Assessing the blank carbon contribution, isotope mass balance, and kinetic isotope fractionation of the Ramped Pyrolysis/Oxidation instrument at NOSAMS
Hemingway, Jordon D.
Gagnon, Alan R.
Grant, Katherine E.
Rosengard, Sarah Z.
McNichol, Ann P.
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We estimate the blank carbon mass over the course of a typical Ramped PyrOx (RPO) analysis (150 to 1000 °C; 5 °C×min-1) to be (3.7 ± 0.6) μg C with an Fm value of 0.555 ± 0.042 and a δ13C value of (-29.0 ± 0.1) ‰ VPDB. Additionally, we provide equations for RPO Fm and δ13C blank corrections, including associated error propagation. By comparing RPO mass-weighted mean and independently measured bulk δ13C values for a compilation of environmental samples and standard reference materials (SRMs), we observe a small yet consistent 13C depletion within the RPO instrument (mean – bulk: μ = -0.8 ‰; ±1σ = 0.9 ‰; n = 66). In contrast, because they are fractionation-corrected by definition, mass-weighted mean Fm values accurately match bulk measurements (mean – bulk: μ = 0.005; ±1σ = 0.014; n = 36). Lastly, we show there exists no significant intra-sample δ13C variability across carbonate SRM peaks, indicating minimal mass-dependent kinetic isotope fractionation during RPO analysis. These data are best explained by a difference in activation energy between 13C- and 12C-containing compounds (13–12ΔE) of 0.3 to 1.8 J×mol-1, indicating that blank and mass-balance corrected RPO δ13C values accurately retain carbon source isotope signals to within 1 to 2‰.
Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here by permission of Arizona Board of Regents on behalf of the University of Arizona for personal use, not for redistribution. The definitive version was published in Radiocarbon 59 (2017): 179-193, doi:10.1017/RDC.2017.3.
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