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Rapid Commun Mass Spectrom


Title:Advances in carbon isotope analysis of trapped methane and volatile hydrocarbons in crystalline rock cores
Author(s):Sanz-Robinson J; Brisco T; Warr O; Jabeen I; Lacrampe-Couloume G; Hanley JJ; Sherwood Lollar B;
Address:"Department of Earth Sciences, University of Toronto, Toronto, Ontario, Canada. Department of Geology, Saint Mary's University, Halifax, Nova Scotia, Canada"
Journal Title:Rapid Commun Mass Spectrom
Year:2021
Volume:35
Issue:20
Page Number:e9170 -
DOI: 10.1002/rcm.9170
ISSN/ISBN:1097-0231 (Electronic) 0951-4198 (Linking)
Abstract:"RATIONALE: The isotopic composition of hydrocarbons trapped in rocks on the microscale (fluid inclusions, mineral grain boundaries, microfractures) can provide powerful information on geological and biological processes but are an analytical challenge due to low concentrations. We present a new approach for the extraction and carbon isotopic analysis of methane (CH(4) ) and hydrocarbons in trapped volatiles in crystalline rocks. METHODS: An off-line crusher with cryogenic trapping and a custom-made silica glass U-trap were attached to an external injector port on a continuous flow gas chromatograph/combustion/isotope ratio mass spectrometer to demonstrate the accuracy, reproducibility, and sensitivity of delta(13) C measurements for CH(4) . RESULTS: The method can isotopically characterize CH(4) in crushed rock samples with concentrations as low as 3.5 x 10(-9) mol/g of rock, and both sample and isotopic standards are analyzed with an accuracy and reproducibility of +/-0.5 per thousand. High H(2) O/CH(4) ratios of 98 to 500 have no effect on measured delta(13) C(CH4) values. The method is successfully applied to natural samples from the north range of Sudbury Basin, Ontario, Canada. The delta(13) C isotopic signatures of CH(4) trapped microscopically in rock from the north range overlap significantly with that of CH(4) contained in larger scale flowing fracture fluids from the same part of the Sudbury Basin, indicating a potential genetic link. CONCLUSIONS: A novel method for delta(13) C(CH4) analysis was developed for the extraction of nanomole quantities of CH(4) trapped microscopically in rocks. The technique has an accuracy and reproducibility comparable to that of on-line crushing techniques but importantly provides the capability of crushing larger rock quantities (up to 100 g). The benefit is improved detection levels for trace hydrocarbon species. Such a capability will be important for future extension of such crushing techniques for measurement of (2) H/(1) H for CH(4) , clumped isotopologues of CH(4) and other trapped volatiles species, such as C(2) H(6) , C(3) H(8) , C(4) H(10) , CO(2) and N(2)"
Keywords:
Notes:"PubMed-not-MEDLINESanz-Robinson, Jethro Brisco, Trevor Warr, Oliver Jabeen, Iffat Lacrampe-Couloume, Georges Hanley, Jacob J Sherwood Lollar, Barbara eng 494812/Natural Sciences and Engineering Research Council of Canada (NSERC) Accelerator Grant/ 453949/Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery Grant/ 502356/Nuclear Waste Management Organization/ Canada Research Chairs/ England 2021/07/25 Rapid Commun Mass Spectrom. 2021 Oct 30; 35(20):e9170. doi: 10.1002/rcm.9170"

 
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