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Sources of error in open-path FTIR measurements of N2O and CO2 emitted from agricultural fields

机译:从农业领域发出的N2O和CO2的开放式FTIR测量误差源

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摘要

Open-path Fourier transform infrared spectroscopy (OP-FTIR) is susceptible to environmental variables which can become sources of errors for gas quantification. In this study, we assessed the effects of water vapour, temperature, path length, and wind speed on quantitative uncertainties of nitrous oxide (N2O) and carbon dioxide (CO2) derived from OP-FTIR spectra. The presence of water vapour in spectra underestimated N2O mole fractions by 3% and 12%, respectively, from both lab and field experiments using a classical least squares (CLS) model when the reference and sample spectra were collected at the same temperature (i.e. 30°C). Differences in temperature between sample and reference spectra also underestimated N2O mole fractions due to temperature broadening and the increased interferences of water vapour in spectra of wet samples. Changes in path length resulted in a non-linear response of spectra and bias (e.g. N2O and CO2 mole fractions were underestimated by 30% and 7.5%, respectively, at the optical path of 100m using CLS models). For N2O quantification, partial least squares (PLS) models were less sensitive to water vapour, temperature, and path length and provided more accurate estimations than CLS. Uncertainties in the path-averaged mole fractions increased in low-wind conditions (2ms?1). This study identified the most common interferences that affect OP-FTIR measurements of N2O and CO2, which can serve as a quality assurance/control guide for current or future OP-FTIR users.
机译:开放式傅立叶变换红外光谱(OP-FTIR)易受环境变量的影响,这可能成为气体量化误差的源。在这项研究中,我们评估了水蒸气,温度,路径长度和风速对来自OP-FTIR光谱衍生的二氮氧化物(N2O)和二氧化碳(CO2)的定量不确定性的影响。当在相同温度下收集参考和样品光谱时,使用经典最小二乘(CLS)模型,分别从两种实验室实验中升高3%和12%的水蒸气分别由3%和12%的实验室实验(即30 °C)。样品和参考光谱之间的温度差异也是由于温度展大和湿法样品光谱中的水蒸气的增加而低估了N2O摩尔级分。路径长度的变化导致光谱和偏差的非线性响应(例如,N 2 O和CO2摩尔分量分别在100m的光路上分别在100m的光路上低估了30%和7.5%)。对于N2O定量,部分最小二乘(PLS)模型对水蒸气,温度和路径长度敏感,并且提供比CLS更精确的估计。路径平均摩尔分数中的不确定性在低风条件下增加(2ms?1)。本研究确定了影响N2O和CO2的OP-FTIR测量的最常见的干扰,其可以作为当前或未来的OP-FTIR用户的质量保证/控制指南。

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