Quantum cascade laser absorption spectrometer with a low temperature multipass cell for precision clumped CO<sub>2</sub> measurement

Nataraj, Akshay; Gianella, Michele; Prokhorov, Ivan; Tuzson, Béla; Bertrand, Mathieu; Mohn, Joachim; Faist, Jérôme; Emmenegger, Lukas

doi:10.1364/oe.447172

Cited by 7 publications

(22 citation statements)

References 34 publications

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“…Finally, due to its versatility, our approach can be extended to rare isotopic species of simple molecules such as clumped CO 2 (already demonstrated by Nataraj et al), CH 4 , or N 2 O and other volatile organic compounds, thereby opening new perspectives in environmental sciences and fundamental research.…”

Section: Resultsmentioning

confidence: 86%

“…QCLAS Setup. The spectrometer is an adaptation of a previous setup described in detail by Nataraj et al 17 A schematic of the optical setup is shown in Figure 2. Briefly, it uses a distributed feedback quantum cascade laser (DFB-QCL, Alpes Lasers) as light source emitting in the spectral region around 1385 cm −1 .…”

Section: T H Imentioning

confidence: 99%

“…Optical absorption techniques are known to provide precise and accurate information about the intramolecular properties of the molecule, and they are increasingly used in isotope research. − In the case of more complex molecules, however, the optical absorption techniques face two main challenges: larger molecules tend to have congested and overlapping spectral features, and line-by-line assignments are often not available in spectral databases. While high-resolution IR spectra of natural propane exist, , spectral information on propane’s site-specific isotopomers is lacking.…”

Section: Introductionmentioning

confidence: 99%

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Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy

et al. 2023

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Intramolecular or position-specific carbon isotope a n a l y s i s o f p r o p a n e ( 1 3 C H 3 − 1 2 C H 2 − 1 2 C H 3 a n d 12 CH 3 − 13 CH 2 − 12 CH 3 ) provides unique insights into its formation mechanism and temperature history. The unambiguous detection of such carbon isotopic distributions with currently established methods is challenging due to the complexity of the technique and the tedious sample preparation. We present a direct and nondestructive analytical technique to quantify the two singly substituted, terminal ( 13 C t ) and central ( 13 C c ), propane isotopomers, based on quantum cascade laser absorption spectroscopy. The required spectral information on the propane isotopomers was first obtained using a high-resolution Fourier-transform infrared (FTIR) spectrometer and then used to select suitable mid-infrared regions with minimal spectral interference to obtain the optimum sensitivity and selectivity. We then measured high-resolution spectra around 1384 cm −1 of both singly substituted isotopomers by mid-IR quantum cascade laser absorption spectroscopy using a Stirling-cooled segmented circular multipass cell (SC-MPC). The spectra of the pure propane isotopomers were acquired at both 300 and 155 K and served as spectral templates to quantify samples with different levels of 13 C at the central (c) and terminal (t) positions. A prerequisite for the precision using this reference template fitting method is a good match of amount fraction and pressure between the sample and templates. For samples at natural abundance, we achieved a precision of 0.33 ‰ for δ 13 C t and 0.73 ‰ for δ 13 C c values within 100 s integration time. This is the first demonstration of sitespecific high-precision measurements of isotopically substituted non-methane hydrocarbons using laser absorption spectroscopy. The versatility of this analytical approach may open up new opportunities for the study of isotopic distribution of other organic compounds.

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Section: Resultsmentioning

confidence: 86%

Section: T H Imentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy

et al. 2023

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“…16,17 Recent work has demonstrated that laser spectroscopy circumvents these challenges and is a promising method for accurate clumped isotope measurements of CO 2 and other gases. [18][19][20][21][22][23][24][25][26] Compared to IRMS systems, laser spectrometers are nondestructive, highly sensitive, and efficient, which makes them ideal for high-throughput, precise clumped isotope measurements. As each isotopologue of CO 2 has a unique absorption spectrum, laser spectrometers can directly measure single isotopologues (e.g., 16 O 13 C 18 O) and remove the need for and uncertainty with correcting for mass contributions from "unwanted" isotopologues.…”

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confidence: 99%

Development of a quantum cascade laser absorption spectrometer for simultaneous measurement of ¹³C–¹⁸O and ¹⁸O–¹⁸O clumping in CO₂

Wieman,

Kapit,

Michel

et al. 2024

Rapid Comm Mass Spectrometry

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RationaleDual clumped isotope paleothermometry determines carbonate formation temperatures by measuring the frequency of 13C–18O (∆638) and 18O–18O (∆828) pairs in carbonates. It resolves isotopic kinetic biases and thus enables more accurate paleotemperature reconstructions. However, high‐precision measurements of 18O–18O clumping using current techniques requires large sample sizes and long acquisition times.MethodsWe developed a mid‐infrared isotope ratio laser spectrometer (IRLS) for simultaneous measurement of the isotopologue ratios ∆638 and ∆828 in gas‐phase carbon dioxide (CO2) at room temperature. Our IRLS uses a single laser scanning from 2290.7 to 2291.1 cm−1 and a 31 m pathlength optical cell, and it simultaneously measures the five isotopologues required for calculating ∆638 and ∆828: 16O12C16O, 16O13C16O, 16O12C18O, 16O13C18O, and 18O12C18O. In addition, our IRLS can measure 16O12C17O, enabling ∆17O analysis.ResultsAt ~20°C and a CO2 pressure of ~2 Torr, our IRLS system achieved precisions of 0.128‰ and 0.140‰ within 20 s for abundances of the clumped isotopologues 16O13C18O and 18O12C18O, respectively, and precisions of 0.267‰, 0.245‰, and 0.128‰ for 16O12C16O, 16O13C16O, and 16O12C18O. This yielded precisions of 0.348‰ (∆638) and 0.302‰ (∆828) within 25 s. Simulated sample–reference switching highlights the potential of our system and the need for further development.ConclusionsWe demonstrated simultaneous measurements of ∆638 and ∆828 in CO2 to precisions of <0.35‰ within 25 s using a room‐temperature, single‐laser IRLS. Future developments on better resolving 16O12C16O and 16O13C16O peaks and system temperature control could further improve the measurement precision.

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“…The main analytical challenge of methane isotopologues analysis is the requirement for high analytical accuracy, generally in the sub-per-mille range, at low relative abundances. Measurements of 13 CH 4 / 12 CH 4 ratios are routinely performed with commercial tunable mid-IR laser direct absorption and cavity-ring down spectrometers at atmospheric abundances, , while 12 CH 3 D/ 12 CH 4 analysis in ambient air requires precedent preconcentration. , In the case of doubly substituted isotopologue analysis, there are currently two competing analytical techniques, both applied on pure or high-concentration samples: high-resolution isotope ratio mass spectrometry (HR-IRMS) , and quantum cascade laser absorption spectroscopy (QCLAS). − To date, both methods are capable of achieving precision of better than 0.1‰ and 1‰ for Δ 13 CH 3 D and Δ 12 CH 2 D 2 , respectively.…”

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confidence: 99%

CleanEx: A Versatile Automated Methane Preconcentration Device for High-Precision Analysis of ¹³CH₄, ¹²CH₃D, and ¹³CH₃D

Prokhorov

Mohn

2022

Anal. Chem.

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The relative abundance of methane isotopologues offers key insights into the global methane (CH 4 ) cycle. Advances in laser spectroscopy enable routine high-precision measurements even for rare deuterated methane isotopologues, 12 CH 3 D and 13 CH 3 D, provided there are sufficiently high methane amount fractions and reproducible measurement conditions, which can be achieved by CH 4 adsorption−desorption techniques. We present a new cryogen-free automated preconcentration device�CleanEx�designed for quantitative extraction of CH 4 from large volumes of sample gas and for cleaning by stepwise temperature-controlled desorption to separate interferant gases. We show that CleanEx has the capability to preconcentrate methane by almost 2000-fold from ∼18 L of air. The performance is demonstrated in a range of methane amount fractions between 2 ppm (μmol mol −1 ), which corresponds to the present-day ambient air, up to 1000 ppm, representative for close to source or process conditions. Advantages over existing devices are a significantly larger primary adsorption trap and a secondary cryo-focusing step, which ensures separation of methane from major atmospheric compounds, i.e., O 2 , Ar, and CO 2 . We have demonstrated quantitative extraction of methane, with no significant isotopic fractionation and high repeatability of 0.2‰, 0.6‰, and 0.8‰ (n = 42) for the studied isotopologue ratios, 13 CH 4 / 12 CH 4 , 12 CH 3 D/ 12 CH 4 , and 13 CH 3 D/ 12 CH 4 , during cryogenic adsorption−desorption on HayeSep D material. The developed device in combination with a suitable laser spectrometer offers a robust and autonomous method for precise continuous monitoring of δ 13 C-CH 4 and δD-CH 4 in ambient air and optionally Δ 13 CH 3 D in process-derived methane.M ethane (CH 4 ) is both an important fossil and regenerative energy source and a potent greenhouse gas and air pollutant. This poses multiple research questions with respect to origin and conditions of formation in energy exploration 1,2 but also in atmospheric budgeting. 3 Isotope ratios 13 C/ 12 C and D/H measured through singly substituted 13

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Quantum cascade laser absorption spectrometer with a low temperature multipass cell for precision clumped CO₂ measurement

Cited by 7 publications

References 34 publications

Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy

Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy

Development of a quantum cascade laser absorption spectrometer for simultaneous measurement of ¹³C–¹⁸O and ¹⁸O–¹⁸O clumping in CO₂

CleanEx: A Versatile Automated Methane Preconcentration Device for High-Precision Analysis of ¹³CH₄, ¹²CH₃D, and ¹³CH₃D

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Quantum cascade laser absorption spectrometer with a low temperature multipass cell for precision clumped CO2 measurement

Cited by 7 publications

References 34 publications

Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy

Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy

Development of a quantum cascade laser absorption spectrometer for simultaneous measurement of 13C–18O and 18O–18O clumping in CO2

CleanEx: A Versatile Automated Methane Preconcentration Device for High-Precision Analysis of 13CH4, 12CH3D, and 13CH3D

Contact Info

Product

Resources

About

Quantum cascade laser absorption spectrometer with a low temperature multipass cell for precision clumped CO₂ measurement

Development of a quantum cascade laser absorption spectrometer for simultaneous measurement of ¹³C–¹⁸O and ¹⁸O–¹⁸O clumping in CO₂

CleanEx: A Versatile Automated Methane Preconcentration Device for High-Precision Analysis of ¹³CH₄, ¹²CH₃D, and ¹³CH₃D