of CHBr₃ and desorbs only from the Pt surface.     

Measurements of mid-stratospheric formaldehyde from the Odin/SMR instrument

Measurements of mid-stratospheric formaldehyde (H₂CO) have been obtained from the limb-viewing sub-millimeter radiometer (SMR) instrument aboard the Odin satellite. The analysis is based upon the only weak (8₀₈→7₀₇) rotational transition line of H₂CO that can be measured by Odin/SMR at 576.7083150 GHz in the band dedicated to the measurement of carbon monoxide (CO). The signal-to-noise ratio is increased by averaging about 1000 spectra within 2-km width vertical layers in the stratosphere over periods from 1 to 7 days and within 3 latitude bands: Southern Hemisphere (90°S-45°S), tropics (30°S-30°N), and Northern Hemisphere (45°N-90°N). The faint H₂CO line can then be retrieved using the standard scientific ground-segment developed for the Odin/SMR measurements. The mid-stratospheric H₂CO shows maxima in the tropics for every period considered (January 2006, February 2005, March 2005, and September 2005). The spring-time extra-tropical mid-stratospheric H₂CO is more intense than the fall-time extra-tropical amounts. The simulations from the three-dimensional chemical-transport model Reprobus satisfactorily show these general features.     

On the quality of the Nimbus 7 LIMS version 6 ozone for studies of the middle atmosphere

The Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) radiance profile dataset of 1978/79 was reconditioned and reprocessed to Version 6 (V6) profiles of temperature and species that are improved significantly over those from Version 5 (V5). The LIMS V6 dataset was archived for public use in 2002. Improvements for its ozone include: (1) a more accurate accounting for instrument and spacecraft motion effects in the radiances, (2) the use of better spectroscopic line parameters for its ozone forward model, (3) retrievals of all its scans, (4) more accurate and compatible temperature versus pressure profiles (or T(p)) that are needed for the registration of the ozone radiances and for the removal of temperature effects from them, and (5) a better accounting for interfering species in the lower stratosphere. The retrieved V6 ozone profiles extend from near cloud top altitudes to about 80 km and from 64S to 84N latitude with better sampling along the orbit than for the V5 dataset. Calculated estimates of the single-profile precision and accuracy are provided; precision estimates based on the data themselves are of order 3% or better from 1 to 30 hPa. Estimates of total systematic error are hard to generalize because the separate sources of error may not all be of the same sign, and they depend somewhat on the atmospheric state. It is estimated that the accuracy of the V6 zonal mean ozone distribution is within ±9% from 50-10 hPa, improving to ±7% in the uppermost stratosphere. Simulation studies show that the LIMS T(p) retrievals are underestimating slightly the small amplitudes of the atmospheric temperature tides, which affect the retrieved day/night ozone differences. There are also small biases in the middle to lower stratosphere for the ascending versus descending node LIMS ozone, due principally to not accounting for the asymmetric weighting of its radiance within the tangent layer. The total accuracy for the LIMS ozone was assessed by comparing its daily zonal mean, daytime distributions against those from the Nimbus 7 SBUV Version 8 (V8) dataset for the same period. The LIMS V6 ozone agrees well with SBUV, except between 2 and 5 hPa where the LIMS ozone is greater. That bias is related to the differing vertical resolutions and forward models for the two experiments. The accuracy for LIMS V6 ozone in the lower stratosphere is improved over that reported for V5, as indicated by a small set of V6 comparisons with ECC ozonesonde profiles. Comparisons of diurnal, photochemical model calculations with the monthly-averaged, upper stratospheric ozone obtained with LIMS V6 indicate only a slight ozone deficit for the model at about 2 hPa. However, that deficit exhibits little to no seasonal variation and is in good agreement with similar model comparisons for a seasonal time series of ozone obtained with ground-based microwave instruments. Because the LIMS V6 ozone has improved accuracy and sampling versus that of V5 for the lower stratosphere it should now be possible to conduct quantitative studies of ozone transport and chemistry for the northern hemisphere, polar winter/spring of 1978/79—a time period when the catalytic loss of ozone due to reactive chlorine should not have been a major factor for the Arctic stratosphere.