Transportable mid-infrared laser heterodyne radiometer operating in the shot-noise dominated regime.

A transportable laser heterodyne radiometer (LHR) based on an external cavity quantum cascade laser, operating in the mid-infrared (mid-IR) around 8 µm, was developed for ground-based remote sensing of multiple greenhouse gases. A newly available novel flexible mid-IR polycrystalline fiber was first exploited to couple solar radiation, real-time captured using a portable sun-tracker, to the LHR receiver. Compared to free space coupling of sunlight, the technique usually used nowadays in the mid-IR, such fiber coupling configuration makes the LHR system readily more stable, simpler, and robust. Operation of the LHR with quasi-shot-noise limited performance was analyzed and experimentally achieved by optimizing local oscillator power. To the best of our knowledge, no such performance approaching the fundamental limit has been reported for a transportable LHR operating at a long mid-IR wavelength around 8 µm. CH4 and N2O were simultaneously measured in the atmospheric column using the developed mid-IR LHR. The experimental LHR spectrum of CH4 and N2O was compared and is in good agreement with a referenced Fourier-transform infrared spectrum from the Total Carbon Column Observing Network observation site and with a simulation spectrum from atmospheric transmission modeling.

Spectroscopic Measurements of Methane Solid-Gas Equilibrium Clapeyron Curve between 40 and 77 K.

The infrared gas-phase absorption spectrum of methane was used to determine its Clapeyron solid-gas equilibrium curve in the 40-77 K temperature range. For comparative purposes and to obtain more reliable results, two different optical experimental setups were used. At higher temperatures (53-77 K), a single pass cryogenically cooled cell was coupled to a standard low-resolution Fourier transform infrared spectrometer. The second system was a state-of-the-art vertical-external-cavity surface-emitting laser tunable source operating at around 2.3 µm, combined with a 7 m path Herriott cell, to record methane absorption features down to 40 K. From the measurements, the vapor pressure curve ln( p/Pa) = -(1191.92 ± 8.92)/( T/K) + (22.49 ± 0.16) was derived in the range 40-77 K. This corresponds to a value of 9910 ± 75 J mol-1 for the sublimation enthalpy. The relation was validated down to 40 K, increasing our knowledge of the saturation pressure by 2 orders of magnitude. Data were compared with available pressure measurements from the literature, obtained by manometric or mass spectrometry techniques, and the sublimation enthalpy was compared with a thermodynamic approach based on heat capacity measurements in the solid and gas phases.

UV photodesorption of interstellar CO ice analogues: from subsurface excitation to surface desorption.

Carbon monoxide is after H(2) the most abundant molecule identified in the interstellar medium (ISM), and is used as a major tracer for the gas phase physical conditions. Accreted at the surface of water-rich icy grains, CO is considered to be the starting point of a complex organic--presumably prebiotic--chemistry. Non-thermal desorption processes, and especially photodesorption by UV photons, are seen as the main cause that drives the gas-to-ice CO balance in the colder parts of the ISM. The process is known to be efficient and wavelength-dependent, but, the underlying mechanism and the physical-chemical parameters governing the photodesorption are still largely unknown. Using monochromatized photons from a synchrotron beamline, we reveal that the molecular mechanism responsible for CO photoejection is an indirect, (sub)surface-located process. The local environment of the molecules plays a key role in the photodesorption efficiency, and is quenched by at least an order of magnitude for CO interacting with a water ice surface.

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.