First on-line isotopic characterization of N<sub>2</sub>O above intensively managed grassland

The analysis of the four main isotopic N<sub>2</sub>O species (<sup>14</sup>N<sup>14</sup>N<sup>16</sup>O, <sup>14</sup>N<sup>15</sup>N<sup>16</sup>O, <sup>15</sup>N<sup>14</sup>N<sup>16...

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Bibliographic Details
Main Authors: B. Wolf, L. Merbold, C. Decock, B. Tuzson, E. Harris, J. Six, L. Emmenegger, J. Mohn
Format: Article
Language:English
Published: Copernicus Publications 2015-04-01
Series:Biogeosciences
Online Access:http://www.biogeosciences.net/12/2517/2015/bg-12-2517-2015.pdf
Description
Summary:The analysis of the four main isotopic N<sub>2</sub>O species (<sup>14</sup>N<sup>14</sup>N<sup>16</sup>O, <sup>14</sup>N<sup>15</sup>N<sup>16</sup>O, <sup>15</sup>N<sup>14</sup>N<sup>16</sup>O, <sup>14</sup>N<sup>14</sup>N<sup>18</sup>O) and especially the intramolecular distribution of <sup>15</sup>N ("site preference", SP) has been suggested as a tool to distinguish source processes and to help constrain the global N<sub>2</sub>O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass-spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows the selective high-precision analysis of N<sub>2</sub>O isotopic species at trace levels and is suitable for in situ measurements. <br><br> Here, we present results from the first field campaign, conducted on an intensively managed grassland site in central Switzerland. N<sub>2</sub>O mole fractions and isotopic composition were determined in the atmospheric surface layer (at 2.2 m height) at a high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N<sub>2</sub>O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11&permil; for δ<sup>15</sup>N<sup>&alpha;</sup>, δ<sup>15</sup>N<sup>&beta;</sup> and δ<sup>18</sup>O, respectively. Simultaneous eddy-covariance N<sub>2</sub>O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N<sub>2</sub>O. <br><br> Our measurements indicate that, in general, nitrifier-denitrification and denitrification were the prevalent sources of N<sub>2</sub>O during the campaign and that variations in isotopic composition were due to alterations in the extent to which N<sub>2</sub>O was reduced to N<sub>2</sub> rather than to other pathways, such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intramolecular <sup>15</sup>N site preference (SP), δ<sup>15</sup>N<sup>bulk</sup> and δ<sup>18</sup>O, suggesting that nitrifier-denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. The flux-averaged isotopic composition of N<sub>2</sub>O from intensively managed grassland was 6.9 ± 4.3, −17.4 ± 6.2 and 27.4 ± 3.6&permil; for SP, δ<sup>15</sup>N<sup>bulk</sup> and δ<sup>18</sup>O, respectively. The approach presented here is capable of providing long-term data sets also for other N<sub>2</sub>O-emitting ecosystems, which can be used to further constrain global N<sub>2</sub>O inventories.
ISSN:1726-4170
1726-4189