An Infrared Laser Sensor for Monitoring Gas-Phase CO2 in the Headspace of Champagne Glasses under Wine Swirling Conditions.

In wine tasting, tasters commonly swirl their glasses before inhaling the headspace above the wine. However, the consequences of wine swirling on the chemical gaseous headspace inhaled by tasters are barely known. In champagne or sparkling wine tasting, starting from the pouring step, gas-phase carbon dioxide (CO2) is the main gaseous species that progressively invades the glass headspace. We report the development of a homemade orbital shaker to replicate wine swirling and the upgrade of a diode laser sensor (DLS) dedicated to monitoring gas-phase CO2 in the headspace of champagne glasses under swirling conditions. We conduct a first overview of gas-phase CO2 monitoring in the headspace of a champagne glass, starting from the pouring step and continuing for the next 5 min, with several 5 s swirling steps to replicate the natural orbital movement of champagne tasters. The first results show a sudden drop in the CO2 concentration in the glass headspace, probably triggered by the liquid wave traveling along the glass wall following the action of swirling the glass.

How Does Gas-Phase CO2 Evolve in the Headspace of Champagne Glasses?

The chemical space perceived by a consumer of champagne or other sparkling wines is progressively modified all along tasting. Real-time monitoring of gas-phase CO2 concentration was performed, through a CO2-diode laser sensor, along a two-dimensional array of nine points in the headspace of three types of glasses poured with champagne. Two original glasses with distinct headspace volumes were compared with the standard INAO tasting glass. For each of the three glass types, a kind of temperature-dependent CO2 fingerprint was revealed and discussed as a function of the glass geometry and headspace volume. Moreover, a simple model was developed, which considers the rate of decrease of the concentration of gas-phase CO2 in the headspace of a glass after the pouring process as being mainly ruled by natural air convection in ambient air. The timescale which controls the rate of decrease of gas-phase CO2 was found to highly depend on the ratio of the headspace volume to the open aperture of the glass.

Widely-Tunable Quantum Cascade-Based Sources for the Development of Optical Gas Sensors.

Spectroscopic techniques based on Distributed FeedBack (DFB) Quantum Cascade Lasers (QCL) provide good results for gas detection in the mid-infrared region in terms of sensibility and selectivity. The main limitation is the QCL relatively low tuning range (~10 cm-1) that prevents from monitoring complex species with broad absorption spectra in the infrared region or performing multi-gas sensing. To obtain a wider tuning range, the first solution presented in this paper consists of the use of a DFB QCL array. Tuning ranges from 1335 to 1387 cm-1 and from 2190 to 2220 cm-1 have been demonstrated. A more common technique that will be presented in a second part is to implement a Fabry-Perot QCL chip in an external-cavity (EC) system so that the laser could be tuned on its whole gain curve. The use of an EC system also allows to perform Intra-Cavity Laser Absorption Spectroscopy, where the gas sample is placed within the laser resonator. Moreover, a technique only using the QCL compliance voltage technique can be used to retrieve the spectrum of the gas inside the cavity, thus no detector outside the cavity is needed. Finally, a specific scheme using an EC coherent QCL array can be developed. All these widely-tunable Quantum Cascade-based sources can be used to demonstrate the development of optical gas sensors.

Monitoring gas-phase CO2 in the headspace of champagne glasses through combined diode laser spectrometry and micro-gas chromatography analysis.

During Champagne or sparkling wine tasting, gas-phase CO2 and volatile organic compounds invade the headspace above glasses, thus progressively modifying the chemical space perceived by the consumer. Gas-phase CO2 in excess can even cause a very unpleasant tingling sensation perturbing both ortho- and retronasal olfactory perception. Monitoring as accurately as possible the level of gas-phase CO2 above glasses is therefore a challenge of importance aimed at better understanding the close relationship between the release of CO2 and a collection of various tasting parameters. Here, the concentration of CO2 found in the headspace of champagne glasses served under multivariate conditions was accurately monitored, all along the 10 min following pouring, through a new combined approach by a CO2-Diode Laser Sensor and micro-gas chromatography. Our results show the strong impact of various tasting conditions (volume dispensed, intensity of effervescence, and glass shape) on the release of gas-phase CO2 above the champagne surface.

Challenges in the design and fabrication of a lab-on-a-chip photoacoustic gas sensor.

The favorable downscaling behavior of photoacoustic spectroscopy has provoked in recent years a growing interest in the miniaturization of photoacoustic sensors. The individual components of the sensor, namely widely tunable quantum cascade lasers, low loss mid infrared (mid-IR) waveguides, and efficient microelectromechanical systems (MEMS) microphones are becoming available in complementary metal-oxide-semiconductor (CMOS) compatible technologies. This paves the way for the joint processes of miniaturization and full integration. Recently, a prototype microsensor has been designed by the means of a specifically designed coupled optical-acoustic model. This paper discusses the new, or more intense, challenges faced if downscaling is continued. The first limitation in miniaturization is physical: the light source modulation, which matches the increasing cell acoustic resonance frequency, must be kept much slower than the collisional relaxation process. Secondly, from the acoustic modeling point of view, one faces the limit of validity of the continuum hypothesis. Namely, at some point, velocity slip and temperature jump boundary conditions must be used, instead of the continuous boundary conditions, which are valid at the macro-scale. Finally, on the technological side, solutions exist to realize a complete lab-on-a-chip, even if it remains a demanding integration problem.

Carbon dioxide and ethanol release from champagne glasses, under standard tasting conditions.

A simple glass of champagne or sparkling wine may seem like the acme of frivolity to most people, but in fact, it may rather be considered as a fantastic playground for any fluid physicist or physicochemist. In this chapter, results obtained concerning various steps where the CO2 molecule plays a role (from its ingestion in the liquid phase during the fermentation process to its progressive release in the headspace above the tasting glass) are gathered and synthesized to propose a self-consistent and global overview of how gaseous and dissolved CO2 impact champagne and sparkling wine science. Some recent investigations, conducted through laser tomography techniques, on ascending bubbles and ascending-bubble-driven flow patterns found in champagne glasses are reported, which illustrate the fine interplay between ascending bubbles and the fluid around under standard tasting conditions. The simultaneous monitoring of gaseous CO2 and ethanol in the headspace of both a flute and a coupe filled with champagne was reported, depending on whether or not the glass shows effervescence. Both gaseous CO2 and ethanol were found to be enhanced by the presence of ascending bubbles, thus confirming the close link between ascending bubbles, ascending-bubble-driven flow patterns, and the release of gaseous CO2 and volatile organic compounds.

Unraveling the evolving nature of gaseous and dissolved carbon dioxide in champagne wines: a state-of-the-art review, from the bottle to the tasting glass.

In champagne and sparkling wine tasting, the concentration of dissolved CO(2) is indeed an analytical parameter of high importance since it directly impacts the four following sensory properties: (i) the frequency of bubble formation in the glass, (ii) the growth rate of rising bubbles, (iii) the mouth feel, and (iv) the nose of champagne, i.e., its so-called bouquet. In this state-of-the-art review, the evolving nature of the dissolved and gaseous CO(2) found in champagne wines is evidenced, from the bottle to the glass, through various analytical techniques. Results obtained concerning various steps where the CO(2) molecule plays a role (from its ingestion in the liquid phase during the fermentation process to its progressive release in the headspace above the tasting glass) are gathered and synthesized to propose a self-consistent and global overview of how gaseous and dissolved CO(2) impact champagne and sparkling wine science.

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.