Cavity Ring-down Spectroscopy Research Articles

Measurements of N2 + ions in an inductively coupled plasma using saturated cavity ringdown spectroscopy

Abstract This paper presents a unique study of the bulk plasma characteristics in a low pressure inductively coupled nitrogen plasma. Saturated cavity ringdown spectroscopy (sat-CRDS) has been used to determine the absolute number densities and translational temperatures of N2 +(X, ν = 0). The effect of saturation is readily accounted for by using an effective saturation parameter, Seff , and determined by a simple method employing measurements at two different gain settings of the detection system. The appropriateness of this method is confirmed by comparison with fitting individual ringdown data using a time-dependent saturation parameter, S(t), within the local approximation model for sat-CRDS; the two methods are in excellent agreement in returning absolute number densities and translational temperatures. N2 +(X, ν = 0) number densities are determined across a matrix of pressure (10 − 100 mTorr) and rf power (200 − 400 W) conditions with maximum number densities of ca. 1.3 × 1010 cm−3 while translational temperatures range from 600 − 1500 K.

Precipitation in the mountains of Central Asia: isotopic composition and source regions

Abstract. Over 900 event-based precipitation samples were collected in 2019–2021 in the Tien Shan and its foothills and analysed using cavity ring-down spectroscopy. δD and δ18O values were highest in summer and lowest in winter, and annual cycles of deuterium excess (d-excess) varied between sites, reflecting local conditions. The δ18O and δD values increased from north to south in all seasons except autumn, and latitude was a statistically significant predictor of δ18O and δD in the overall data set, along with elevation in winter and elevation and longitude in autumn. Elevation was a significant predictor of d-excess in all seasons, and local air temperature was a more important control over δ18O and δD than precipitation depth. Local meteoric water lines were derived using seven regression methods applied to non-weighted and weighted precipitation. Non-weighted ordinary least squares regression and reduced major axis regression methods are recommended overall, except for summer when the precipitation-weighted least squares regression should be used, particularly in the south. Atmospheric back-trajectory and mixing-model analyses were applied in combination to identify air mass source regions and their relative contribution to precipitation. Recycled moisture from irrigated land in the Amu Darya and Syr Darya basins and from the study catchments accounted for 29 %–71 % of precipitation, depending on the site and season. In the Chon Kyzyl-Suu catchment, local re-evaporation from Issyk-Kul accounted for up to 85 % of precipitation. These findings highlight the importance of moisture from terrestrial sources, especially irrigated land, for the formation of precipitation in the Tien Shan.

Protocols for bulk off-line fluid inclusion extraction for the analysis of δ13C-CH4 and δ13C-CO2 using a cavity ring-down spectroscopy (CRDS) analyser

Fluid inclusions are a window into deep geological fluids, providing unique access to their nature and composition. The isotopic composition of CO2 and CH4 hosted in fluid inclusions is a powerful proxy to assess the origin and transformation of deep geological fluids, giving insights into carbon sources, fluxes, and degassing in a wide variety of geodynamic settings. Over the last 5 decades, techniques have been developed to extract fluid inclusions from their host minerals and measure their bulk composition. These techniques are often challenged by analytical artifacts including high blank levels of CO2 and CH4, fluid re-speciation, gas adsorption, and diffusion. Since these processes may alter the pristine composition of gases liberated from fluid inclusions, rigorous protocols are needed in order to evaluate the isotopic integrity of the extracted volatile species. In this study, we introduce new protocols for bulk off-line fluid inclusion extraction for the analysis of δ13C-CH4 and δ13C-CO2 using a Cavity Ring-Down Spectroscopy (CRDS) analyser (Picarro G2201-i). Two mechanical fluid extraction techniques are compared: ball milling in ZrO2 jars and sample crushing in a stainless steel sealed tube under a hydraulic press. Blanks and isotopically labelled tests with the ball milling technique suggest that rotation speed, grinding stock filling degree and filling type alter the CH4 and CO2 concentrations and isotopic compositions measured by the CRDS analyser. In contrast, the crushing technique does not generate measurable quantities of blank CH4 and CO2. The protocols presented in this study allow to extract, detect, and analyse δ13C of CH4 and CO2 for concentrations above 10 and 1,000 ppm respectively. Interlaboratory experiments allowed to replicate previously measured δ13C-CH4 values in natural fluid inclusions within 1‰ with both extraction techniques. This study highlights the potential of combining simple bulk off-line fluid inclusion extraction techniques with a CRDS analyser for δ13C analysis of CO2 and CH4 without gas separation being required.

Development and deployment of a mid-cost CO2 sensor monitoring network to support atmospheric inverse modeling for quantifying urban CO2 emissions in Paris

Abstract. To effectively monitor highly heterogeneous urban CO2 emissions using atmospheric observations, there is a need to deploy cost-effective CO2 sensors at multiple locations within the city with sufficient accuracy to capture the concentration gradients in urban environments. These dense measurements could be used as input of an atmospheric inversion system for the quantification of emissions at the sub-city scale or to separate specific sectors. Such quantification would offer valuable insights into the efficacy of local initiatives and could also identify unknown emission hotspots that require attention. Here we present the development and evaluation of a mid-cost CO2 instrument designed for continuous monitoring of atmospheric CO2 concentrations with a target accuracy of 1 ppm for hourly mean measurements. We assess the sensor sensitivity in relation to environmental factors such as humidity, pressure, temperature and CO2 signal, which leads to the development of an effective calibration algorithm. Since July 2020, eight mid-cost instruments have been installed within the city of Paris and its vicinity to provide continuous CO2 measurements, complementing the seven high-precision cavity ring-down spectroscopy (CRDS) stations that have been in operation since 2016. A data processing system, called CO2calqual, has been implemented to automatically handle data quality control, calibration and storage, which enables the management of extensive real-time CO2 measurements from the monitoring network. Colocation assessments with the high-precision instrument show that the accuracies of the eight mid-cost instruments are within the range of 1.0 to 2.4 ppm for hourly afternoon (12:00–17:00 UTC) measurements. The long-term stability issues require manual data checks and instrument maintenance. The analyses show that CO2 measurements can provide evidence for underestimations of CO2 emissions in the Paris region and a lack of several emission point sources in the emission inventory. Our study demonstrates promising prospects for integrating mid-cost measurements along with high-precision data into the subsequent atmospheric inverse modeling to improve the accuracy of quantifying the fine-scale CO2 emissions in the Paris metropolitan area.

CRDS‐based measurement of CO/CO2 concentration ratios for assessing transformer insulation aging

AbstractA gas analyzer has been developed using cavity ring‐down spectroscopy (CRDS) technology, designed to simultaneously measure the concentrations of CO2 and CO. These gases are critical indicators of transformer insulation degradation. The analyzer covers a CO2 concentration range from a few ppm to several thousand ppm and can measure CO/CO2 concentration ratios from 0.076 to 0.8. The selected absorption lines for CO and CO2 are centered at 6337.99 and 6338.59 cm−1, respectively. The two candidate lines are proximate to each other and nonoverlapping. The experimental results indicate that the system accurately fits the measured and calculated signals, enabling concentration measurements at the ppm level. This confirms its ability to measure the gas concentrations and ratios critical for assessing the condition of transformer insulation. This CRDS‐based system offers a reliable and sensitive method for early detection of potential transformer faults.

Buffer-gas cooling of hydrogen cyanide quantified by cavity-ringdown spectroscopy

We describe an instrument that uses continuous-wave (CW) cavity-ringdown spectroscopy to measure the translational and rotational temperature of buffer-gas cooled molecules and demonstrate its use on hydrogen cyanide. This instrument can access the near-infrared region around 1.5 μm—a rich spectral region that features the rotationally resolved first overtone of the C-H stretch for many astrophysically relevant molecules. Molecules are probed directly inside the buffer-gas cell, further enabling quantitative measurements of the effectiveness of this cooling technique.

Ternary Association Reaction of Vibrationally Cold N2+ Ions in Ambient Helium.

The rate coefficients for the ternary association reaction of vibrationally cold N2+ ions with N2 and He were measured in an afterglow plasma in the temperature range of 140-250 K: kN4+ = (1.02 ± 0.39)(300/T)(1.28±0.08) × 10-29 cm6 s-1. The rotational and vibrational state populations of N2+ ions were probed in situ by time-resolved cavity ring-down spectroscopy. The rate coefficient for Penning ionization of N2 by helium metastable atoms was also determined: km = [(2.70 ± 0.17) + (84.3 ± 5.9)e-(877±36)/T] × 10-11 cm3 s-1.

Cavity ring-down spectroscopy of 14N216O near 0.83 µm

The cavity ring-down spectra (CRDS) of nitrous oxide were recorded at a pressure of 10 hPa in the 11,937–12,223 cm-1 range with a threshold sensitivity to absorption coefficient of the order of 6.5 × 10–11 cm-1. Three bands (ν1+5ν3, 6ν1+2ν3, and 3ν1+4ν3) were detected. The line centers and intensities were recovered from the observed spectra. The spectroscopic constants of the upper vibrational states and the vibrational transition dipole moment parameters were fitted to the measured line positions and intensities, respectively. It was found that the 3ν1+4ν3 band is in the interpolyad Coriolis resonance interaction with the 7ν1+7ν21 band. This interaction leads to the appearance in the spectra of the four extra lines of the 7ν1+7ν21 band.

The ring-shaped spatial distribution of the argon excimer, Ar2∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Ar}_2^{*}$$\\end{document}, in the effluent of the kINPen-sci

Spatially resolved measurements of the argon excimer, Ar2∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Ar}_2^{*}$$\\end{document}, were performed in the effluent of a cold atmospheric plasma jet (CAPJ), the so called kINPen-sci, using cavity ringdown spectroscopy. The spatial distribution of the density of Ar2∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Ar}_{2}^{*}$$\\end{document} could be distinguished into two distinct populations: a Gaussian and a toroidally shaped distribution. The production mechanisms of these populations seem to differ. On the one hand, a strong correlation was found between the Gaussian Ar2∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Ar}_{2}^{*}$$\\end{document} population and the spatial distribution of the filaments produced in the effluent of the kINPen-sci. On the other hand, measurements performed while varying the experimental conditions under which the kINPen-sci was operated indicate that the gas flow velocity must play a major role in the formation of the toroidal Ar2∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Ar}_2^{*}$$\\end{document} population. However, the mechanism of formation of the toroid Ar2∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Ar}_{2}^{*}$$\\end{document} population remains unclear.

Fast and accurate extraction of ultrahigh quality factors from cavity ringdown measurement.

Cavity ringdown spectroscopy is an essential test to measure ultrahigh quality factor (UHQ) optical cavities, which is, however, frequently misinterpreted due to lack of a specified analysis guideline. Here we clarify the basic property of cavity ringdown and present a step-by-step method that enables extraction of the overall quality factor, as well as the intrinsic loss and coupling state of UHQ cavities with better fidelity and simplicity than prior schemes. Our work can facilitate an accurate design and characterization of UHQ cavities for ultra-low noise lasers, high finesse reference cavities, and ultra-narrow optical filters.

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.

Effect of Carbon Chain Length on Nascent Yields of Stabilized Criegee Intermediates in Ozonolysis of a Series of Terminal Alkenes.

The yields of stabilized Criegee intermediates (sCIs), CH2OO and RCHOO (C2H5CHOO, C3H7CHOO, C4H9CHOO, and C5H11CHOO), produced from ozonolysis of asymmetrical 1-alkenes (1-butene, 1-pentene, 1-hexene, and 1-heptene) were investigated at low pressures (5-16 Torr) using cavity ring-down spectroscopy and chemical titration with sulfur dioxide (SO2). By extrapolating the low-pressure measurements to zero-pressure limit, nascent sCI yields were obtained. Combined with our previous studies on ethene and propene ozonolysis, the nascent sCI yields demonstrated an intriguing trend of increasing with the addition of CH2 groups and eventually reached a plateau at around 31% for longer chain 1-alkenes. In particular, the fraction of nascent stabilized CH2OO reached the plateau from 1-butene, indicating that CH2OO was produced with nearly the same internal energy distribution from 1-butene to 1-heptene. The comparison between the experiments and RRKM calculations suggests that the dissociation of primary ozonide (POZ) of O3 + ethene and propene can be treated by statistical theory, while that of O3 + 1-butene to 1-heptene is nonstatistical and intramolecular vibrational redistribution of the initial energy on the 1,2,3-trioxolane of POZ throughout the entire molecule was incomplete on the dissociation time scale.

Numerical simulation and experimental verification of dynamic cooling and temperature control of the optical cavity in a CO2 isotope analyzer

Accurate measurement of CO2 generated from different emission sources is the basis for controlling CO2 emissions and mitigating global warming. With advantages of high accuracy and rapid response, isotope analyzers using spectroscopic techniques, particularly those using cavity ring-down spectroscopy, have been widely used for CO2 emissions monitoring. However, these analyzers often face challenges such as spectral interference from impurity gases and unstable temperature control within the optical cavity in isotope analyzers. To address these challenges, this paper proposes a low-temperature optical cavity scheme utilizing a split Stirling-type pulse tube cryocooler. Combining thermal boundary conditions with particle swarm optimization, a dynamic cooling and temperature control model of the optical cavity was established in MATLAB. The model subsequently analyzed the cooling process, temperature control, and stability of the optical cavity. After 120 h, the simulations showed that the central part of the optical cavity had cooled to 126.4 K with a heat leakage of 8.90 W, in agreement with the experimental results that stabilized at 126.8 K. The temperature fluctuations remained within 0.1 K/h while controlling an overall temperature of 170 K with a temperature difference of ± 5 K. Changes in the electrical input power of cryocooler had no influence on the temperature distribution. This advancement not only lowers the operating temperature of the optical cavity to minimize spectral interference but also enhances the precision and efficiency of temperature control.

Open-Path Cavity Ring-Down Spectroscopy for Simultaneous Detection of Hydrogen Chloride and Particles in Cleanroom Environment.

The present study addresses advanced monitoring techniques for particles and airborne molecular contaminants (AMCs) in cleanroom environments, which are crucial for ensuring the integrity of semiconductor manufacturing processes. We focus on quantifying particle levels and a representative AMC, hydrogen chloride (HCl), having known detrimental effects on equipment longevity, product yield, and human health. We have developed a compact laser sensor based on open-path cavity ring-down spectroscopy (CRDS) using a 1742 nm near-infrared diode laser source. The sensor enables the high-sensitivity detection of HCl through absorption by the 2-0 vibrational band with an Allan deviation of 0.15 parts per billion (ppb) over 15 min. For quantifying particle number concentrations, we examine various detection methods based on statistical analyses of Mie scattering-induced ring-down time fluctuations. We find that the ring-down distributions' 3rd and 4th standard moments allow particle detection at densities as low as ~105 m-3 (diameter > 1 μm). These findings provide a basis for the future development of compact cleanroom monitoring instrumentation for wafer-level monitoring for both AMC and particles, including mobile platforms.

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.

Simultaneous onboard analysis of seawater dissolved inorganic carbon (DIC) concentration and stable isotope ratio (δ13C‐DIC)

AbstractDissolved inorganic carbon (DIC) and its stable carbon isotope (δ13C‐DIC) are valuable parameters for studying the aquatic carbon cycle and quantifying ocean anthropogenic carbon accumulation rates. However, the potential of this coupled pair is underexploited as only 15% or less of cruise samples have been analyzed for δ13C‐DIC because the traditional isotope analysis is labor‐intensive and restricted to onshore laboratories. Here, we improved the analytical precision and reported the protocol of an automated, efficient, and high‐precision method for ship‐based DIC and δ13C‐DIC analysis based on cavity ring‐down spectroscopy (CRDS). We also introduced a set of stable in‐house standards to ensure accurate and consistent DIC and δ13C‐DIC measurements, especially on prolonged cruises. With this method, we analyzed over 1600 discrete seawater samples over a 40‐d cruise along the North American eastern ocean margin in summer 2022, representing the first effort to collect a large dataset of δ13C‐DIC onboard of any oceanographic expedition. We evaluated the method's uncertainty, which was 1.2 μmol kg−1 for the DIC concentration and 0.03‰ for the δ13C‐DIC value (1σ). An interlaboratory comparison of onboard DIC concentration analysis revealed an average offset of 2.0 ± 3.8 μmol kg−1 between CRDS and the coulometry‐based results. The cross‐validation of δ13C‐DIC in the deep‐ocean data exhibited a mean difference of only −0.03‰ ± 0.07‰, emphasizing the consistency with historical data. Potential applications in aquatic biogeochemistry are discussed.

Author correction to “Saturated cavity ring-down spectroscopy of 12C16O2 near 1.57 μm”

We regret to announce that there is an error in one of fund numbers in the acknowledgements of the paper titled “Saturated Cavity Ring-Down Spectroscopy of 12C16O2 near 1.57 µm” due to the author’s typing errors. The acknowledgements were published in Chin. J. Chem. Phys. 37, 17 (2024). The corrected acknowledgements are below: This work was jointly supported by the National Natural Science Foundation of China (No.22273096, No.41905018, and No.21903080) and the Ministry of Science and Technology of China (No.2022YFF0606500).

Contrast and Complexity in the Low-Temperature Kinetics of CN(v = 1) with O2 and NO: Simultaneous Kinetics and Ringdown in a Uniform Supersonic Flow.

Bimolecular rate coefficients were determined for the reaction CN(v = 1) + NO and O2 using continuous wave cavity ringdown spectroscopy in a uniform supersonic flow (UF-CRDS). The well-matched time scales for ringdown and reaction under pseudo-first-order conditions allow for the use of the SKaR method (simultaneous kinetics and ringdown) in which the full kinetic trace is obtained on each ringdown. The reactions offer an interesting contrast in that the CN(v = 1) + NO system is nonreactive and proceeds by complex-mediated vibrational relaxation, while the CN(v = 1) + O2 reaction is primarily reactive. The measured rate coefficients at 70 K are (2.49 ± 0.08) × 10-11 and (10.49 ± 0.22) × 10-11 cm3 molecule-1 s-1 for the reaction with O2 and NO, respectively. The rate for reaction with O2 is a factor 2 lower than previously reported for v = 0 in the same temperature range, a surprising result, while that for NO is consistent with extrapolation of previous high-temperature measurements to 70 K. The latter is also discussed in light of theoretical calculations and measurements of the rate constants for the association reaction in the high-pressure limit. The measurements are complicated by the presence of a metastable population of high-J CN formed by photolysis of the precursor BrCN, and a kinetic model is developed to treat the competing relaxation and reaction. It is particularly problematic for reactions at low temperatures where the rotational relaxation and reaction have similar rates, precluding a reliable determination of the rate coefficients at 30 K. Also presented are important modifications to the data acquisition and control for the instrument that have yielded considerably enhanced stability and throughput.

Integrating the controlled evaporation mixer with cavity ring-down spectroscopy for enhanced water vapor isotope calibration

Accurate measurement of water vapor isotopes (δ18O and δ2H) is fundamental for advancing our understanding of the hydrological cycle and improving hydrological model accuracy. This study introduces an innovative calibration methodology using a controlled evaporation mixer (CEM) for determining stable isotopic ratios in atmospheric water vapor via cavity ring-down spectroscopy. The CEM technique reliably produces a stable water vapor stream, crucial for enhancing the precision and accuracy of isotopic measurements. Its rapid adaptation to changes in water vapor concentration and compatibility with different water standards enhance calibration reliability. Demonstrated reproducibility in generating water vapor across a broad concentration range from 900 to over 25,000 ppmv, coupled with a substantial reduction in memory effects, makes this approach highly effective in both laboratory and field settings. This calibration advancement greatly enhances research capabilities for continuous atmospheric water vapor analysis, providing deeper insights into hydrological processes and atmospheric dynamics.

The Uncertainty Evaluation of Determining the Trace H2S in SF6/N2 Insulating Gas Mixture by Cavity Ring-Down Spectroscopy

Abstract H2S is one of the most important characteristic components of sulfur hexafluoride gas insulated electrical equipment. The detection of trace H2S is of great significance for early fault diagnosis of such equipment. Based on the 1578 nm wavelength distributed feedback diode laser (DFB-DL), cavity ring-down spectroscopy (CRDS) can effectively measure the concentration of trace H2S in SF6/N2 gas mixtures. Starting from the principle of methodology, this article establishes a mathematical model for evaluating the measurement uncertainty of CRDS and analyzes its sources of uncertainty: gas constant R1 , temperature T, Avogadro constant NA , gas pressure p in the optical cavity, volume V of the optical cavity, speed c of light, the absorption cross-section parameter σ(ν) of H2S molecules in the laser frequency ν, the ring-down time τ with absorption sample H2S and the ring-down time τ0 without absorption sample. After evaluating the uncertainty components, it was found that the main component was σ(ν) and the secondary components were τ and τ0. The H2S content in the 80% SF6-20% N2 mixed gas measured is (7.64 ± 0.12) × 10−6 mol/mol.