Mid-infrared Laser Absorption Spectroscopy Research Articles

Time-resolved characterization of non-thermal plasma-assisted photocatalytic removal of nitric oxide

We performed time-resolved characterization of plasma-photocatalytic removal of nitric oxide (NO) in a ceramic foam packing double dielectric barrier discharge reactor using mid-infrared laser absorption spectroscopy. Non-thermal plasma (NTP) was generated in the porous ceramic foam coated with mesoporous TiO2 thin film. Real-time NO monitoring was performed using a quantum cascade laser at 5.26 µm combined with a custom-designed multipass gas cell, leading to a sub-ppm detection limit at 0.1 s measurement time. By analyzing the feed gas of 90 ppm NO/1% O2 balanced in N2, the plasma treatment without TiO2 photocatalyst had no effect on NO removal when the discharge power was below 45 W. In comparison, the NTP-TiO2 system achieved an efficiency of 49% for NO removal even at the relatively low discharge power of 18 W. The synergy between NTP and TiO2 photocatalyst effectively promotes the NO removal at low plasma discharge powers. However, we also observed a negative effect of TiO2 photocatalyst on NO removal at a relatively high discharge power of 135 W.

Quantitative measurements of formaldehyde in the low-temperature oxidation of iso-octane using mid-infrared absorption spectroscopy

Time-resolved quantitative measurements of formaldehyde (HCHO) in the low-temperature oxidation of iso-octane using a rapid compression machine have been performed with mid-infrared laser absorption spectroscopy. Due to the weak interference of the broadband absorption of iso-octane, a two-color detection scheme was applied to HCHO detection. The cross-sections of HCHO and iso-octane in two colors were measured using the rapid compression machine in the temperature range of 450–737 K and pressure range of 100–700 kPa. The time-resolved quantitative HCHO profiles in the low-temperature oxidation of iso-octane at 0.77 MPa, 645 K, and an equivalence ratio of 1.0 were successfully obtained. The calculated HCHO profiles using the latest chemical kinetic model of iso-octane show the same tendency as the experimental profiles.

Influence of Light Coupling Configuration and Alignment on the Stability of HWG-Based Gas Sensor System for Real-Time Detection of Exhaled Carbon Dioxide

A mid-infrared tunable diode laser absorption spectroscopy (TDLAS) gas sensor based on hollow waveguide (HWG) gas cell for real-time exhaled carbon dioxide (eCO2) detection is reported. A $2.73~\mu \text{m}$ distributed feedback (DFB) laser was used to target a strong CO2 absorption line, and wavelength modulation spectroscopy (WMS) with the second harmonic (WMS- $2f$ ) was used to retrieve the CO2 concentration with high sensitivity. The influence of different parameters, including coupling configuration of HWG, laser-to-HWG and HWG-to-detector coupling alignment on the stability of the HWG sensor is systematically studied. The HWG eCO2 sensor showed a fast response time of 2.7s, detection limit of 17 ppmv, and measurement precision of 20.9 ppmv with a 0.54 s temporal resolution. The eCO2 concentrations changed in breath cycles were measured in real time. The Allan variance indicated that the detection limit can reach 1.7 ppmv, corresponding to a detection sensitivity of $1.3\times 10^{\mathbf {-8}}$ cm−1 Hz−1/2, as the integration time increases to 26 s. This work demonstrates the performance characteristics and merits of HWG eCO2 sensor for exhaled breath analysis and potential detection for other exhaled gases.

Mid-infrared laser absorption spectroscopy of the Ne-NO(X2Π) complex.

The rovibrational spectrum of the Ne-NO(X2Π) open-shell complex has been measured in the 5.3 µm region using distributed feed-back quantum cascade lasers to probe the direct absorption in a slit-jet supersonic expansion. Three P-subbands (P' ← P″: 1/2 ← 1/2, 3/2 ← 1/2, and 5/2 ← 3/2) were observed, where P is the projection of the angular momentum J along the inertial a-axis of the complex. The hyperfine structure due to the nuclei spin of 14N (I = 1) was partially resolved in the P' ← P″: 1/2 ← 1/2 and 3/2 ← 1/2 subbands. The observed mid-infrared spectrum of Ne-NO (X2Π) together with the previously reported microwave spectrum was analyzed using a modified semirigid asymmetric rotor Hamiltonian for a planar open-shell complex. The band origin is located at 1876.0606(97) cm-1, which is blue-shifted from that of the NO monomer by only 0.0888 cm-1. The complex shows strong structural relaxation upon excitation of the overall rotation and the internal rotation of the NO subunit.

Quantitative analysis of ammonia adsorption in Ag/AgI-coated hollow waveguide by mid-infrared laser absorption spectroscopy

The adsorption effect of ammonia gas molecules on the inner surface of silver and silver iodide-coated hollow waveguides (Ag/AgI-HWGs) was studied by using a direct absorption spectrometry system with a 9.56-µm quantum cascade laser as the light source. The dynamic changes in ammonia concentration in the Ag/AgI-HWG during the process of NH3 influx and N2 purge were measured with a high time resolution. The adsorption and desorption processes of ammonia were quantitatively analyzed. The results indicate that the density of ammonia molecules adsorbed on the inner wall surface of the Ag/AgI-HWG was 1015 molecules/cm2, characterized as multilayer adsorption, and the corresponding F value (a dimensionless number commonly used to characterize influence of the adsorption effect) was about 5.89. The adsorption capacity increased with the pressure and decreased with the temperature, which is consistent with Le Chatelier's principle. The differential heats of adsorption were deduced to be 7.6 and 6.1 kJ/mol for monolayer and multilayer adsorption, respectively, and the Brunauer-Emmett-Teller model was established and agreed well with our measurement results. The adsorption kinetic process also fit well to both the pseudo-first-order and pseudo-second-order kinetic model. This study fills in the gap in the research of Ag/AgI-HWGs adsorption and is meaningful for accurate gas detection using HWG-based spectroscopy systems.

Fitting of single-exhalation profiles using a pulmonary gas exchange model—application to carbon monoxide

Real-time breath gas analysis coupled to gas exchange modeling is emerging as promising strategy to enhance the information gained from breath tests. It is shown for exhaled breath carbon monoxide (eCO), a potential biomarker for oxidative stress and respiratory diseases, that a weighted, nonlinear least-squares fit of simulated to measured expirograms can be used to extract physiological parameters, such as airway and alveolar concentrations and diffusing capacities. Experimental CO exhalation profiles are acquired with high time-resolution and precision using mid-infrared tunable diode laser absorption spectroscopy and online breath sampling. A trumpet model with axial diffusion is employed to generate eCO profiles based on measured exhalation flow rates and volumes. The concept is demonstrated on two healthy non-smokers exhaling at a flow rate of 250 ml s−1 during normal breathing and at 120 ml s−1 after 10 s of breath-holding. The obtained gas exchange parameters of the two subjects are in a similar range, but clearly distinguishable. Over a series of twenty consecutive expirograms, the intra-individual variation in the alveolar parameters is less than 6%. After a 2 h exposure to 10 ± 2 ppm CO, end-tidal and alveolar CO concentrations are significantly increased (by factors of 2.7 and 4.9 for the two subjects) and the airway CO concentration is slightly higher, while the alveolar diffusing capacity is unchanged compared to before exposure. Using model simulations, it is found that a three-fold increase in maximum airway CO flux and a reduction in alveolar diffusing capacity by 60% lead to clearly distinguishable changes in the exhalation profile shape. This suggests that extended breath CO analysis has clinical relevance in assessing airway inflammation and chronic obstructive pulmonary disease. Moreover, the novel methodology contributes to the standardization of real-time breath gas analysis.

Multi-species trace gas sensing with dual-wavelength QCLs

Instrumentation for environmental monitoring of gaseous pollutants and greenhouse gases tends to be complex, expensive, and energy demanding, because every compound measured relies on a specific analytical technique. This work demonstrates an alternative approach based on mid-infrared laser absorption spectroscopy with dual-wavelength quantum cascade lasers (QCLs). The combination of two dual- and one single-DFB QCL yields high-precision measurements of CO (0.08 ppb), CO2 (100 ppb), NH3 (0.02 ppb), NO (0.4 ppb), NO2 (0.1 ppb), N2O (0.045 ppb), and O3 (0.11 ppb) simultaneously in a compact setup (45 × 45 cm2). The lasers are driven time-multiplexed in intermittent continuous wave mode with a repetition rate of 1 kHz. The individual spectra are real-time averaged (1 s) by an FPGA-based data acquisition system. The instrument was assessed for environmental monitoring and benchmarked with reference instrumentation to demonstrate its potential for compact multi-species trace gas sensing.

Mid-IR spectrometer for mobile, real-time urban NO<sub>2</sub> measurements

Abstract. Detailed knowledge about the urban NO2 concentration field is a key element for obtaining accurate pollution maps and individual exposure estimates. These are required for improving the understanding of the impact of ambient NO2 on human health and for related air quality measures. However, city-scale NO2 concentration maps with high spatio-temporal resolution are still lacking, mainly due to the difficulty of accurate measurement of NO2 at the required sub-ppb level precision. We contribute to close this gap through the development of a compact instrument based on mid-infrared laser absorption spectroscopy. Leveraging recent advances in infrared laser and detection technology and a novel circular absorption cell, we demonstrate the feasibility and robustness of this technique for demanding mobile applications. A fully autonomous quantum cascade laser absorption spectrometer (QCLAS) has been successfully deployed on a tram, performing long-term and real-time concentration measurements of NO2 in the city of Zurich (Switzerland). For ambient NO2 concentrations, the instrument demonstrated a precision of 0.23 ppb at one second time resolution and of 0.03 ppb after 200 s averaging. Whilst the combined uncertainty estimated for the retrieved spectroscopic values was less than 5 %, laboratory intercomparison measurements with standard CLD instruments revealed a systematic NO2 wall loss of about 10 % within the laser spectrometer. For the field campaign, the QCLAS has been referenced to a CLD using urban atmospheric air, despite the potential cross sensitivity of CLD to other nitrogen containing compounds. However, this approach allowed a direct comparison and continuous validation of the spectroscopic data to measurements at regulatory air quality monitoring (AQM) stations along the tram-line. The analysis of the recorded high-resolution time series allowed us to gain more detailed insights into the spatio-temporal concentration distribution of NO2 in an urban environment. Furthermore, our results demonstrate that for reliable city-scale concentration maps a larger data set and better spatial coverage is needed, e.g., by deploying more mobile and stationary instruments to account for mainly two shortcomings of the current approach: (i) limited residence time close to sources with large short-term NO2 variations, and (ii) insufficient representativeness of the tram tracks for the complex urban environment.

On improved understanding of plasma-chemical processes in complex low-temperature plasmas

Over the last years, chemical sensing using optical emission spectroscopy (OES) in the visible spectral range has been combined with methods of mid infrared laser absorption spectroscopy (MIR-LAS) in the molecular fingerprint region from 3 to 20 μm, which contains strong rotational–vibrational absorption bands of a large variety of gaseous species. This optical approach established powerful in situ diagnostic tools to study plasma-chemical processes of complex low-temperature plasmas. The methods of MIR-LAS enable to detect stable and transient molecular species in ground and excited states and to measure the concentrations and temperatures of reactive species in plasmas. Since kinetic processes are inherent to discharges ignited in molecular gases, high time resolution on sub-second timescales is frequently desired for fundamental studies as well as for process monitoring in applied research and industry. In addition to high sensitivity and good temporal resolution, the capacity for broad spectral coverage enabling multicomponent detection is further expanding the use of OES and MIR-LAS techniques. Based on selected examples, this paper reports on recent achievements in the understanding of complex low-temperature plasmas. Recently, a link with chemical modeling of the plasma has been provided, which is the ultimate objective for a better understanding of the chemical and reaction kinetic processes occurring in the plasma.

Measurement of multispecies concentration and gas temperature in an ammonium-dinitramide-based thruster by tunable diode lasers

In this paper, quantitative experiments were made to measure the concentration of key intermediate products (CO, N2O, and NO) and the gas temperature for combustion flow based on near-infrared and mid-infrared laser absorption spectroscopy. This paper used the developed diagnostic system to study two main ignition modes of a real 1-Newton thruster based on ammonium dinitramide (ADN): steady-state firing and pulse-mode firing over a feed pressure of 5-12bar. The steady-state firing experiments distinguished the whole process into catalytic decomposition stage and combustion stage, experimentally demonstrating the combustion kinetics mechanism of an ADN monopropellant. Experiments for pulse-mode firing showed the measured multispecies concentration and temperature were consistent with pulse trains, verifying good performance for the thruster pulse-mode firing operation. The performance of the thruster was given based on the optical measurements, and characteristic velocity for the ADN-based thruster standard operation was higher than the corresponding 1-Newton hydrazine thruster.

基于中红外激光吸收光谱的低浓度一氧化氮测量

基于中红外激光吸收光谱的低浓度一氧化氮测量

High-Precision Simultaneous 18O/16O, 13C/12C, and 17O/16O Analyses for Microgram Quantities of CaCO3 by Tunable Infrared Laser Absorption Spectroscopy.

Stable isotope ratios (18O/16O, 13C/12C, and 17O/16O) in carbonates have contributed greatly to the understanding of Earth and planetary systems, climates, and history. The current method for measuring isotopologues of CO2 derived from CaCO3 is primarily gas-source isotope ratio mass spectroscopy (IRMS). However, IRMS has drawbacks, such as mass overlap by multiple CO2 isotopologues and contaminants, the requirement of careful sample purification, and the use of major instrumentation needing permanent installation and a high power electrical supply. Here, we report simultaneous 18O/16O, 13C/12C, and 17O/16O analyses for microgram quantities of CaCO3 using a tunable mid-infrared laser absorption spectroscopy (TILDAS) system, which has no mass overlap problem and yields high sensitivity/precision measurements on small samples, as small as 0.02 μmol of CO2 (equivalent to 2 μg of CaCO3) with standard errors of less than 0.08 ‰ for 18O/16O and 13C/12C (±0.136 ‰ and ±0.387 ‰ repeatability; n = 10). In larger samples of CO2, 0.68 μmol (or 68 μg of CaCO3), standard error is less than 0.04 ‰ for 18O/16O and 13C/12C (< ±0.1 ‰ repeatability; n = 10) and 0.03 ‰ for 17O/16O (±0.069 ‰ repeatability; n = 10). We also show, for the first time, the relationship between 17O/16O ratios measured using the TILDAS system and published δ17O values of international standard materials (NBS-18 and -19) measured by IRMS. The benchtop TILDAS system, with cryogen-free sample preparation vacuum lines for microgram quantities of carbonates, is therefore a significant advance in carbonate stable isotope ratio geochemistry and is a new alternative to conventional IRMS.

Mid-infrared laser absorption spectroscopy of NO2 at elevated temperatures

A mid-infrared quantum cascade laser absorption sensor was developed for in-situ detection of NO2 in high-temperature gas environments. A cluster of spin-split transitions near 1599.9cm−1 from the ν3 absorption band of NO2 was selected due to the strength of these transitions and the low spectral interference from water vapor within this region. Temperature- and species-dependent collisional broadening parameters of ten neighboring NO2 transitions with Ar, O2, N2, CO2 and H2O were measured and reported. The spectral model was validated through comparisons with direct absorption spectroscopy measurements of NO2 seeded in various bath gases. The performance of the scanned wavelength modulation spectroscopy (WMS)-based sensor was demonstrated in a combustion exhaust stream seeded with varying flow rates of NO2, achieving reliable detection of 1.45 and 1.6ppm NO2 by mole at 600K and 800K, respectively, with a measurement uncertainty of ±11%. 2σ noise levels of 360ppb and 760ppb were observed at 600K and 800K, respectively, in an absorption path length of 1.79m.

In situ measurement of CO2 and water vapour isotopic compositions at a forest site using mid-infrared laser absorption spectroscopy

ABSTRACTWe conducted continuous, high time-resolution measurements of CO2 and water vapour isotopologues (16O12C16O, 16O13C16O and 18O12C16O for CO2, and H218O for water vapour) in a red pine forest at the foot of Mt. Fuji for 9 days from the end of July 2010 using in situ absorption laser spectroscopy. The δ18O values in water vapour were estimated using the δ2H–δ18O relationship. At a scale of several days, the temporal variations in δ18O-CO2 and δ18O-H2O are similar. The orders of the daily Keeling plots are almost identical. A possible reason for the similar behaviour of δ18O-CO2 and δ18O-H2O is considered to be that the air masses with different water vapour isotopic ratios moved into the forest, and changed the atmosphere of the forest. A significant correlation was observed between δ18O-CO2 and δ13C-CO2 values at nighttime (r2≈0.9) due to mixing between soil (and/or leaf) respiration and tropospheric CO2. The ratios of the discrimination coefficients (Δa/Δ) for oxygen (Δa) and carbon (Δ) isotopes during photosynthesis were estimated in the range of 0.7–1.2 from the daytime correlations between δ18O-CO2 and δ13C-CO2 values.

Real-time analysis of &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;13&amp;lt;/sup&amp;gt;C- and &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;D-CH&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt; in ambient air with laser spectroscopy: method development and first intercomparison results

Abstract. In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, µmole mole−1) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.

Air broadening coefficients for the ν3 band of hydroperoxyl radicals

Using mid-infrared laser absorption spectroscopy, we investigated the room-temperature pressure broadening coefficients for hydroperoxyl radicals (HO2) in nitrogen and oxygen over the 1060.0–1065.5cm−1 range of the ν3 band. The HO2 radicals were produced by flash photolysis of a chlorine/1,4-cyclohexadiene/oxygen mixture. The 20 measured absorption profiles were analyzed with Voigt functions. Air broadening coefficients were estimated from the nitrogen- and oxygen-broadening results and compared with previous results. We discuss the dependence of air broadening on rotational states.

Sensitive detection of CO2 concentration and temperature for hot gases using quantum-cascade laser absorption spectroscopy near 4.2 μm

Mid-infrared quantum-cascade laser (QCL) absorption spectroscopy of CO2 near 4.2 mu m has been developed for measurement of temperature and concentration in hot gases. With stronger absorption line-strengths than transitions near 1.5, 2.0, and 2.7 mu m used previously, the fundamental band (00(0)1-00(0)0) of CO2 near 4.2 mu m provides greatly enhanced sensitivity and accuracy to sense CO2 in high-temperature gases. Line R(74) and line R(96) are chosen as optimum pair for sensitive temperature measurements due to their high-temperature sensitivity, equal signal-to-noise ratio (SNR), weak interference of H2O transitions, as well as relatively strong line-strengths in high temperature and weak absorption in room temperature. The high-resolution absorption spectrum of the far wings of the R-branch (R56-R100) in the fundamental vibrational band of CO2 is measured in a heated cell over the range 2,384-2,396 cm(-1) at different temperatures from 700 to 1,200 K. Taking three factors into consideration, including SNR, concentration detectability, and uncertainty sensitivity, the absorption line R(74) is selected to calculate CO2 concentration. The tunable QCL absorption sensor is validated in mixtures of CO2 and N-2 in a static cell for temperature range of 700-1,200 K, achieving an accuracy of +/- 6 K for temperature and +/- 5 % for concentration measurements.

A singular value decomposition approach for the retrieval of N2O concentrations and fluxes by quantum cascade laser absorption spectroscopy

In this paper, we discuss the interest of the singular value decomposition (SVD) data processing method applied to the in situ monitoring of gases (N2O) b mid-infrared quantum cascade laser absorption spectroscopy. An approach by simulation is used to determine the most appropriate parameters of the SVD treatment for this specific laser sensing application. The simulation is further used to estimate the effectiveness of the SVD in terms of improvement of the concentration data precision. Finally, the proposed SVD method is applied to experimental N2O measurements achieved in the laboratory with calibrated gas samples and with N2O flux measurements yielded during a field campaign in farm parcels.

Site selective real-time measurements of atmospheric N&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O isotopomers by laser spectroscopy

Abstract. We describe the first high precision real-time analysis of the N2O site-specific isotopic composition at ambient mixing ratios. Our technique is based on mid-infrared quantum cascade laser absorption spectroscopy (QCLAS) combined with an automated preconcentration unit. The QCLAS allows for simultaneous and specific analysis of the three main stable N2O isotopic species, 14N15N16O, 15N14N16O, 14N14N16O, and the respective site-specific relative isotope ratio differences δ15Nα and δ 15Nβ. Continuous, stand-alone operation is achieved by using liquid nitrogen free N2O preconcentration, a quasi-room-temperature quantum cascade laser (QCL), quantitative sample transfer to the QCLAS and an optimized calibration algorithm. The N2O site-specific isotopic composition (δ15Nα and δ15Nβ) can be analysed with a long-term precision of 0.2‰. The potential of this analytical tool is illustrated by continuous N2O isotopomer measurements above a grassland plot over a three week period, which allowed identification of microbial source and sink processes.

Influence of age and sex in exhaled breath samples investigated by means of infrared laser absorption spectroscopy

Breath gas analysis provides insight into human metabolism of healthy and ill individuals. As an innovative and non-invasive method, it opens up options to improve diagnostics, monitoring and treatment decisions. Mid-infrared laser absorption spectroscopy is utilized to detect CH4, H2O, CO2, NH3 and CH3OH in exhaled human breath. An off-line approach using breath sampling by means of Tedlar bags is applied. The breath gas samples are measured within the population-based epidemiological Study of Health in Pomerania (SHIP-TREND) performed at the University of Greifswald. The study covers about 5000 adult subjects aged 20–79 years within 3 years. Besides breath gas analysis many other examinations are conducted. It is expected to find associations between distinct concentration levels of species in the exhaled breath and diseases assessed in this study. The study will establish reference values for exhaled breath components and serve as background population for case-control studies. In the long run, morbidity and mortality follow-ups will be conducted, which will answer the question whether end-expiratory breath gas components predict future diseases and death. As first results, we present data from 45 dialysis patients (23 males, 22 females) which were recruited in a preliminary study in preparation for SHIP-TREND.