Cavity Enhanced Absorption Spectroscopy Technique Research Articles

Frequency-based dispersion Lamb-dip spectroscopy in a high finesse optical cavity.

Frequency-based cavity mode-dispersion spectroscopy (CMDS), previously applied for Doppler-limited molecular spectroscopy, is now employed for the first time for saturation spectroscopy. Comparison with two intensity-based, cavity-enhanced absorption spectroscopy techniques, i.e. cavity mode-width spectroscopy (CMWS) and the well-established cavity ring-down spectroscopy (CRDS), shows the predominance of the CMDS. The method enables measurements in broader pressure range and shows high immunity of the Lamb dip position to the incomplete model of saturated cavity mode shape. Frequencies of transitions from the second overtone of CO are determined with standard uncertainty below 500 Hz which corresponds to relative uncertainty below 3 × 10-12. The pressure shift of the Lamb dips, which has not been detected for these transitions in available literature data, is observed.

Shock-Tube Measurement of Acetone Dissociation Using Cavity-Enhanced Absorption Spectroscopy of CO.

A direct measurement for the rate constant of the acetone dissociation reaction (CH3COCH3 = CH3CO + CH3) was conducted behind reflected shock wave, utilizing a sub-ppm sensitivity CO diagnostic achieved by cavity-enhanced absorption spectroscopy (CEAS). The current experiment eliminated the influence from secondary reactions and temperature change by investigating the clean pyrolysis of <20 ppm acetone in argon. For the first time, the acetone dissociation rate constant (k1) was directly measured over 5.5 orders of magnitude with a high degree of accuracy: k1 (1004-1494 K, 1.6 atm) = 4.39 × 10(55) T(-11.394) exp(-52 140K/T) ± 24% s(-1). This result was seen to agree with most previous studies and has bridged the gap between their temperature and pressure conditions. The current work also served as an example demonstration of the potential of using the CEAS technique in shock-tube kinetics studies.

Development of a cavity-enhanced absorption spectrometer for airborne measurements of CH&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt; and CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;

Abstract. High-resolution CH4 and CO2 measurements were made on board the FAAM BAe-146 UK (Facility for Airborne Atmospheric Measurements, British Aerospace-146) atmospheric research aircraft during a number of field campaigns. The system was based on an infrared spectrometer using the cavity-enhanced absorption spectroscopy technique. Correction functions to convert the mole fractions retrieved from the spectroscopy to dry-air mole fractions were derived using laboratory experiments and over a 3 month period showed good stability. Long-term performance of the system was monitored using WMO (World Meteorological Office) traceable calibration gases. During the first year of operation (29 flights) analysis of the system's in-flight calibrations suggest that its measurements are accurate to 1.28 ppb (1σ repeatability at 1 Hz = 2.48 ppb) for CH4 and 0.17 ppm (1σ repeatability at 1 Hz = 0.66 ppm) for CO2. The system was found to be robust, no major motion or altitude dependency could be detected in the measurements. An inter-comparison between whole-air samples that were analysed post-flight for CH4 and CO2 by cavity ring-down spectroscopy showed a mean difference between the two techniques of −2.4 ppb (1σ = 2.3 ppb) for CH4 and −0.22 ppm (1σ = 0.45 ppm) for CO2. In September 2012, the system was used to sample biomass-burning plumes in Brazil as part of the SAMBBA project (South AMerican Biomass Burning Analysis). From these and simultaneous CO measurements, emission factors for savannah fires were calculated. These were found to be 2.2 ± 0.2 g (kg dry matter)−1 for CH4 and 1710 ± 171 g (kg dry matter)−1 for CO2, which are in excellent agreement with previous estimates in the literature.

Inherent calibration of a blue LED-CE-DOAS instrument to measure iodine oxide, glyoxal, methyl glyoxal, nitrogen dioxide, water vapour and aerosol extinction in open cavity mode

Abstract. The combination of Cavity Enhanced Absorption Spectroscopy (CEAS) with broad-band light sources (e.g. Light-Emitting Diodes, LEDs) lends itself to the application of cavity enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) to perform sensitive and selective point measurements of multiple trace gases and aerosol extinction with a single instrument. In contrast to other broad-band CEAS techniques, CE-DOAS relies only on the measurement of relative intensity changes, i.e. does not require knowledge of the light intensity in the absence of trace gases and aerosols (I0). We have built a prototype LED-CE-DOAS instrument in the blue spectral range (420–490 nm) to measure nitrogen dioxide (NO2), glyoxal (CHOCHO), methyl glyoxal (CH3COCHO), iodine oxide (IO), water vapour (H2O) and oxygen dimers (O4). We demonstrate the first direct detection of methyl glyoxal, and the first CE-DOAS detection of CHOCHO and IO. The instrument is further inherently calibrated for light extinction from the cavity by observing O4 or H2O (at 477 nm and 443 nm) and measuring the pressure, relative humidity and temperature independently. This approach is demonstrated by experiments where laboratory aerosols of known size and refractive index were generated and their extinction measured. The measured extinctions were then compared to the theoretical extinctions calculated using Mie theory (3–7 × 10−7cm−1). Excellent agreement is found from both the O4 and H2O retrievals. This enables the first inherently calibrated CEAS measurement at blue wavelengths in open cavity mode, and eliminates the need for sampling lines to supply air to the cavity, i.e., keep the cavity enclosed and/or aerosol free. Measurements in open cavity mode are demonstrated for CHOCHO, CH3COCHO, NO2, H2O and aerosol extinction. Our prototype LED-CE-DOAS provides a low cost, yet research grade innovative instrument for applications in simulation chambers and in the open atmosphere.

Cavity enhanced detection methods for probing the dynamics of spin correlated radical pairs in solution

Cavity enhanced absorption spectroscopy (CEAS) combined with phase-sensitive detection is employed to study the effects of static magnetic fields on radical recombination reactions. The chemical system comprises the photochemically generated thionine semiquinone radical and a 1,4-diazabicyclo[2.2.2]octane (DABCO) cationic radical in a micellar solution of sodium dodecyl sulphate. Data obtained using the modulated CEAS technique, describing the magnetic field effect (MFE) on reaction yields, are shown to be superior to those obtained using conventional transient absorption (TA) flash photolysis methods typically employed for these measurements. The high sensitivity afforded by modulated CEAS detection is discussed in terms of the new possibilities it offers such as the measurement of magnetic field effects in real biological systems which have hitherto been largely beyond the detection capabilities of existing techniques.

Cavity Enhanced Absorption Spectroscopy Sensor

The paper presents opportunities of cavity enhanced absorption spectroscopy technique application in nitrogen oxides (NOx) detection. In this method the concentration of an absorbing gas is determined by measure of decay time of the light pulse trapped in an optical cavity. The measurements are not sensitive to fluctuation of both laser power and photodetector sensitivity. The cavity enhanced absorption spectroscopy technique is a modification of cavity ring down spectroscopy technique where the o-axis adjustment of the resonator is used. NOx detection is carried out in the visible and infrared range. The signal is registered with a developed low noise photoreceiver. Features of the presented sensor show that it is possible to build a portable trace gases sensor. Its sensitivity could be comparable with chemical detectors. Such a system has several advantages: relatively low price, small size and weight, and detection possibility of other gases.

4 Cavity ring-down and cavity enhanced spectroscopy using diode lasers

Continuous wave (cw) diode lasers are increasingly being used as light sources in the visible and near-IR regions of the spectrum for cavity ring-down spectroscopy (CRDS) and cavity enhanced absorption spectroscopy (CEAS); the latter technique is also widely known as integrated cavity output spectroscopy (ICOS). The very high sensitivities to weak absorptions that are possible with cw CRDS and CEAS, coupled with the quantitative nature of the absorption measurements, are enabling a rapidly expanding range of applications. We review the benefits and practical implementation of these techniques; methods of data analysis for extraction of quantitative absorption data; the sensitivities of cw CRDS and CEAS, and how they might be optimised; and applications of cw CRDS and CEAS in molecular spectroscopy, atmospheric chemistry, plasma and flame chemistry, analytical science, and medical diagnosis via breath analysis. The development of CRDS and CEAS techniques exploiting cw diode lasers and, very recently, high luminosity light-emitting diodes, has stimulated a wealth of high-sensitivity measurements. Highlights include quantitative measurement of various ultra-trace gases such as: NO3, NO2 and ethene in ambient air samples; CO2 isotopologues, ethane and other organic compounds in human breath samples; and excited electronic states of N2 and O2 in plasmas and discharges. Exciting developments include wavelength extension into the mid-IR and UV regions, and use of novel locked-cavity techniques to increase data acquisition rates and sensitivities.

Characterization of an inductively coupled N2 plasma using sensitive diode laser spectroscopy

In this paper, we present an optical study of the state of N2 produced in an inductively coupled plasma. The operation of the discharge was characterized using ion flux measurements and broadband optical emission, and a clear change from capacitively to inductively coupled behaviour was observed with increasing applied power. The typical ion flux at 100 W and 10 mTorr was found to be 1.8 × 1018 m2 s−1, from which a ion density of ∼1.5 × 109 cm−3 was inferred. Diode laser cavity enhanced absorption spectroscopy (CEAS) was used to probe the state via the band at 686 nm. P33 band head spectra were used to determine both the translational (Ttr) and rotational (Trot) temperatures of the molecules at the v = 0 level. These were found to be in equilibrium but dependent on plasma parameters; in a 10 mTorr discharge, Trot ≈ Ttr, varying from ∼300 K at 5 W to ∼450 K at 400 W applied power. Absolute number densities in individual spin–rotation states were determined by calibrating the CEAS technique using the cavity ringdown time to measure the mirror reflectivity. The overall population in the v = 0 level was found to be (1.19 ± 0.07) × 1010 cm−3 under typical conditions of 100 W radio frequency power and 10 mTorr pressure, corresponding to a discharge efficiency for the production of this level of ∼10−5. A kinetic scheme is presented to account for the pressure and power dependence of the A-state concentration in the v = 0 level.