Guides optiques infrarouges pour la détection du CO2

session affiches A7 " Instrumentation, Caractérisation et Capteurs " [A7.1]National audienceL'équipe Verres et Céramiques développe des fibres optiques originales qui sont à la base de la réalisation de capteur optique opérant dans l'infrarouge. L'intérêt et le potentiel de ces capteurs ont été démontrés dans des domaines variés, notamment en biologie et en médecine. L'objet de ce travail consiste à exploiter ce savoir faire pour réaliser des guides optiques permettant la détection et le monitoring du CO2. Des premiers résultats ont été obtenus en transmission classique entre deux fibres infrarouges. Ils ont montré qu'il est possible de détecter jusqu'à 0.5% de CO2. L'objectif actuel est d'améliorer la sensibilité de détection au dioxyde de carbone par une augmentation de la surface de contact gaz-fibre, en utilisant des fibres microstructurées. Une autre voie consiste à fabriquer des guides planaires qui nous permettent d'envisager, à terme, la réalisation de micro-composants optiques en verre de chalcogénure avec une robustesse et une compacité accrue

Surface gas geochemistry above the natural CO2 reservoir of Montmiral (Drôme, France), source tracking and gas exchange between the soil, biosphere and atmosphere

International audienceOne of the options considered to mitigate greenhouse gas concentrations in the atmosphere is underground storage of CO2. There is a strong need for enhancing and developing methods that would help throughout the duration life of such underground storage, to ensure the safety and able to monitor the evolution of the injected CO2 plume. Among these, geochemical methods can play an important role. Here, we describe results acquired under the research programme “Géocarbone-Monitoring”, partially funded by the French National Research Agency, on the Montmiral natural analogue in South-Eastern France. Other results obtained under the same research programme in the French Massif Central are reported elsewhere in this volume.Spot sampling methods allowing a great geographical coverage and continuous measurements on selected points were undertaken in 2006 and 2007, in order to determine soil gas concentrations and fluxes as well as carbon isotope ratio determinations. One important result is that without any evidence of deep CO2 leakage, both CO2 concentrations and fluxes appear to be higher than can be explained only by biological activities. Further investigations are thus needed to understand the gas evolution better throughout the year

Geochemical Study of Natural CO2 Emissions in the French Massif Central: How to Predict Origin, Processes and Evolution of CO2 Leakage

International audienceThis study presents an overview of some results obtained within the French ANR (National Agency of Research) supported Géocarbone-Monitoring research program. The measurements were performed in Sainte-Marguerite, located in the French Massif Central. This site represents a natural laboratory for CO2/fluid/rock interactions studies, as well as CO2 migration mechanisms towards the surface. The CO2 leaking character of the studied area also allows to test and validate measurements methods and verifications for the future CO2 geological storage sites. During these surveys, we analyzed soil CO2 fluxes and concentrations. We sampled and analyzed soil gases, and gas from carbo-gaseous bubbling springs. A one-month continuous monitoring was also tested, to record the concentration of CO2 both in atmosphere and in the soil at a single point. We also developed a new methodology to collect soil gas samples for noble gas abundances and isotopic analyses, as well as carbon isotopic ratios. Our geochemical results, combined with structural geology, show that the leaking CO2 has a very deep origin, partially mantle derived. The gas rises rapidly along normal and strike-slip active faults. CO2 soil concentrations (also showing a mantle derived component) and CO2 fluxes are spatially variable, and reach high values. The recorded atmospheric CO2 is not very high, despite the important CO2 degassing throughout the whole area

Local thermodynamic equilibrium and related metrological issues involving collisional-radiative model in laser-induced aluminum plasmas

We present a collisional-radiative approach of the theoretical analysis of laser-induced breakdown spectroscopy (LIBS) plasmas. This model, which relies on an optimized effective potential atomic structure code, was used to simulate a pure aluminum plasma. The description of aluminum involved a set of 220 atomic levels representative of three different stages of ionization (Al0, Al+ and Al++). The calculations were carried for stationary plasmas, with input parameters (ne and Te) ranging respectively between 1013-18 cm− 3 and 0.3-2 eV. A comparison of our atomic data with some existing databases is made. The code was mainly developed to address the validity of the local thermodynamic equilibrium (LTE) assumption. For usual LIBS plasma parameters, we did not reveal a sizeable discrepancy of the radiative equilibrium of the plasma towards LTE. For cases where LTE was firmly believed to stand, the Boltzmann plot outputs of this code were used to check the physical accuracy of the Boltzmann temperature, as it is currently exploited in several calibration-free laser-induced breakdown spectroscopy (CF-LIBS) studies. In this paper, a deviation ranging between 10 and 30% of the measured Boltzmann temperature to the real excitation temperature is reported. This may be due to the huge dispersion induced on the line emissivities, on which the Boltzmann plots are based to extract this parameter. Consequences of this fact on the CF-LIBS procedure are discussed and further insights to be considered for the future are introduced

Local thermodynamic equilibrium and related metrological issues involving collisional-radiative model in laser-induced aluminum plasmas

We present a collisional-radiative approach of the theoretical analysis of laser-induced breakdown spectroscopy (LIBS) plasmas. This model, which relies on an optimized effective potential atomic structure code, was used to simulate a pure aluminum plasma. The description of aluminum involved a set of 220 atomic levels representative of three different stages of ionization (Al0, Al+ and Al++). The calculations were carried for stationary plasmas, with input parameters (ne and Te) ranging respectively between 1013-18 cm− 3 and 0.3-2 eV. A comparison of our atomic data with some existing databases is made. The code was mainly developed to address the validity of the local thermodynamic equilibrium (LTE) assumption. For usual LIBS plasma parameters, we did not reveal a sizeable discrepancy of the radiative equilibrium of the plasma towards LTE. For cases where LTE was firmly believed to stand, the Boltzmann plot outputs of this code were used to check the physical accuracy of the Boltzmann temperature, as it is currently exploited in several calibration-free laser-induced breakdown spectroscopy (CF-LIBS) studies. In this paper, a deviation ranging between 10 and 30% of the measured Boltzmann temperature to the real excitation temperature is reported. This may be due to the huge dispersion induced on the line emissivities, on which the Boltzmann plots are based to extract this parameter. Consequences of this fact on the CF-LIBS procedure are discussed and further insights to be considered for the future are introduced

In Situ Semi-Quantitative Analysis of Polluted Soils by Laser-Induced Breakdown Spectroscopy (LIBS)

Time-saving, low-cost analyses of soil contamination are required to ensure fast and efficient pollution removal and remedial operations. In this work, laser-induced breakdown spectroscopy (LIBS) has been successfully applied to in situ analyses of polluted soils, providing direct semi-quantitative information about the extent of pollution. A field campaign has been carried out in Brittany (France) on a site presenting high levels of heavy metal concentrations. Results on iron as a major component as well as on lead and copper as minor components are reported. Soil samples were dried and prepared as pressed pellets to minimize the effects of moisture and density on the results. LIBS analyses were performed with a Nd:YAG laser operating at 1064 nm, 60 mJ per 10 ns pulse, at a repetition rate of 10 Hz with a diameter of 500 lm on the sample surface. Good correlations were obtained between the LIBS signals and the values of concentrations deduced from inductively coupled plasma atomic emission spectroscopy (ICP-AES). This result proves that LIBS is an efficient method for optimizing sampling operations. Indeed, ''LIBS maps'' were established directly on-site, providing valuable assistance in optimizing the selection of the most relevant samples for future expensive and time-consuming laboratory analysis and avoiding useless analyses of very similar samples. Finally, it is emphasized that in situ LIBS is not described here as an alternative quantitative analytical method to the usual laboratory measurements but simply as an efficient time-saving tool to optimize sampling operations and to drastically reduce the number of soil samples to be analyzed, thus reducing costs. The detection limits of 200 ppm for lead and 80 ppm for copper reported here are compatible with the thresholds of toxicity; thus, this in situ LIBS campaign was fully validated for these two elements. Consequently, further experiments are planned to extend this study to other chemical elements and other matrices of soils.Technique Ionisation Chimique Evaluation pour les SOL

Infrared monitoring of underground CO2 storage using chalcogenide glass fibers

International audienceAn optical-fiber-based system suitable for monitoring the presence of carbon dioxide, so-called "greenhouse gas", is investigated. Since each pollutant gas shows a characteristic optical absorption spectrum in the mid-infrared (mid-IR), it is possible to detect selectively and quantitatively the presence of gases in a given environment by analysing mid-IR spectra. The main infrared signature of carbon dioxide gas is a double absorption peak located at 4.2 μm. Chalcogenide optical fibers, which can transmit light in the 1-6 μm range, are well-adapted for CO2 analysis. In this wavelength range, they show attenuation losses that compare favourably with other types of fiber such as silver halide fibers. In this paper, the detection limit of CO2 is established as a function of optical path length. The dynamic parameters of the sensors, such as reversibility, response time and recovery time, are also studied. It is concluded that optical fibers based on chalcogenide glasses could be used to transport infrared light from a black body source to a remote CO2 geological storage zone in order to monitor, in real time, CO2 gas leakage

Rare-earth doped chalcogenide optical waveguide in near and mid-IR for optical potential application

Mid-infrared (IR) emissions are motivating for a variety of applications including environmental sensing, LIDAR and military counter-measures. In this research field, halcogenide fi bres as host materials for rare earth ions can play a major part. Moreover, the fabrication of amplifying integrated optical structures is of great interest in the fi eld of modern telecommunication technologies or optical sensing. These optical components can be applied to compensate waveguide losses, coupling and splitting losses, as well as to fabricate integrated laser sources, operating in the telecom bands or middle IR. With high refractive index values and an appropriate rare-earth (RE) solubility, chalcogenide glasses exhibit high spontaneous emission probabilities and, consequently large emission cross-sections for radiative electronic transitions of RE3+ ions. The low phonon energy of these materials (~ 350 cm-1 for sulphides and ~ 250 cm-1 for selenides) limits the non-radiative multiphonon relaxation rates. All these properties result in high quantum effi ciencies for rare earth ion transitions in chalcogenide glasses. However, infrared emissions beyond 3 μm originating from rare earth ion doped amorphous chalcogenide fi bres or planar waveguide are reported more rarely. The development of the Er3+ and Dy3+-doped sulphide and selenide fi bres and sputtered fi lms will be described focusing on their relevant compositional, structural and optical characteristics