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Development and verification of a novel isotopic N2O measurement technique for discrete static chamber samples using cavity ring-down spectroscopy

Rationale: N2O isotopomers are a useful tool to study soil N cycling processes. The reliability of such measurements requires a consistent set of international N2O isotope reference materials to improve inter-laboratory and inter-instrument comparability and avoid reporting inaccurate results. All these are the more important given the role of N2O in anthropogenic climate change and the pressing need to develop our understanding of soil N cycling and N2O emission to mitigate such emissions. Cavity ring-down spectroscopy (CRDS) could potentially overcome resource requirements and technical challenges, making N2O isotopomer measurements more feasible and less expensive than previous approaches (e.g., gaschromatography [GC] and isotope ratio mass spectrometry [IRMS]). Methods: A combined laser spectrometer and small sample isotope module (CRDS &SSIM) method enabled N2O concentration, 15Nbulk, δ15Nα, δ15Nβand site preference(SP) measurements of sample volumes <20 mL, such as static chamber samples. Sample dilution and isotopic mixing as well as N2O concentration dependence were corrected numerically. A two-point calibration procedure normalised δ values to the international isotope-ratio scales. The CRDS & SSIM repeatability was determined using a reference gas (Ref Gas). CRDS & SSIM concentration measurements were compared with those obtained by GC, and the isotope ratio measurements from two different mass spectrometers were compared. Results: The repeatability (mean ± 1σ; n = 10) of the CRDS & SSIM measurements of the Ref Gas was 710.64 ppb (± 8.64), 2.82‰ (± 0.91), 5.41‰ (± 2.00), 0.23‰ (± 0.22) and 5.18‰ (± 2.18) for N2O concentration, δ15Nbulk, δ15Nα, δ15Nβ and SP, respectively. The CRDS & SSIM concentration measurements were strongly correlated with GC (r= 0.99), and they were more precise than those obtained using GC except when the N2O concentrations exceeded the specified operating range. Normalising CRDS & SSIM δ values to the international isotope-ratio scales using isotopic N2O standards (AK1 and Mix1) produced accurate results when the samples were bracketed within the range of the δ values of the standards. The CRDS & SSIM δ 15Nbulk and SP precision was approximately one order of magnitude less than the typical IRMS precision. Conclusions: CRDS & SSIM is a promising approach that enables N2O concentrations and isotope ratios to be measured by CRDS for samples <20 mL. The CRDS & SSIM repeatability makes this approach suitable for N2O “isotopomer mapping” to distinguish dominant source pathways, such as nitrification and denitrification, and requires less extensive lab resources than the traditionally used GC/IRMS. Current study limitations highlighted potential improvements for future users of this approach to consider, such as automation and physical removal of interfering trace gases before sample analysis.

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