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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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https://doi.org/10.5194/amt-2020-197
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-2020-197
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 04 Jun 2020

Submitted as: research article | 04 Jun 2020

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This preprint is currently under review for the journal AMT.

A novel injection technique: using a field-based quantum cascade laser for the analysis of gas samples derived from static chambers

Anne R. Wecking1, Vanessa M. Cave2, Lìyĭn L. Liáng3, Aaron M. Wall1, Jiafa Luo2, David I. Campbell1, and Louis A. Schipper1 Anne R. Wecking et al.
  • 1School of Science and Environmental Research Institute, The University of Waikato, Private Bag 3105, Hamilton 3240, Aotearoa, New Zealand
  • 2AgResearch Ruakura, Private Bag 3123, Hamilton 3240, Aotearoa, New Zealand
  • 3Manaaki Whenua –Landcare Research, Palmerston North 4442, Aotearoa, New Zealand

Abstract. The development of fast-response analysers for the measurement of nitrous oxide (N2O) has resulted in exciting opportunities for new experimental techniques beyond commonly used static chambers and gas chromatography (GC) analysis. For example, quantum cascade laser absorption spectrometers (QCL) are now being used with eddy covariance (EC) or automated chambers. However, using a field-based QCL EC system to also quantify N2O concentrations in gas samples taken from static chambers has not yet been explored. Gas samples from static chambers are commonly analysed by GC that often requires labour and time consuming procedures off-site. Here, we developed a novel, field-based injection technique that allowed the use of a single QCL for: (1) micrometeorological EC; and (2) immediate manual injection of headspace samples taken from static chambers. To test this approach across a range of low to high N2O fluxes, we applied ammonium nitrate (AN) at 0, 300, 600 and 900 kg N ha−1 (AN0, AN300, AN600, AN900) to plots on a pasture soil. After analysis, calculated N2O fluxes from QCL (FN2O_QCL) were compared with fluxes determined by a standard method, i.e. here laboratory-based GC (FN2O_GC). Subsequent comparison of QCL and GC derived data was tested using orthogonal regression, Bland Altman and bioequivalence statistics. For the AN treated plots, the mean cumulative N2O emissions across the seven day campaign were 0.97 (AN300), 1.26 (AN600) and 2.00 (AN900) kg N2O-N ha−1 for FN2O_QCL and 0.99 (AN300), 1.31 (AN600) and 2.03 (AN900) kg N2O-N ha−1 for FN2O_GC. These FN2O_QCL and FN2O_GC were highly correlated (r = 0.996, n = 81) based on orthogonal regression, in agreement following the Bland Altman approach (i.e. within ± 1.96 standard deviations of the mean) and shown to be for all intents and purposes the same (i.e. bioequivalent). The FN2O_QCL and FN2O_GC derived under near-zero flux conditions (AN0) were weakly correlated (r = 0.306, n = 27) and not found to agree or to be bioequivalent. This was likely caused by the calculation of small but apparent positive and negative FN2O when in fact the actual flux was zero, i.e. below the detection limit of static chambers. Our study demonstrated (1) that the capability of using one QCL to measure N2O at different scales, including manual injections, offered a great potential to advance field measurements of N2O (and other greenhouse gases) in future; and (2) that suitable statistics have to be adopted when formally assessing the agreement and difference (not only the correlation) between two methods of measurement.

Anne R. Wecking et al.

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Anne R. Wecking et al.

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Short summary
Nitrous oxide (N2O) is a relevant greenhouse gas emitted from soils to the atmosphere. Human activities, e.g. intensive farming, have contributed to the increase of atmospheric N2O concentrations with time. Therefore, measurements of N2O are crucial to understand climate change. Our study developed a new technique that enables N2O measurement at small (point) and large (paddock) scales by using only one analyser. Using this new method will accelerate and advance N2O measurements in future.
Nitrous oxide (N2O) is a relevant greenhouse gas emitted from soils to the atmosphere. Human...
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