Cavity ring-down Faraday rotation spectroscopy (CRD-FRS) is a technique for trace gas measurements of paramagnetic species that retrieves the molecular concentration from the polarization rotation measured as the difference between simultaneously recorded ring-down times of two orthogonal polarization states. The differential measurement is inherently insensitive to nonabsorber related losses, which makes off-resonance measurements redundant. We exploit this unique property by actively line-locking to a molecular transition for calibration-free trace gas concentration retrieval. In addition, we enhance the effective duty-cycle of the system by implementing a Pound-Drever-Hall laser lock to the cavity resonance, which allows for ring-down rates of up to 9 kHz. The system performance is demonstrated by measurements of trace oxygen with a minimum detection limit at the ppmv/√Hz-level.
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http://dx.doi.org/10.1364/OL.43.005046 | DOI Listing |
Appl Spectrosc
January 2025
Department of Earth Sciences, Geological Institute, , ETH Zurich, Zurich, Switzerland.
Cavity ring-down spectroscopy (CRDS) is rapidly becoming an invaluable tool to measure hydrogen (δ²H) and oxygen (δO) isotopic compositions in water, yet the long-term accuracy and precision of this technique remain relatively underreported. Here, we critically evaluate one-year performance of CRDS δ²H and δO measurements at ETH Zurich, focusing on high throughput (~200 samples per week) while maintaining required precision and accuracy for diverse scientific investigations. We detail a comprehensive methodological and calibration strategy to optimize CRDS reliability for continuous, high-throughput analysis using Picarro's "Express" mode, an area not extensively explored previously.
View Article and Find Full Text PDFACS Earth Space Chem
December 2024
School of Chemistry, The University of Edinburgh, Joseph Black Building, David Brewster Road, King's Buildings, Edinburgh EH9 3FJ, Scotland, U.K.
Identification of the molecular carriers of diffuse interstellar bands (DIBs) requires gas phase electronic spectra of suitable candidate structures. Recording the spectra of these in the laboratory is challenging because they include large, carbon-rich molecules, many of which are likely to be ionic. The electronic spectra of ions are often obtained using action spectroscopy methods, which can induce small perturbations to the absorption characteristics and hinder comparison with astronomical observations.
View Article and Find Full Text PDFACS Omega
December 2024
VTT Technical Research Centre of Finland Ltd, P.O. Box 1000, Espoo, FI-02044, VTT, Finland.
Radiocarbon analysis of nuclear waste produced in nuclear facilities lacks fast, in situ detection methods. Moreover, the amount of radiocarbon desorbing from graphitic waste is not well known. In this study, we demonstrate the use of mid-infrared cavity ring-down spectroscopy combined with an automatic sample processing unit as a method to examine radiocarbon concentration in three types of nuclear waste: spent ion-exchange resin, graphite, and graphite outgassing in sealed storage crates.
View Article and Find Full Text PDFACS Earth Space Chem
November 2024
Department of Chemistry, University of Oxford, Oxford OX1 3QZ, U.K.
The radiative forcing caused by atmospheric aerosol represents one of the largest uncertainties in climate models. In part, these uncertainties derive from poor characterizations of the optical properties of light-absorbing brown carbon (BrC) containing aerosols. Here, single particle cavity ring-down spectroscopy (SP-CRDS) is used to determine the complex refractive index at the optical wavelength of 405 nm for aqueous particles composed of an abundant BrC species, 4-nitrocatechol.
View Article and Find Full Text PDFIn a wide range of laser applications, the optical losses of optical materials used in the laser systems are closely linked to the laser-induced damage and laser beam quality deterioration. It is demonstrated in this paper that when the pulsed cavity ring-down (CRD) technique is employed to measure the optical loss of uncoated substrates inserted in the ring-down cavity with normal incidence, the surface reflection of the uncoated substrate causes a significant overestimation of the optical loss. The degree of overestimation increases rapidly with the increasing surface reflectance.
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