The first balloon-borne sample analysis of atmospheric carbonaceous components reveals new insights into formation processes.

Atmospheric aerosol optical, physical, and chemical properties play a fundamental role in the Earth's climate system. A better understanding of the processes involved in their formation, evolution, and interaction with radiation and the water cycle is critical. We report the analysis of atmospheric molecules/particles collected with a new sampling system that flew under regular weather balloons for the first time. The flight took place on January 18, 2022 from Reims (France). The samples were subsequently analyzed by high-resolution mass spectrometry (Orbitrap) to specifically infer hundreds of organic components present in 4 different layers from the troposphere to the stratosphere (up to 20 km). Additional measurements of O3, CO, and aerosol concentrations a few hours before this flight took place to contextualize the sampling. After separating common species found on each filter that might be common to atmospheric layers or residuals for contaminations, we found that each sample yields significant differences in the number and size of organic species detected that should reflect the unique composition of atmospheric layers. While tropospheric samples yield significantly oxidized and saturated components, with carbon numbers below 30 that might be explained by complex organics chemistry from local and distant source emissions, the upper tropospheric and stratospheric samples were associated with increased carbon numbers (C > 30), with a significantly reduced unsaturation number for the stratosphere, that might be induced by strong UV radiations. The multimodal distributions of carbon numbers in chemical formulas observed between 15 and 20 km suggest that oligomerization and growth of organic molecules may take place in aged air masses of tropical origin that are known to carry organic compounds even several km above the tropopause where their lifetime significantly increases. In addition, the presence of organics may also reflect the extended influence of wildfires smoke injected during the spring and summer in the NH hemisphere before the in situ observations and their long-lifetime in the upper troposphere and stratosphere.

Atmospheric Measurements by Ultra-Light SpEctrometer (AMULSE) Dedicated to Vertical Profile in Situ Measurements of Carbon Dioxide (CO2) Under Weather Balloons: Instrumental Development and Field Application.

The concentration of greenhouse gases in the atmosphere plays an important role in the radiative effects in the Earth's climate system. Therefore, it is crucial to increase the number of atmospheric observations in order to quantify the natural sinks and emission sources. We report in this paper the development of a new compact lightweight spectrometer (1.8 kg) called AMULSE based on near infrared laser technology at 2.04 µm coupled to a 6-m open-path multipass cell. The measurements were made using the Wavelength Modulation Spectroscopy (WMS) technique and the spectrometer is hence dedicated to in situ measuring the vertical profiles of the CO2 at high precision levels (σAllan = 0.96 ppm in 1 s integration time (1σ)) and with high temporal/spatial resolution (1 Hz/5 m) using meteorological balloons. The instrument is compact, robust, cost-effective, fully autonomous, has low-power consumption, a non-intrusive probe and is plug & play. It was first calibrated and validated in the laboratory and then used for 17 successful flights up to 10 km altitude in the region Champagne-Ardenne, France in 2014. A rate of 100% of instrument recovery was validated due to the pre-localization prediction of the Météo-France based on the flight simulation software.

Characterization of the stray light in a space borne atmospheric AOTF spectrometer.

Acousto-optic tunable filter (AOTF) spectrometers are being criticized for spectral leakage, distant side lobes of their spectral response function (SRF), or the stray light. SPICAM-IR is the AOTF spectrometer in the range of 1000-1700 nm with a resolving power of 1800-2200 operating on the Mars Express interplanetary probe. It is primarily dedicated to measurements of water vapor in the Martian atmosphere. SPICAM H(2)O retrievals are generally lower than simultaneous measurements with other instruments, the stray light suggested as a likely explanation. We report the results of laboratory measurements of water vapor in quantity characteristic for the Mars atmosphere (2-15 precipitable microns) with the Flight Spare model of SPICAM-IR. We simulated the measured spectra with HITRAN-based synthetic model, varying the water abundance, and the level of the stray light, and compared the results to the known amount of water in the cell. The retrieved level of the stray light, assumed uniformly spread over the spectral range, is below 1-1.3·10(-4). The stray may be responsible for the underestimation of water abundance of up to 8%, or 0.6 pr. µm. The account for the stray light removes the bias completely; the overall accuracy to measure water vapor is ~0.2 pr. µm. We demonstrate that the AOTF spectrometer dependably measures the water abundance and can be employed as an atmospheric spectrometer.

Wavelet denoising for infrared laser spectroscopy and gas detection.

After a brief introduction to wavelet theory, this paper discusses the critical parameters to be considered in wavelet denoising for infrared laser spectroscopy. In particular, it is shown that measurement dispersion as well as sensibility can be dramatically improved when using wavelet denoising for gas detection by infrared laser absorption spectroscopy.

Self-induced pressure shift and temperature dependence measurements of CO2 at 2.05µm with a tunable diode laser spectrometer.

By using a high resolution tunable diode laser absorption spectrometer combined with a cryogenically cooled optical multi-pass cell, we have measured the self-induced pressure shift coefficients for 8 transitions in the R branch of the (20(0)1)(III)←(00(0)0)(I) band of carbon dioxide around 2.05µm. This spectral region is of particular interest for the monitoring of atmospheric CO(2) with Differential Absorption Lidars (DiAL). The measurement of these shift coefficients was realized at five different temperatures ranging from 218 to 292K in order to determine their temperature dependence. The results are thoroughly compared to previous values reported in the literature for the (20(0)1)(III)←(00(0)0)(I) band of CO(2). The temperature dependence of the self-induced pressure shifts are reported experimentally for the first time for this specific CO(2) band.

Laser diode absorption spectroscopy for accurate CO(2) line parameters at 2 microm: consequences for space-based DIAL measurements and potential biases.

Space-based active sensing of CO(2) concentration is a very promising technique for the derivation of CO(2) surface fluxes. There is a need for accurate spectroscopic parameters to enable accurate space-based measurements to address global climatic issues. New spectroscopic measurements using laser diode absorption spectroscopy are presented for the preselected R30 CO(2) absorption line ((20(0)1)(III)<--(000) band) and four others. The line strength, air-broadening halfwidth, and its temperature dependence have been investigated. The results exhibit significant improvement for the R30 CO(2) absorption line: 0.4% on the line strength, 0.15% on the air-broadening coefficient, and 0.45% on its temperature dependence. Analysis of potential biases of space-based DIAL CO(2) mixing ratio measurements associated to spectroscopic parameter uncertainties are presented.

Diode laser spectroscopy of two acetylene isotopologues ((12)C2H2, (13)C(12)CH2) in the 1.533 microm region for the PHOBOS-Grunt space mission.

Several line intensities of the nu(1) + nu(3)(Sigma(u)(+)) - 0(Sigma(g)(+)) bands of (12)C(2)H(2) and (13)C(12)CH(2) at 1.533 microm have been revised at room temperature. These molecular transitions were selected to measure acetylene within the framework of the Martian space mission PHOBOS-Grunt. In the spectral region ranging from 6518 to 6530 cm(-1), 10 lines of both isotopologues have been analyzed using a high resolution tunable diode laser spectrometer. These transitions are well appropriate to the monitoring of C(2)H(2) by laser absorption spectroscopy with standard telecommunication laser diodes. Both the Voigt and the Rautian models are used to fit the molecular line shape and to provide accurate line strengths. Our data are thoroughly compared to existing database (including HITRAN08) and former experimental measurements.

Alternative method for gas detection using pulsed quantum-cascade-laser spectrometers.

Pulsed quantum-cascade-laser (QCL) spectrometers are usually used to detect atmospheric gases with either the interpulse technique (short pulses, typically 5-20 ns) or the intrapulse technique (long pulses, typically 500-800 ns). Each of these techniques has many drawbacks, which we present. Particularly the gas absorption spectra are generally distorted. We demonstrate the possibility to use intermediate pulses (typically 50-100 ns) for gas detection using pulsed QCL spectrometers. IR spectra of ammonia recorded in the 10 microm region are presented in various conditions of pulse emission. These experiences demonstrate the large influence of the pulse shape on the recorded spectrum and the importance to use our alternative method for gas detection with pulsed QCL spectrometers.

Inter-comparison of 2 microm Heterodyne Differential Absorption Lidar, Laser Diode Spectrometer, LICOR NDIR analyzer and flasks measurements of near-ground atmospheric CO2 mixing ratio.

Remote sensing and in situ instruments are presented and compared in the same location for accurate CO(2) mixing ratio measurements in the atmosphere: (1) a 2.064 microm Heterodyne DIfferential Absorption Lidar (HDIAL), (2) a field deployable infrared Laser Diode Spectrometer (LDS) using new commercial diode laser technology at 2.68 microm, (3) LICOR NDIR analyzer and (4) flasks. LDS, LICOR and flasks measurements were made in the same location, LICOR and flasks being taken as reference. Horizontal HDIAL measurements of CO(2) absorption using aerosol backscatter signal are reported. Using new spectroscopic data in the 2 microm band and meteorological sensor measurements, a mean CO(2) mixing ratio is inferred by the HDIAL in a 1 km long path above the 15m height location of the CO(2) in situ sensors. We compare HDIAL and LDS measurements with the LICOR data for 30 min of time averaging. The mean standard deviation of the HDIAL and the LDS CO(2) mixing ratio results are 3.3 ppm and 0.89 ppm, respectively. The bias of the HDIAL and the LDS measurements are -0.54 ppm and -0.99 ppm, respectively.

Development of a spectrometer using a continuous wave distributed feedback quantum cascade laser operating at room temperature for the simultaneous analysis of N2O and CH4 in the Earth's atmosphere.

We report on the development and performance of a gas sensor based on a distributed feedback quantum cascade laser operating in continuous wave at room temperature for simultaneous measurement of nitrous oxide (N(2)O) and methane (CH(4)) concentrations at ground level. The concentrations of the gases are determined by a long path infrared diode laser absorption spectroscopy. The long-term stability of the instrument is evaluated using the Allan variance technique. A preliminary evaluation of the instrument performance is realized by in situ measurements of N(2)O and CH(4) concentrations at ground level during 1 day. The sensor has also been applied to study the time response of N(2)O concentrations to a fertilizer addition in a soil sample and for the comparison between various types of soils.

New improvements in methane detection using a Helmholtz resonant photoacoustic laser sensor: a comparison between near-IR diode lasers and mid-IR quantum cascade lasers.

Atmospheric methane was detected by combining a photoacoustic (PA) sensor with several lasers emitting in both the near- and mid-infrared spectral ranges to check the achievable detection limits. The PA spectrometer is based on differential Helmholtz resonance. Near-infrared telecommunication-type laser diodes of increasing power, from Sensors Unlimited Inc. and Anritsu, were first used to scan the 2 nu(3) band of CH(4) near 1.65 microm. The best achieved detection limit is 0.15 ppm of methane at atmospheric pressure and with a 1s integration time. The PA sensor was then operated in conjunction with a quantum cascade laser from Alpes Lasers emitting near 7.9 microm on the nu(4) band of CH(4). The achieved detection limit is then of 3 ppb. The dramatic improvement in the detection limit obtained with the QC laser is due to the stronger optical power as well as to the capability of reaching the fundamental bands of methane lying in the mid-infrared spectral range.