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

摘要

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 (QCL) absorption spectrometers 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 often analysed by GC, a method that 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 concentrations and fluxes, we applied ammonium nitrate (AN) at 0, 300, 600 and 900kgNha?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. laboratory-based GC (FN2O_GC). Subsequently, the comparability of QCL and GC data was tested using orthogonal regression, Bland–Altman and bioequivalence statistics. For AN-treated plots, mean cumulative N2O emissions across the 7d campaign were 0.97 (AN300), 1.26 (AN600) and 2.00kgN2O-Nha?1 (AN900) for FN2O_QCL and 0.99 (AN300), 1.31 (AN600) and 2.03kgN2O-Nha?1 (AN900) 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 deviation of the mean difference) and shown to be for all intents and purposes the same (i.e. equivalent). 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 equivalent. This was likely caused by the calculation of small, but apparent positive and negative, FN2O when in fact the actual flux was 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, offers great potential to advance field measurements of N2O (and other greenhouse gases) in the 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.