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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., gas chromatography [GC] and isotope ratio mass spectrometry [IRMS]). Methods: A combined laser spectrometer and small sample isotope module (CRDS & SSIM) method enabled N2O concentration, δ15Nbulk, δ15Nα, δ15Nβ and 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 d 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 ± 1s; 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 d 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 d values of the standards. The CRDS & SSIM δ15Nbulk 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. [ABSTRACT FROM AUTHOR]

Nitrous oxide (N 2 O) is a potent greenhouse gas (GHG) emitted from agricultural soils and is influenced by nitrogen (N) fertiliser management and weather and soil conditions. Source partitioning N 2 O emissions related to management practices and soil conditions could suggest effective mitigation strategies. Multispecies swards can maintain herbage yields at reduced N fertiliser rates compared to grass monocultures and may reduce N losses to the wider environment. A restricted-simplex centroid experiment was used to measure daily N 2 O fluxes and associated isotopomers from eight experimental plots (7.8 m 2 ) post a urea-N fertiliser application (40 kg N ha -1 ). Experimental pastures consisted of differing proportions of grass, legume and forage herb represented by perennial ryegrass (Lolium perenne), white clover (Trifolium repens) and ribwort plantain (Plantago lanceolata), respectively. N 2 O isotopomers were measured using a cavity ring down spectroscopy (CRDS) instrument adapted with a small sample isotope module (SSIM) for the analysis of gas samples ≤20 mL. Site preference (SP = δ 15 N α - δ 15 N β ) and δ 15 N bulk ((δ 15 N α + δ 15 N β ) / 2) values were used to attribute N 2 O production to nitrification, denitrification or a mixture of both nitrification and denitrification over a range of soil WFPS (%). Daily N 2 O fluxes ranged from 8.26 to 86.86 g N 2 O-N ha -1 d -1 . Overall, 34.2% of daily N 2 O fluxes were attributed to nitrification, 29.0% to denitrification and 36.8% to a mixture of both. A significant diversity effect of white clover and ribwort plantain on predicted SP and δ 15 N bulk indicated that the inclusion of ribwort plantain may decrease N 2 O emission through biological nitrification inhibition under drier soil conditions (31%-75% WFPS). Likewise, a sharp decline in predicted SP indicates that increased white clover content could increase N 2 O emissions associated with denitrification under elevated soil moisture conditions (43%-77% WFPS). Biological nitrification inhibition from ribwort plantain inclusion in grassland swards and management of N fertiliser source and application timing to match soil moisture conditions could be useful N 2 O mitigation strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)