Precise measurements of the total concentration of atmospheric CO2 and 13CO2/12CO2 isotopic ratio using a lead-salt laser diode spectrometer.

We have developed a tunable diode laser spectrometer, called SIMCO (spectrometer for isotopic measurements of CO(2)), for determining the concentrations of (12)CO(2) and (13)CO(2) in atmospheric air, from which the total concentration of CO(2) and the isotopic composition (expressed in delta units) delta(13)CO(2) are calculated. The two concentrations are measured using a pair of lines around 2290.1 cm(-1), by fitting a line profile model, taking into account the confinement narrowing effect to achieve a better accuracy. Using the Allan variance, we have demonstrated (for an integration time of 25 s) a precision of 0.1 ppmv for the total CO(2) concentration and of 0.3[per thousand] for delta(13)CO(2). The performances on atmospheric air have been tested during a 3 days campaign by comparing the SIMCO instrument with a gas chromatograph (GC) for the measurement of the total CO(2) concentration and with an isotopic ratio mass spectrometer (MS) for the isotopic composition. The CO(2) concentration measurements of SIMCO are in very good agreement with the GC data with a mean difference of Delta(CO(2))=0.16+/-1.20 ppmv for a comparison period of 45 h and the linearity of the concentration between the two instruments is also very good (slope of correlation: 0.9996+/-0.0003) over the range between 380 and 415 ppmv. For delta(13)CO(2), the comparison with the MS data shows a larger mean difference of Delta(delta(13)CO(2))=(-1.9+/-1.2)[per thousand], which could be partly related to small residual fluctuations of the overall SIMCO instrument response.

Concentration measurements of ozone in the 1200-300ppbv range: an intercomparison between the BNM ultraviolet standard and infrared methods.

Simultaneous ultraviolet (UV) and infrared (IR) measurements of ozone concentration in air in the 1200-300 ppbv range have been performed using the ultraviolet absorption in the Hartley band at 0.2537 microm and the infrared absorption of a doublet at 9.507 microm in the nu(3) vibration-rotation band. Infrared concentration measurements were achieved using the tunable diode laser spectrometer of LPMA in Paris with interferometric control of the emitted wavelength while the UV concentration measurements were performed with the 49PS Megatec ozone generator of the Bureau National de Metrologie (BNM). The simultaneous recording of spectra of a reference cell filled with pure distilled ozone and of a low concentration mixture inside a long absorbing path Herriott cell allows to carry out infrared concentration measurements with an accuracy of the same order as the ultraviolet ones and provides the instrumental parameters of the spectrometer corresponding to each concentration measurement, which reduces systematic errors. Within the respective absolute uncertainties proper to the two techniques, no systematic discrepancy was evidenced between the IR and the UV measurements. The ozone ultraviolet absorption coefficient value determined by Hearn (308.3 +/- 4 cm(-1)atm(-1)) and used by the BNM and the National Institute of Standards and Technology (NIST) is confirmed by the present work.

SPIRALE: a multispecies in situ balloonborne instrument with six tunable diode laser spectrometers.

The balloonborne SPIRALE (a French acronym for infrared absorption spectroscopy by tunable diode lasers) instrument has been developed for in situ measurements of several tracer and chemically active species in the stratosphere. Laser absorption takes place in an open Herriott multipass cell located under the balloon gondola, with six lead salt diode lasers as light sources. One mirror is located at the extremity of a deployable mast 3.5 m below the gondola, enabling the measurement of very low abundance species throughout a very long absorption path (up to 544 m). Three successful flights have produced concentration measurements of O3, CO, CO2, CH4, N2O, NO2, NO, HNO3, HCl, HOCl, COF2, and H2O2. Fast measurements (every 1.1 s) allow one to obtain a vertical resolution of 5 m for the profiles. A detection limit of a few tens of parts per trillion in volume has been demonstrated. Uncertainties of 3%-5% are estimated for the most abundant species rising to about 30% for the less abundant ones, mainly depending on the laser linewidth and the signal-to-noise ratio.

Diode-Laser Spectroscopy: Line Profiles of H(2)O in the Region of 1.39 &mgr;m.

Using a stabilized diode-laser spectrometer, we have studied the line profiles of water vapor near 7185.59 cm(-1). With low pressures of pure gas (

Balloonborne calibrated spectroradiometer for atmospheric nadir sounding.

Laboratoire de Physique Moléculaire et Applications (LPMA)/Infrared Atmospheric Sounding interferometer (IASI) balloon is a calibrated infrared Fourier transform spectrometer that is used to measure the Earth's atmospheric emission (650-3000 cm(-1)). Operating under a stratospheric balloon, this spectroradiometer provides radiometrically calibrated spectra with an apodized spectral resolution of 0.1 cm(-1), which can be used to retrieve the concentration of atmospheric trace gases such as H2O, CO2, CO, O3, N2O, and CH4. The radiometric calibration is performed by use of two reference blackbodies. A reference cavity (LPMA blackbody) has been developed to validate the radiometric calibration procedure and to characterize the instrument performances. One goal of the LPMA/IASI balloon is the preparation of the IASI mission, which is a satellite instrument dedicated primarily to operational meteorology. A description of the LPMA/IASI balloon, its performances, and the results obtained during the first flight of the instrument are presented.

Retrieval of CO from nadir remote-sensing measurements in the infrared by use of four different inversion algorithms.

Four inversion schemes based on various retrieval approaches (digital gas correlation, nonlinear least squares, global fit adjustment, and neural networks) developed to retrieve CO from nadir radiances measured by such downward-looking satelliteborne instruments as the Measurement of Pollution in the Troposphere (MOPITT), the Tropospheric Emission Spectrometer (TES), and the Infrared Atmospheric Sounding Interferometer (IASI) instruments were compared both for simulated cases and for atmospheric spectra recorded by the Interferometric Monitor for Greenhouse Gases (IMG). The sensitivity of the retrieved CO total column amount to properties that may affect the inversion accuracy (noise, ancillary temperature profile, and water-vapor content) was investigated. The CO column amounts for the simulated radiance spectra agreed within 4%, whereas larger discrepancies were obtained when atmospheric spectra recorded by the IMG instrument were analyzed. The assumed vertical temperature profile is shown to be a critical parameter for accurate CO retrieval. The instrument's line shape was also identified as a possible cause of disagreement among the result provided by the groups of scientist who are participating in this study.