A combustion setup to precisely reference &delta;<sup>13</sup>C and &delta;<sup>2</sup>H isotope ratios of pure CH<sub>4</sub> to produce isotope reference gases of &delta;<sup>13</sup>C-CH<sub>4</sub> in synthetic air

oleh: H. Schaefer, T. J. Popp, T. M. Jenk, C. J. Sapart, C. Buizert, M. Guillevic, P. Sperlich, T. Blunier

Format: Article
Diterbitkan: Copernicus Publications 2012-09-01

Deskripsi

Isotope records of atmospheric CH<sub>4</sub> can be used to infer changes in the biogeochemistry of CH<sub>4</sub>. One factor currently limiting the quantitative interpretation of such changes are uncertainties in the isotope measurements stemming from the lack of a unique isotope reference gas, certified for &delta;<sup>13</sup>C-CH<sub>4</sub> or &delta;<sup>2</sup>H-CH<sub>4</sub>. We present a method to produce isotope reference gases for CH<sub>4</sub> in synthetic air that are precisely anchored to the VPDB and VSMOW scales and have &delta;<sup>13</sup>C-CH<sub>4</sub> values typical for the modern and glacial atmosphere. We quantitatively combusted two pure CH<sub>4</sub> gases from fossil and biogenic sources and determined the &delta;<sup>13</sup>C and &delta;<sup>2</sup>H values of the produced CO<sub>2</sub> and H<sub>2</sub>O relative to the VPDB and VSMOW scales within a very small analytical uncertainty of 0.04&permil; and 0.7&permil;, respectively. We found isotope ratios of −39.56&permil; and −56.37&permil; for &delta;<sup>13</sup>C and −170.1&permil; and −317.4&permil; for &delta;<sup>2</sup>H in the fossil and biogenic CH<sub>4</sub>, respectively. We used both CH<sub>4</sub> types as parental gases from which we mixed two filial CH<sub>4</sub> gases. Their &delta;<sup>13</sup>C was determined to be −42.21&permil; and −47.25&permil; representing glacial and present atmospheric &delta;<sup>13</sup>C-CH<sub>4</sub>. The &delta;<sup>2</sup>H isotope ratios of the filial CH<sub>4</sub> gases were found to be −193.1&permil; and −237.1&permil;, respectively. Next, we mixed aliquots of the filial CH<sub>4</sub> gases with ultrapure N<sub>2</sub>/O<sub>2</sub> (CH<sub>4</sub> &leq; 2 ppb) producing two isotope reference gases of synthetic air with CH<sub>4</sub> mixing ratios near atmospheric values. We show that our method is reproducible and does not introduce isotopic fractionation for &delta;<sup>13</sup>C within the uncertainties of our detection limit (we cannot conclude this for &delta;<sup>2</sup>H because our system is currently not prepared for &delta;<sup>2</sup>H-CH<sub>4</sub> measurements in air samples). The general principle of our method can be applied to produce synthetic isotope reference gases targeting &delta;<sup>2</sup>H-CH<sub>4</sub> or other gas species.