Optical Feedback Cavity-enhanced Absorption Spectroscopy Research Articles

Comparison of optical-feedback cavity-enhanced absorption spectroscopy and gas chromatography for ground-based and airborne measurements of atmospheric CO concentration

Abstract. We present the first comparison of carbon monoxide (CO) measurements performed with a portable laser spectrometer that exploits the optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS) technique, against a high-performance automated gas chromatograph (GC) with a mercuric oxide reduction gas detector (RGD). First, measurements of atmospheric CO mole fraction were continuously collected in a Paris (France) suburb over 1 week. Both instruments showed an excellent agreement within typically 2 ppb (part per billion in volume), fulfilling the World Meteorological Organization (WMO) recommendation for CO inter-laboratory comparison. The compact size and robustness of the OF-CEAS instrument allowed its operation aboard a small aircraft employed for routine tropospheric air analysis over the French Orléans forest area. Direct OF-CEAS real-time CO measurements in tropospheric air were then compared with later analysis of flask samples by the gas chromatograph. Again, a very good agreement was observed. This work establishes that the OF-CEAS laser spectrometer can run unattended at a very high level of sensitivity ( < 1 ppb) and stability without any periodic calibration.

ICL-Based OF-CEAS: A Sensitive Tool for Analytical Chemistry.

Optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS) using mid-infrared interband cascade lasers (ICLs) is a sensitive technique for trace gas sensing. The setup of a V-shaped optical cavity operating with a 3.29 μm cw ICL is detailed, and a quantitative characterization of the injection efficiency, locking stability, mode matching, and detection sensitivity is presented. The experimental data are supported by a model to show how optical feedback affects the laser frequency as it is scanned across several longitudinal modes of the optical cavity. The model predicts that feedback enhancement effects under strongly absorbing conditions can cause underestimations in the measured absorption, and these predictions are verified experimentally. The technique is then used in application to the detection of nitrous oxide as an exemplar of the utility of this technique for analytical gas phase spectroscopy. The analytical performance of the spectrometer, expressed as noise equivalent absorption coefficient, was estimated as 4.9 × 10-9 cm -1 Hz-1/2, which compares well with recently reported values.

Accurate laboratory determination of the near‐infrared water vapor self‐continuum: A test of the MT_CKD model

AbstractThe semi‐empirical MT_CKD model of the absorption continuum of water vapor is widely used in atmospheric radiative transfer codes of the atmosphere of Earth and, recently, of exoplanets but lacks of experimental validation in the atmospheric windows. Recent laboratory measurements by Fourier transform Spectroscopy led to self‐continuum cross sections much larger than the MT_CKD values in the near‐infrared transparency windows. We report on accurate measurements by Cavity Ring Down Spectroscopy (CRDS) and Optical Feedback‐Cavity‐Enhanced Absorption Spectroscopy (OF‐CEAS) at selected spectral points of the transparency windows centered around 4.0, 2.1, and 1.25 µm. The temperature dependence of the absorption continuum at 4.38 µm is measured in the 23–39°C range. The self‐continuum water vapor absorption is derived either from the baseline variation of water vapor spectra recorded for a series of pressure values over a small spectral interval or from baseline monitoring at fixed laser frequency during pressure ramps. After subtraction of the local water monomer lines contribution, self‐continuum cross sections, Cs, are determined with an accuracy better than 10% from the pressure squared dependence of the continuum absorption measured up to about 15 Torr. Together with our previous measurements in the 2.1 and 1.6 µm windows, the present results provide a unique set of water vapor cross sections for testing the MT_CKD model in four transparency windows. Although showing some important deviations of the absolute values (up to about a factor 4), our accurate measurements validate the overall frequency dependence of the most recent version (V2.8) of the MT_CKD model.

Detection of HO2 in an atmospheric pressure plasma jet using optical feedback cavity-enhanced absorption spectroscopy

Cold non-equilibrium atmospheric pressure plasma jets are increasingly applied in material processing and plasma medicine. However, their small dimensions make diagnosing the fluxes of generated species a challenge. Here we report on the detection of the hydroperoxyl radical, HO2, in the effluent of a plasma jet by the use of optical feedback cavity-enhanced absorption spectroscopy. The spectrometer has a minimum detectable absorption coefficient of cm−1 with a 100 second acquisition, equivalent to of HO2 (under ideal conditions). Concentrations in the range of (3.1–7.8) × 1013 cm−3 were inferred in the 4 mm wide effluent of the plasma jet.

Optical-feedback cavity-enhanced absorption spectroscopy with an interband cascade laser: application to SO2 trace analysis

The combination of interband cascade lasers (ICL) with cavity-enhanced absorption spectroscopy (CEAS) offers new perspectives in trace analysis and isotope ratio measurements. ICLs cover a mid-infrared spectral window (3–4 µm), in between those covered by Ga(InAs)Sb diode lasers and quantum cascade lasers (QCL), where strong molecular transitions can be found. While ICLs have lower emission power than QCLs, their thermal dissipation is much closer to that of telecom diode lasers and their current tuning range larger, which are both major advantages for developing compact instruments. We present an OF-CEAS implementation with an ICL at 4.015 µm, in which optical feedback (OF) enables efficient injection into the high-finesse cavity. In this paper, we also discuss a procedure allowing to obtain an accurate measurement of the OF rate. With regard to performance, we obtain a rms noise-equivalent absorption of 7.7 × 10−9 cm−1 for one acquired spectrum (80 ms) with a cavity of finesse 3900, which translates to a normalized figure of merit of 2.2 × 10−9 cm−1/√Hz, allowing for SO2 trace analysis down to ppbv levels with a response time of seconds.

Sensitive CH4 detection applying quantum cascade laser based optical feedback cavity-enhanced absorption spectroscopy.

We report on sensitive detection of atmospheric methane employing quantum cascade laser based optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS). An instrument has been built utilizing a continuous-wave distributed feedback quantum cascade laser (cw-QCL) with a V-shaped cavity, a common arrangement that reduces feedback to the laser from non-resonant reflections. The spectrometer has a noise equivalent absorption coefficient of 3.6 × 10-9 cm-1 Hz-1/2 for a spectral scan of CH4 at 7.39 μm. From an Allan-Werle analysis a detection limit of 39 parts per trillion of CH4 at atmospheric pressure within 50 s acquisition time was found.

Accurate measurements and temperature dependence of the water vapor self-continuum absorption in the 2.1 μm atmospheric window

In spite of its importance for the evaluation of the Earth radiative budget, thus for climate change, very few measurements of the water vapor continuum are available in the near infrared atmospheric windows especially at temperature conditions relevant for our atmosphere. In addition, as a result of the difficulty to measure weak broadband absorption signals, the few available measurements show large disagreements. We report here accurate measurements of the water vapor self-continuum absorption in the 2.1 μm window by Optical Feedback Cavity Enhanced Absorption Spectroscopy (OF-CEAS) for two spectral points located at the low energy edge and at the center of the 2.1 μm transparency window, at 4302 and 4723 cm(-1), respectively. Self-continuum cross sections, CS, were retrieved with a few % relative uncertainty, from the quadratic dependence of the spectrum base line level measured as a function of water vapor pressure, between 0 and 16 Torr. At 296 K, the CS value at 4302 cm(-1) is found 40% higher than predicted by the MT_CKD V2.5 model, while at 4723 cm(-1), our value is 5 times larger than the MT_CKD value. On the other hand, these OF-CEAS CS values are significantly smaller than recent measurements by Fourier transform spectroscopy at room temperature. The temperature dependence of the self-continuum cross sections was also investigated for temperatures between 296 K and 323 K (23-50 °C). The derived temperature variation is found to be similar to that derived from previous Fourier transform spectrometer (FTS) measurements performed at higher temperatures, between 350 K and 472 K. The whole set of measurements spanning the 296-472 K temperature range follows a simple exponential law in 1/T with a slope close to the dissociation energy of the water dimer, D0 ≈ 1100 cm(-1).

Optical-feedback cavity-enhanced absorption spectroscopy in a linear cavity: model and experiments

Optical-feedback cavity-enhanced absorption spectroscopy is a highly sensitive trace gas sensing tech- nique that relies on feedback from a resonant intracav- ity field to successively lock the laser to the cavity as the wavelength is scanned across a molecular absorption with a comb of resonant frequencies. V-shaped optical cavities have been favoured in the past in order to avoid additional feedback fields from non-resonant reflections that poten - tially suppress the locking to the resonant cavity frequency. A model of the laser-cavity coupling demonstrates, how- ever, that the laser can stably lock to a resonant linear cav- ity, within certain constraints on the relative intensity of the two feedback sources. By mode mismatching the field into the linear cavity, we have shown that it is theoretically and practically possible to spatially filter out the unwanted non- resonant component in order for the resonant field to domi - nate the feedback competition at the laser. A 5.3 µm cw quantum cascade laser scanning across a CO2 absorption feature demonstrated stable locking to achieve a minimum detectable absorption coefficient of 2.7 × 10 �9 cm �1 for 1-s averaging. Detailed investigations of feedback effects on the laser output verified the validity of our theoretical models.

Optical feedback cavity-enhanced absorption spectroscopy with a 3.24 μm interband cascade laser

The development of interband cascade lasers (ICLs) has made the strong C-H transitions in the 3 μm spectral region increasingly accessible. We present the demonstration of a single mode distributed feedback ICL coupled to a V-shaped optical cavity in an optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) experiment. We achieved a minimum detectable absorption coefficient, αmin, of (7.1±0.2)×10−8 cm−1 for a spectrum of CH4 at 3.24 μm with a two second acquisition time (100 scans averaged). This corresponds to a detection limit of 3 ppb CH4 at atmospheric pressure, which is comparable to previously reported OF-CEAS instruments with diode lasers or quantum cascade lasers. The ability to frequency lock an ICL source in the important 3 μm region to an optical cavity holds great promise for future spectroscopic applications.

Invited article: SUBGLACIOR: an optical analyzer embedded in an Antarctic ice probe for exploring the past climate.

This article describes the advances made in the development of a specific optical spectrometer based on the Optical Feedback-Cavity Enhanced Absorption Spectroscopy technique for exploring past climate by probing the original composition of the atmosphere stored in the ice sheet of a glacier. Based on significant technological progresses and unconventional approaches, SUBGLACIOR will be a revolutionary tool for ice-core research: the optical spectrometer, directly embedded in the drilling probe, will provide in situ real-time measurements of deuterium isotopic variations (δ(2)H ) and CH4 concentrations down to 3500 m of ice depth within a single Antarctic season. The instrument will provide simultaneous and real-time vertical profiles of these two key climate signatures in order to evaluate if a target site can offer ice cores as old as 1.5 million years by providing direct insight into past temperatures and climate cycles. The spectrometer has a noise equivalent absorption coefficient of 2.8 × 10(-10) cm(-1) Hz(-1/2), corresponding to a detection limit of 0.2 ppbv for CH4 and a precision of 0.2‰ on the δ(2)H of H2O within 1 min acquisition time.

Real-time measurements of endogenous carbon monoxide production in isolated pig lungs

Ischemia-reperfusion injuries are a critical determinant of lung transplantation success. The endogenous production of carbon monoxide (CO) is triggered by ischemia-reperfusion injuries. Our aim was, therefore, to assess the feasibility of exhaled CO measurements during the ex vivo evaluation of lungs submitted to ischemia-reperfusion injuries. Five pigs were euthanized and their lungs removed after pneumoplegia. After cold storage (30 min, 4°C), the lungs were connected to an extracorporeal membrane oxygenation circuit, slowly warmed-up, and ventilated. At the end of a 45-min steady state, CO measurements were performed by optical-feedback cavity-enhanced absorption spectroscopy, a specific laser-based technique for noninvasive and real-time low gas concentration measurements. Exhaled CO concentration from isolated lungs reached 0.45±0.19 ppmv and was above CO concentration in ambient air and in medical gas. CO variations peaked during the expiratory phase. Changes in CO concentration in ambient air did not alter CO concentrations in isolated lungs. Exhaled CO level was also found to be uncorrelated to heme oxygenase (HO-1) gene expression. These results confirm the feasibility of accurate and real-time CO measurement in isolated lungs. The presented technology could help establishing the exhaled CO concentration as a biomarker of ischemia-reperfusion injury in ex vivo lung perfusion.

Simultaneous cavity-enhanced and cavity ringdown absorption spectroscopy using optical feedback

We present a scheme of optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) including a fast optical switch to produce cavity ringdown spectra (OF-CRDS) simultaneously. This also works as a dynamically adjustable variable attenuator allowing to compensate for reduced signal levels in correspondence with absorption lines. For this, an acousto-optic deflector is used in a double-pass configuration to eliminate the single-pass frequency shift, which is incompatible with optical feedback. This is probably the most effective device providing the required fast response and the high extinction ratio necessary to perform clean ringdown measurements. The resulting direct comparison of OF-CEAS and OF-CRDS shows that these produce almost equivalent spectral data, with 0.3 % maximal difference at the top of an absorption line having a signal-to-noise ratio (S/N) of 3,300. OF-CEAS is largely winning on the short-term noise level while OF-CRDS appears to be more immune from interference fringes, delivering cleaner spectra after longer averaging.

Linear cavity optical-feedback cavity-enhanced absorption spectroscopy with a quantum cascade laser

A cw distributed feedback quantum cascade laser (DFB-QCL) coupled to a two-mirror linear optical cavity has been used to successfully demonstrate optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS) at 5.5 μm. The noise-equivalent absorption coefficient, α(min), was 2.4×10(-8) cm(-1) for 1 s averaging, limited by etalon-fringing. The temporal stability of the instrument allows NO detection down to 5 ppb in 2 s.

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum-cascade laser yields the lowest formaldehyde detection limit

We report on the first application of Optical Feedback-Cavity Enhanced Absorption Spectroscopy to formaldehyde trace gas analysis at mid-infrared wavelengths. A continuous-wave room-temperature, distributed-feedback quantum cascade laser emitting around 1,769 cm−1 has been successfully coupled to an optical cavity with finesse 10,000 in an OF-CEAS spectrometer operating on the ν2 fundamental absorption band of formaldehyde. This compact setup (easily transportable) is able to monitor H2CO at ambient concentrations within few seconds, presently limited by the sample exchange rate. The minimum detectable absorption is 1.6 × 10−9 cm−1 for a single laser scan (100 ms, 100 data points), with a detectable H2CO mixing ratio of 60 pptv at 10 Hz. The corresponding detection limit at 1 Hz is 5 × 10−10 cm−1, with a normalized figure of merit of 5 × 10−11cm $$^{-1}/\sqrt{\rm Hz}$$ (100 data points recorded in each spectrum taken at 10 Hz rate). A preliminary Allan variance analysis shows white noise averaging down to a minimum detection limit of 5 pptv at an optimal integration time of 10 s, which is significantly better than previous results based on multi-pass or cavity-enhanced tunable QCL absorption spectroscopy.

Optical feedback cavity enhanced absorption spectroscopy: effective adjustment of the feedback-phase

Optical-feedback cavity enhanced absorption spectroscopy (OF-CEAS) is a very sensitive technique for the detection of trace amounts of gaseous absorbers. The most crucial parameter in an OF-CEAS setup is the optical phase of the light fed back into the laser source, which is usually controlled by the position of a piezo driven mirror. Various approaches for the analysis of the cavity transmitted light with respect to feedback-phase are presented, and tested on simulated phase and frequency dependent cavity transmission. Finally, we present the performance of a digital signal processor based regulator—employing one of these approaches—in a real OF-CEAS experiment. The results of the simulation show that several algorithms are well suited for the task of control signal generation. They confirm also that with the presented approach, a mode by mode correction of the feedback-phase is possible. Consequently, a regulatory bandwidth of 37 Hz was achieved. This maximum control frequency was limited by the piezo system.

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum cascade laser

Optical-feedback cavity-enhanced absorption spectroscopy is demonstrated in the mid-IR by using a quantum cascade laser (emitting at 4.46 μm). The laser linewidth reduction and frequency locking by selective optical feedback from the resonant cavity field turns out to be particularly advantageous in this spectral range: It allows strong cavity transmission, which compensates for low light sensitivity, especially when using room-temperature detectors. We obtain a noise equivalent absorption coefficient of 3 × 10(-9)/cm for 1 s averaging of spectra composed by 100 independent points. At 4.46 μm, this yields a detection limit of 35 parts in 10(12) by volume for N(2)O at 50 mbar, corresponding to 4 × 10(7) molecules/cm(3), or still to 1 fmol in the sample volume.

A quantum cascade laser-based optical feedback cavity-enhanced absorption spectrometer for the simultaneous measurement of CH4 and N2O in air

Optical feedback cavity-enhanced absorption spectroscopy (OF CEAS) has been demonstrated with a thermoelectrically cooled continuous wave distributed feedback quantum cascade laser (QCL) operating at wavelengths around 7.84 μm. The QCL is coupled to an optical cavity which creates an absorption pathlength greater than 1000 m. The experimental design allows optical feedback of infra-red light, resonant within the cavity, to the QCL, which initiates self-locking at each TEM00 cavity mode frequency excited. The QCL linewidth is narrowed to below the mode linewidth, greatly increasing the efficiency of injection of light into the cavity. At the frequency of each longitudinal cavity mode, the absorption coefficient of an intracavity sample is obtained from the transmission at the mode maximum, measured with a thermoelectrically cooled detector: spectral line profiles of CH4 and N2O in ambient air were recorded simultaneously and with a resolution of 0.01386 cm−1. A minimum detectable absorption coefficient of 5.5×10−8 cm−1 was demonstrated after an averaging time of 1 s for this completely thermoelectrically cooled system. The bandwidth-normalised limit for a single cavity mode is 5.6×10−9 cm−1 Hz−1/2 (1σ).

Development and airborne operation of a compact water isotope ratio infrared spectrometer†

A sensitive laser spectrometer, named IRIS (water isotope ratio infrared spectrometer), was developed for the in situ detection of the isotopic composition of water vapour in the upper troposphere and the lower stratosphere. Isotope ratio measurements can be used to quantify troposphere–stratosphere exchange, and to study the water chemistry in the stratosphere. IRIS is based on the technique of optical feedback cavity-enhanced absorption spectroscopy. It uses a room temperature near-infrared laser, and does not require cryogenic cooling of laser or detectors. The instrument weighs 51 kg including its support structure. Airborne operation was demonstrated during three flights aboard the European M55-Geophysica stratospheric research aircraft, as part of the AMMA/SCOUT-03 (African Monsoon Multidisciplinary Analysis/Stratospheric Climate links with emphasis on the Upper Troposphere and lower stratosphere) campaign in Burkina Faso in August 2006. One-second averaged, vertical profiles of δ2H, δ17O and δ18O in the upper troposphere are shown, as are the δ17O–δ18O and δ2H–δ18O relations. The data are discussed with reference to a Rayleigh distillation model. As expected, there is no indication of non-mass-dependent fractionation (also known as mass-independent fractionation) in the troposphere. Furthermore, improvements to the thermal management system and a move to a (cryogen-free) longer-wavelength laser source are discussed, which together should result in approximately two orders of magnitude improvement of the sensitivity.

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) in a ring cavity

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) has been demonstrated by coupling a distributed feedback diode laser to a ring cavity. Frequency-selected light decaying from the ring cavity is retro-reflected, inducing a counter-propagating intra-cavity beam, and providing optical feedback to the laser. At specific laser-to-cavity distances, all cavity mode frequencies return to the diode laser with the same phase, allowing spectra to be accumulated across the range of frequencies of the current-tuned laser. OF-CEAS has been used to measure very weak oxygen isotopologue (16O18O and 16O17O) absorptions in ambient air at wavelengths near 762 nm using the electric-dipole forbidden O2 A-band. A bandwidth reduced minimum detectable absorption coefficient of 2.2×10−9 cm−1 Hz−1/2 is demonstrated.

A Microdrop Generator for the Calibration of a Water Vapor Isotope Ratio Spectrometer

Abstract A microdrop generator is described that produces water vapor with a known isotopic composition and volume mixing ratio for the calibration of a near-infrared diode laser water isotope ratio spectrometer. The spectrometer is designed to measure in situ the water vapor deuterium and oxygen (17O and 18O) isotope ratios from the low troposphere up to the lower stratosphere with a high temporal resolution, and is based on ultrasensitive optical-feedback cavity-enhanced absorption spectroscopy. To calibrate the spectrometer, a commercial microdrop generator (Microdrop GmbH) is used to inject water droplets of known size at a preset repetition frequency into a stream of dry nitrogen or synthetic air. Complete evaporation of the small droplets ensures that there is no isotopic fractionation between the liquid phase and the generated moist “air.” The water mixing ratio of the synthetic air is controlled by the repetition rate and gas flow. The current system spans a water mixing ratio range from about 10 to 5000 ppmv, representing the range of conditions expected in the lower to upper troposphere. Both lower and higher mixing ratios can be produced after small modifications to the injector’s operating conditions or the system’s design.