An optimized sampling system for highly reproducible isotope ratio measurements (δ 13C and δ 18O) of pure CO2 gas by infrared spectroscopy

Metrologia ◽  
2020 ◽  
Vol 57 (5) ◽  
pp. 055004
Author(s):  
Joële Viallon ◽  
Edgar Flores ◽  
Philippe Moussay ◽  
Ian Chubchenko ◽  
Francesca Rolle ◽  
...  
2020 ◽  
Author(s):  
Edgar Flores ◽  
Philippe Moussay ◽  
Eric Mussell Webber ◽  
Ian Chubchenko ◽  
Francesca Rolle ◽  
...  

<p>This paper will describe the characteristics and performance of a system to prepare up to ten 50 mL samples of pure CO<sub>2</sub> with on-demand <sup>13</sup>C/<sup>12</sup>C ratios, together with an optimized calibration system for measurements by Isotope Ratio Infrared Spectroscopy (IRIS) that has allowed measurement of δ<sup>13</sup>C and δ<sup>18</sup>O values with 0.02 ‰ reproducibility (1 σ).</p><p>The needs for improved quality infrastructure and appropriate reference gases for CO<sub>2</sub> isotope ratio measurements has been a driver for recent research and development activities within the National Metrology Institutes, and the decision of the Gas Analysis Working Group of the CCQM to plan an international comparison (CCQM-P204) of capabilities of measurements of these quantities. The comparison will be coordinated by the BIPM, which has the mission of preparing the comparison samples, and the IAEA, who will assign their isotopic composition on reference scales. The BIPM has developed a preparation facility based on blending of different pure CO<sub>2</sub> sources of very different isotopic compositions, followed by cryogenic trapping and transfer to ten 50 mL cylinders. The target isotopic ratio <sup>13</sup>C/<sup>12</sup>C can be adjusted by accurate flow measurements.</p><p>A Carousel sampling system with bracketing reference gas calibration and dilution system has been designed at the BIPM to allow rapid and accurate analysis of prepared gas mixtures by IRIS. A key feature of the calibration system is to maintain identical treatment of sample and reference gases allowing two-point calibration of up to 14 samples, and appropriate flushing protocols to remove any biases from memory effects of previously sampled gases. Measurements are performed by the IRIS analyzer at a mole fraction of nominally 700 μmol/mol CO<sub>2</sub> in air, by dilution of pure CO<sub>2</sub> gas controlled by individual low-flow mass flow controllers (0.07 ml/min), and with a feedback loop to control mole fractions to ensure that differences between references and sample gas mole faction stay below 2 μmol/mol. This level of control is necessary to prevent biases in measured isotope ratios, the magnitude of which has also been studied with a sensitivity study that is also reported.</p><p>The Carousel and IRIS measurements have been validated using pure CO<sub>2</sub> samples prepared with the gas blending facility, covering a range in delta values of -1 ‰ to -45 ‰ vs VPDB, and in all cases measurement reproducibility over several days of testing of 0.02‰ or better (1 σ) were achieved for both δ<sup>13</sup>C and δ<sup>18</sup>O, with negligible memory effects.</p><p>Samples produced and characterized with the facility will be distributed to institutes participting in the CCQM-P204 comparison exrecise, with measurements foreseen in the first quarter of 2020.</p>


2021 ◽  
Vol 35 (8) ◽  
Author(s):  
Stefan Graaf ◽  
Hubert B. Vonhof ◽  
Elan J. Levy ◽  
Monika Markowska ◽  
Gerald H. Haug

2015 ◽  
Vol 30 (7) ◽  
pp. 1582-1589 ◽  
Author(s):  
Alkiviadis Gourgiotis ◽  
Gérard Manhès ◽  
Pascale Louvat ◽  
Julien Moureau ◽  
Jérôme Gaillardet

This work is a first attempt to evaluate the potential use of 1012 Ω amplifiers for transient signal isotope analysis. We showed how the transient signal duration influences the accuracy of the isotope ratio measurements.


2011 ◽  
Vol 26 (7) ◽  
pp. 1372 ◽  
Author(s):  
E. Paredes ◽  
D. Goitom Asfaha ◽  
E. Ponzevera ◽  
C. Brach-Papa ◽  
M. Van Bocxstaele ◽  
...  

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