Performance of cryogenic adsorbents for use in methane bulk and clumped isotope analysis

Performance of cryogenic adsorbents for use in methane bulk and clumped isotope analysis | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL Rapid Communications in Mass Spectrometry This is a preprint and has not been peer reviewed. Data may be preliminary. 27 January 2025 V1 Latest version Share on Performance of cryogenic adsorbents for use in methane bulk and clumped isotope analysis Authors : Nico Kueter 0000-0003-3620-5414 [email protected] , Naizhong Zhang , Jan Meissner , Léna Monnereau , Paul M. Magyar , Lukas Emmenegger , Stefano M. Bernasconi , and Joachim Mohn 0000-0002-9799-1001 Authors Info & Affiliations https://doi.org/10.22541/au.173795627.73889528/v1 Published Rapid Communications in Mass Spectrometry Version of record Peer review timeline 429 views 198 downloads Contents Abstract Supplementary Material Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract RATIONALE Cryogenic trapping of methane is essential for bulk and clumped isotope analyses, requiring adsorbent materials that enable efficient recovery and preserve isotopic signatures. This study evaluates the performance – capacity, isotopic fractionation, and ease of use – of silica gels, zeolite molecular sieves, and activated carbon under various trapping and desorption conditions. A focus is set on the preservation of methane clumped isotope signatures. METHODS A well-characterized methane reference gas (40 mL) was cryofocused at 77 K in containers filled with silica gels, zeolite molecular sieves (5A and 13X), or activated carbon alongside non-loaded containers. After loading, the containers were warmed in a water bath (21 to 95 °C) for various dwell times. The bulk (𝛿D-CH 4 and 𝛿 13 C-CH 4 ) and clumped (∆ 13 CH 3 D and ∆ 12 CH 2 D 2 ) isotopic composition of the desorbed methane were measured against the untreated reference gas using novel quantum cascade laser absorption spectroscopy (QCLAS). RESULTS The best results were achieved with coarse-grained (1-3 mm) silica gels heated to 50 °C for at least five minutes or at 21 to 22 °C for a minimum of 120 minutes. Elevated desorption temperatures (80 °C to 95 °C) compromised clumped isotope signatures. Although effective for gas trapping, zeolite molecular sieves, and activated carbon introduced significant bulk and clumped isotopic shifts due to catalytic effects and chromatographic isotopologue separation. Methane cryofocused without adsorbents retained its bulk and clumped isotopic composition without significant fractionation. CONCLUSIONS Among the tested adsorbents, silica gels demonstrated superior performance, preserving δ 13 C-CH 4 , δD-CH 4 , ∆ 13 CH 3 D, and ∆ 12 CH 2 D 2 values close to or within performance targets while offering high adsorption capacity, reproducibility, and ease of regeneration. Adsorbent-free cryotrapping is a viable alternative for sufficiently large methane volumes, where vapor pressure isotope effects (VPIEs) become negligible. However, cryogenic adsorbents remain indispensable for ensuring isotopic accuracy for small sample volumes and high-precision applications. Supplementary Material File (manuscript_and_figures_final.docx) Download 1.50 MB Information & Authors Information Version history V1 Version 1 27 January 2025 Peer review timeline Published Rapid Communications in Mass Spectrometry Version of Record 11 Apr 2025 Published Copyright This work is licensed under a Non Exclusive No Reuse License. Collection Rapid Communications in Mass Spectrometry Keywords adsorbent clumped isotopes laser spectroscopy methane sample purification vapor pressure isotope effect Authors Affiliations Nico Kueter 0000-0003-3620-5414 [email protected] Eidgenossische Technische Hochschule Zurich Departement Erdwissenschaften View all articles by this author Naizhong Zhang Empa View all articles by this author Jan Meissner Eidgenossische Technische Hochschule Zurich Departement Erdwissenschaften View all articles by this author Léna Monnereau Eidgenossische Technische Hochschule Zurich Departement Erdwissenschaften View all articles by this author Paul M. Magyar Empa View all articles by this author Lukas Emmenegger Empa View all articles by this author Stefano M. Bernasconi Eidgenossische Technische Hochschule Zurich Departement Erdwissenschaften View all articles by this author Joachim Mohn 0000-0002-9799-1001 Empa View all articles by this author Metrics & Citations Metrics Article Usage 429 views 198 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Nico Kueter, Naizhong Zhang, Jan Meissner, et al. Performance of cryogenic adsorbents for use in methane bulk and clumped isotope analysis. Authorea . 27 January 2025. DOI: https://doi.org/10.22541/au.173795627.73889528/v1 If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download. For more information or tips please see 'Downloading to a citation manager' in the Help menu . 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