Cavity Ring-down Spectrometer Research Articles

Improvements on the FANTASIO set-up and new spectroscopic results concerning the Ar-H2O van der Waals complex in the 2OH overtone region

We present a series of improvements of the FANTASIO experimental set-up that couples a supersonic expansion to a cavity ring-down spectrometer originally reported by M. Herman, et al., Mol. Phys. 105, 815 (2007). In particular, the implementation of a new pulsed slit valve of 80 mm in length is detailed. The design is based on a powerful piezo stack actuator. Schlieren imaging is used to verify the homogeneity of the molecular beam and the quality of the pulsed slit performance. The ability to form weakly bound van der Waals complexes is assessed using the cavity ring-down spectrometer and a new chirped-pulse Fourier transform microwave spectrometer with the 12–18 GHz operating range. The water hexamer and heptamer were observed using this microwave spectrometer. Following enhancements and an extended laser coverage of the CRDS in the 2OH region, we observed and analyzed seven sub-bands of the Ar-H216O van der Waals complex, along with one sub-band of the much less abundant Ar-H218O isotopologue.

High-precision HD spectroscopy near 1.53 μm

In this study, we report highly precise and accurate measurements of the P(5), P(6), and O(3) transitions of the 2–0 band of HD occurring at approximately 1.5 μm. HD spectra were acquired in the pressure range of 100–900 Torr using a cavity ring-down spectrometer linked to an optical frequency comb. The line-shape analysis was performed using the Hartmann–Tran profile in the so-called β-corrected version. For the P(5) transition, we improved the accuracy of previous line center frequency determinations by more than two orders of magnitude. Moreover, for the P(5) and P(6) line centers, the total standard uncertainty is below 3 MHz, similar to those provided by quantum electrodynamics predictions, making them useful for direct comparisons that might foster future improvements of the theoretical model.

Demonstration of record sensitivity for water vapor detection by means of comb-locked cavity ring-down spectroscopy

We report on the development, characterization, and test of a comb-locked cavity ring-down spectrometer (CL-CRDS) operating in the spectral region around 1.39 µm. The system is based on the use of a hemispherical optical resonator with a finesse as high as ∼507000, which gives an empty-cavity ring-down time of about 285 µs. An Allan-Werle analysis on repeated acquisitions of the ring-down time at a fixed laser frequency suggests a minimum detectable absorption coefficient of 2×10−12cm−1 for the optimum integration time of 45 s. This limit can be exceeded by adopting the strategy of long-term spectral averaging. Taking advantage of the frequency stability guaranteed by the optical frequency comb, the CL-CRDS spectra were averaged over more than two days, thus removing efficiently the effect of mechanical, acoustic, and thermal noises. As a result, we could achieve a minimum detectable absorption coefficient as low as 3.7×10−13cm−1, which corresponds to a limit of detection for H2O in N2 of nine parts per trillion and a H2O partial pressure of 2×10−8 Pa (or 2×10−10 mbar). The potentialities of our approach are demonstrated by recording the absorption features of HD16O and HD18O in flows of ultra-high-purity N2 and ambient air, respectively.

Cavity ring-down spectroscopy of acetylene near [formula omitted]

A continuous-wave cavity ring-down spectrometer was employed to record the spectrum of the acetylene molecule spanning the 12350 - 12790 cm−1 region. A total of 747 lines from the principal isotopologue and 68 lines from 12C13CH2 were identified, with nearly all line intensities retrieved from the spectra. These lines belong to eighteen vibrational bands of 12C2H2 and two vibrational bands of 12C13CH2, among which five vibrational bands are reported here for the first time. Spectroscopic constants were deduced for all the identified bands, and the vibrational dipole moment squared along with Herman–Wallis coefficients were determined for the majority of these bands. Additionally, several resonance interactions were thoroughly explored.

Methodology for the quantification of the absorption potential of greenhouse - and pollutant gases by climbing plants used in façade greening; a case study on ivy (Hedera helix)

How much do specific climbing plants contribute to the cleansing or absorption of harmful greenhouse and pollutant gases; often regarded as the main environmental threat in cities due to their adverse effects on human health? One of the main hurdles in the quantification of such ecosystem services is associated with the difficulty to obtain and design systems that provide detailed information on the interaction between various gases and the plant in question. To tackle these questions, two highly precise and accurate instruments, namely a mid-infrared laser absorption spectrometer (TDL) and a cavity-ring-down spectrometer (CRDS) were used to monitor the fate of gases when exposed to façade climbing plants like ivy. In a laboratory setting, a relaxation type of experiment was used consisting of a reaction chamber equipped with plant species and continuously flushed by synthetic air. This setup was used to determine the timescales of decay after short injections of the above-mentioned gases. After these injections, all gases followed simple exponential decay curves. N2O, a non-reactive (inert) tropospheric gas, was used as a reference to which all other gases were compared and thereby quantified. This paper focuses on the detailed description of methods and processes to analyse the gas-absorptive behaviour of plants when exposed to gaseous pollutants. For demonstration purposes, quantified absorption features of nitrogen oxide (NO2) are presented for ivy of the variety Hedera helix “Plattensee”. Results of this method of quantification showed that - as compared to N2O (control), - NO2 had a reduced residence time (time scale) of 100 s, while N2O resulted in a 600 s residence time (indicating no interference with the plant). This is equivalent to a 0.3 cm/s deposition velocity/ absorption rate of NO2 under light conditions.

Three-dimensional detection of CO2 and wind using a 1.57 µm coherent differential absorption lidar

A 1.57-µm coherent differential absorption lidar is demonstrated for measuring three-dimensional CO2 and wind fields simultaneously. The maximum detection range of CO2 is up to 6 km with a range resolution of 120 m and a time resolution of 1 min. A preliminary assessment of instrument performance is made with a 1-week continuous observation. The CO2 concentration over a column from 1920 to 2040 m is compared with the one measured by an optical cavity ring-down spectrometer placed on a 2 km-away meteorological tower. The concentration is strongly correlated with the in-situ spectrometer with a correlation coefficient and RMSE of 0.91 and 5.24 ppm. The measurement accuracy of CO2 is specified with a mean and standard deviation of 2.05 ppm and 7.18 ppm, respectively. The regional CO2 concentration and the three-dimensional wind fields are obtained through different scanning modes. Further analysis is conducted on vertical mixing and horizontal transport of CO2 by combining with the measured wind fields.

High-resolution investigation of the spin-rotation doublets of 14NO2 at 6.2 µm mid-infrared region using cavity ring-down spectroscopy

Nitrogen dioxide (14NO2) exhibits a unique doublet structure due to the presence of its unpaired electron, which results in a nonzero electronic angular momentum in the ground electronic state of the molecule. In this study, an investigation into high-resolution rovibrational spectral features associated with the spin-rotation doublets of 14NO2 was conducted using an external-cavity quantum cascade laser (EC-QCL)-coupled cavity ring-down spectrometer operating at 6.2 μm. Four spin-split doublets belonging to the RR branch of the (001)-(000) fundamental band were probed in the mid-IR spectral region. The air broadening and self-broadening coefficients were reported explicitly for each doublet component for the first time, to the best of our knowledge. The line-intensities were also quantified, and they were compared to the HITRAN database, revealing good agreement (<4% discrepancy).

Development of a fast‐response system with integrated calibration for high‐resolution mapping of dissolved methane concentration in surface waters

AbstractDissolved gas concentrations in surface waters can have sharp gradients across marine and freshwater environments, which often prove challenging to capture with analytical measurement. Collecting discrete samples for laboratory analysis provides accurate results, but suffers from poor spatial resolution. To overcome this limitation, water equilibrators and gas membrane contactors (GMCs) have been used for the automated underway measurement of dissolved gas concentrations in surface water. However, while water equilibrators can provide continuous measurements, their analytical response times to changes in surface water concentration can be slow, lasting tens of minutes. This leads to spatial imprecisions in the dissolved gas concentration data. Conversely, while GMCs have proven to have much faster analytical response times, often lasting only a few minutes or less, they suffer from poor accuracy and thus require routine calibration. Here we present an analytical system for the high accuracy and high precision spatial mapping of dissolved methane concentration in surface waters. The system integrates a GMC with a cavity ringdown spectrometer for fast analytical response times, with a calibration method involving two Weiss‐style equilibrators and discrete measurements in vials. Data from both the GMC and equilibrators are collected simultaneously, with discrete vial samples collected periodically throughout data collection. We also present a mathematical algorithm integrating all data collected for the routine calibration of the GMC dataset. The algorithm facilitates comparison between the GMC and equilibrator datasets despite the substantial differences in response times (0.7–2.1 and 4.1–17.6 min, respectively). This measurement system was tested with both systematic laboratory experiments and field data collected on a research cruise along the US Atlantic margin. Once calibrated, this system identified numerous sharp peaks of dissolved methane concentration in the US Atlantic margin dataset that would be poorly resolved, or outright missed with previous measurement techniques. Overall, the precision and accuracy for the technique presented here were determined to be 11.2% and 10.4%, respectively, the operating range was 0–1000 ppm methane, and the e‐folding response time to changes in dissolved methane concentration was 0.7–2.1 min.

Theoretically predicted CO2 lines near 700 nm not observed

We present an experimental study of carbon dioxide absorption in the transparency window near 700 nm, where different calculations predicted several extremely weak bands. The measurements were done using the optical frequency comb-assisted cavity ring-down spectrometer reaching sensitivity (noise-equivalent absorption) of 3.1⋅10−12 cm−1. None of 21 lines, predicted by the most comprehensive calculations, were detected in five separate spectral regions near 700 nm. Our estimated detection limit ranges between 3 and 21 times lower than the expected peak absorption in the conditions of the experiment.

CRDS line-shape study of the (7–0) band of CO

We present the results of the spectral line-shape study of the first measurement of the extremely weak (7–0) band of the 12C16O molecule. Measurements were done with a highly sensitive cavity ring-down spectrometer. Collisional narrowing, analyzed in terms of speed-dependent effects, was observed for the first time for transitions with line intensities below 2⋅10−29 cm/molecule at 296 K. We provide a full set of line-shape parameters of the speed-dependent and regular Voigt profile analysis for 14 transitions from P and R branches. Experimental verification of a strong vibrational dependence of the pressure shifting described by the Hartmann model (Hartmann, 2009) is extended up to the sixth overtone highly sensitive to the model parameter.

Collision-broadening of vibration-inversion-rotation ammonia spectral lines in Q(J)-branch at 6.2 µm by cavity ring-down spectroscopy

In this experimental investigation, collision broadening effects on the Q(J)-branch vibration-inversion-rotation spectral lines of ammonia (NH3) within the fundamental ν4 asymmetric bending vibrational band in the 6.2 µm mid-IR region are reported. A continuous-wave external-cavity quantum cascade laser coupled with a high-sensitive cavity ring-down spectrometer was employed to selectively probe 10 transitions in high-resolution, including few inversion doublets of gaseous NH3. Pressure-broadening coefficients, γNH3-Xi (Xi = He, Ar, N2, O2, zero-air) in cm−1 atm−1, characterizing the collision interaction between NH3 and various external perturbing gases, including helium, argon, nitrogen, oxygen, and zero-air, were determined at room temperature (296 K). Mean collision times and optical collision diameters of each collision partner were explored to gain deeper insight into the perturber-induced collision dynamics. This investigation elucidates the intricate intermolecular interactions and collision phenomena induced by various foreign perturbers with NH3, with potential implications for future spectroscopic and atmospheric research of this polyatomic molecule.

Development of a continuous UAV-mounted air sampler and application to the quantification of CO2 and CH4 emissions from a major coking plant

Abstract. The development in uncrewed aerial vehicle (UAV) technologies over the past decade has led to a plethora of platforms that can potentially enable greenhouse gas emission quantification. Here, we report the development of a new air sampler, consisting of a pumped stainless coiled tube of 150 m in length with controlled time stamping, and its deployment from an industrial UAV to quantify CO2 and CH4 emissions from the main coking plant stacks of a major steel maker in eastern China. Laboratory tests show that the time series of CO2 and CH4 measured using the sampling system is smoothed when compared to online measurement by the cavity ring-down spectrometer (CRDS) analyzer. Further analyses show that the smoothing is akin to a convolution of the true time series signals with a heavy-tailed digital filter. For field testing, the air sampler was mounted on the UAV and flown in virtual boxes around two stacks in the coking plant of the Shagang Group (steel producer). Mixing ratios of CO2 and CH4 in air and meteorological parameters were measured from the UAV during the test flight. A mass-balance computational algorithm was used on the data to estimate the CO2 and CH4 emission rates from the stacks. Using this algorithm, the emission rates for the two stacks from the coking plant were calculated to be 0.12±0.014 t h−1 for CH4 and 110±18 t h−1 for CO2, the latter being in excellent agreement with material-balance-based estimates. A Gaussian plume inversion approach was also used to derive the emission rates, and the results were compared with those derived using the mass-balance algorithm, showing a good agreement between the two methods.

Assignment of the methanol OH-stretch overtone spectrum using the pattern recognition method.

We present the measurement and analysis of the 2OH stretching band of methanol between 7165 cm-1 and 7230 cm-1 cooled down to 26 ± 12 K in a buffer gas cooling experiment. Measurements were performed with a cavity ring-down spectrometer having a detection limit αmin = 2 × 10-10 cm-1. A total of 350 rovibrational transitions were assigned and 62 rovibrational transitions were tentatively assigned. This assignment was performed using the pattern recognition method developed by Rakvoský et al. [Phys. Chem. Chem. Phys., 2021, 23, 20193-20200]. In this work, we extended their method by using information on the relative intensities of the transitions to add one criterion to the validation of the assignments, allowing us to firmly assign 188 additional rovibrational transitions and to tentatively assign 14 more compared to the ir work.

A three-channel thermal dissociation cavity ring-down spectrometer for simultaneous measurement of ambient total peroxy nitrates, total alkyl nitrates, and NO2

A newly constructed thermal dissociation cavity ring-down spectrometer (TD-CRDS) for the simultaneous measurement of ambient total peroxy nitrates (ΣPNs, RO2NO2), total alkyl nitrates (ΣANs, RONO2), and NO2 was presented in this work. ΣPNs and ΣANs were detected as NO2 with the CRDS instrument after thermal dissociation. PNs and ANs completely dissociated at 180 °C and 360 °C, with conversion efficiencies of 96 % and 99 %, respectively. The effects of NO2 and NO on measurement in different temperatures and two types of thermal dissociation inlet (TDI) were further explored. The influence of ambient NO2 and NO on PNs and ANs in the improved TDI (TDI-2) was significantly improved. To further enhance the measurement accuracy, the consistency of the observed NO2 in the three channels was tested, which achieved good agreement. The detection limits of the TD-CRDS instrument for NO2, ΣPNs, and ΣANs were determined as 6.5, 6.8, and 8.6 pptv (10 s, 1σ), respectively. Observations of PNs and ANs were conducted in a suburban site in Hefei, China, from September 2–30, 2021, using the TD-CRDS instrument, and the consecutive time series of PNs and ANs were derived, verifying the capability of the TD-CRDS instrument for continuous field observations of ΣPNs and ΣANs.

Mid-infrared supermirrors with finesse exceeding 400 000

For trace gas sensing and precision spectroscopy, optical cavities incorporating low-loss mirrors are indispensable for path length and optical intensity enhancement. Optical interference coatings in the visible and near-infrared (NIR) spectral regions have achieved total optical losses below 2 parts per million (ppm), enabling a cavity finesse in excess of 1 million. However, such advancements have been lacking in the mid-infrared (MIR), despite substantial scientific interest. Here, we demonstrate a significant breakthrough in high-performance MIR mirrors, reporting substrate-transferred single-crystal interference coatings capable of cavity finesse values from 200 000 to 400 000 near 4.5 µm, with excess optical losses (scatter and absorption) below 5 ppm. In a first proof-of-concept demonstration, we achieve the lowest noise-equivalent absorption in a linear cavity ring-down spectrometer normalized by cavity length. This substantial improvement in performance will unlock a rich variety of MIR applications for atmospheric transport and environmental sciences, detection of fugitive emissions, process gas monitoring, breath-gas analysis, and verification of biogenic fuels and plastics.

Development of a cavity ring-down spectrometer toward multi-species composition.

This work presents the development of a cavity ring-down spectrometer (CRDS) designed for the detection of several molecules relevant for air pollution, including the second overtone of ro-vibration transitions from CO at 1.58 µm and NO at 1.79 µm. A unique feature of this CRDS is the use of custom mirrors with a reflectivity of about 99.99% from 1.52 to 1.80 µm, enabling efficient laser coupling into the cavity while ensuring a minimum detectable absorbance of 1.1 × 10-10cm-1 within an integration time of about 1.2s. In this work, the successful implementation of the current CRDS is demonstrated in two different wavelength regions. At 1.79 µm, the transitions R17.5 and R4.5 of the second overtone of NO are detected. At 1.58 µm, carbon dioxide and water vapor from untreated ambient air are measured, serving as an example to investigate the suitability of a post-processing procedure for the determination of the molar fraction in a multi-species composition. This post-processing procedure has the benefit of being calibration-free and SI-traceable. Additionally, CRDS measurements of gas mixtures containing CO and CO2 are also shown. In the future, the advantages of the developed cavity ring-down spectrometer will be exploited in order to perform fundamental studies on the transport processes of heterogeneous catalysis by locally resolving the gas phase near a working catalytic surface. The possibility to cover a broad wavelength region with this CRDS opens up the opportunity to investigate different catalytic reactions, including CO oxidation and NO reduction.

Comparison of photoacoustic spectroscopy and cavity ring-down spectroscopy for ambient methane monitoring at Hohenpeißenberg

Abstract. With an atmospheric concentration of approximately 2000 parts per billion (ppbV, 10−9), methane (CH4) is the second most abundant greenhouse gas (GHG) in the atmosphere after carbon dioxide (CO2). The task of long-term and spatially resolved GHG monitoring to verify whether climate policy actions are effective is becoming more crucial as climate change progresses. In this paper we report the CH4 concentration readings of our photoacoustic (PA) sensor over a 5 d period at Hohenpeißenberg, Germany. As a reference device, a calibrated cavity ring-down spectrometer, Picarro G2301, from the meteorological observatory of the German Weather Service (DWD) was employed. Trace gas measurements with photoacoustic instruments promise to provide low detection limits at comparably low costs. However, PA devices are often susceptible to cross-sensitivities related to fluctuating environmental conditions, e.g. ambient humidity. The obtained results show that for PA sensor systems non-radiative relaxation effects induced by varying humidity are a non-negligible factor. Applying algorithm compensation techniques, which are capable of calculating the influence of non-radiative relaxation effects on the photoacoustic signal, increase the accuracy of the photoacoustic sensor significantly. With an average relative deviation of 1.11 % from the G2301, the photoacoustic sensor shows good agreement with the reference instrument.

A BaGa4Se7 crystal based pulsed mid-infrared light source with a narrow linewidth in 4-12 µm.

We present a BaGa4Se7 (BGSe) crystal based coherent pulsed light source for high resolution mid-infrared (MIR) spectroscopy in the 4-12 µm region. The all-solid-state system consists of an injection seeded optical parametric generator (OPG) and an optical parametric amplifier (OPA) using two KTiOPO4 crystals. The idler output of OPG-OPA and the fundamental output (1064nm) of a wavelength stabilized Nd:YAG laser are employed for difference frequency generation of MIR pulses in the BGSe crystal. Pulsed MIR radiation in the 4-12 µm range is obtained with typical pulse energies higher than 100 µJ and pulse durations of ∼5ns. By measuring H2O absorption lines in the 8 µm region with this MIR light source and a cavity ring-down spectrometer, the linewidth of the MIR source is inferred as 120 ± 10MHz, which is very close to the Fourier-transform limited linewidth of 5ns laser pulses.

Monitoring of Trace Molecular Impurities in Clean-Room Air

A new measurement system has been introduced to perform real-time measurements of molecular air contaminants at different location in a clean room down to a concentration of approximately 0.1 ppb. The system consists of an air sampling unit coupled to a proton transfer mass spectrometer and a Cavity Ring-Down Spectrometer. The measurements show that the time average concentrations of more than 10 different volatile impurity molecules exceed 1 ppb.

Measurement report: Atmospheric CH4 at regional stations of the Korea Meteorological Administration–Global Atmosphere Watch Programme: measurement, characteristics, and long-term changes of its drivers

Abstract. To quantify CH4 emissions at policy-relevant spatial scales, the Korea Meteorological Administration (KMA) started monitoring its atmospheric levels in 1999 at Anmyeondo (AMY) and expanded monitoring to Jeju Gosan Suwolbong (JGS) and Ulleungdo (ULD) in 2012. The monitoring system consists of a cavity ring-down spectrometer (CRDS) and a new cryogenic drying method, with a measurement uncertainty (68 % c.i. (confidence interval)) of ± 0.7–0.8 ppb. To determine the regional characteristics of CH4 at each KMA station, we assessed the CH4 level relative to local background (CH4xs), analyzed local surface winds and CH4 with bivariate polar plots, and investigated CH4 diurnal cycles. We also compared the CH4 levels measured at KMA stations with those measured at the Mt. Waliguan (WLG) station in China and Ryori (RYO) station in Japan. CH4xs followed the order AMY (55.3 ± 37.7 ppb) &gt; JGS (24.1 ± 10.2 ppb) &gt; ULD (7.4 ± 3.9 ppb). Although CH4 was observed in well-mixed air at AMY, it was higher than at other KMA stations, indicating that it was affected not only by local sources but also by distant air masses. Annual mean CH4 was highest at AMY among all East Asian stations, while its seasonal amplitude was smaller than at JGS, which was strongly affected in the summer by local biogenic activities. From the long-term records at AMY, we confirmed that growth rate increased by 3.3 ppb yr−1 during 2006/2010 and by 8.3 ppb yr−1 from 2016 to 2020, which is similar to the global trend. Studies indicated that the recent global accelerated CH4-growth rate was related to biogenic sources. However, δ13CH4 indicates that the CH4 trend in East Asia is derived from both biogenic and fossil fuel sources from 2006 to 2020. We confirmed that long-term high-quality data can help understand changes in CH4 emissions in East Asia.