Abstract
Abstract. We examined potential interferences from water vapor and atmospheric background gases (N2, O2, and Ar), and biases by isotopologues of target species, on accurate measurement of atmospheric CO2 and CH4 by means of wavelength-scanned cavity ring-down spectroscopy (WS-CRDS). Changes of the background gas mole fractions in the sample air substantially impacted the CO2 and CH4 measurements: variation of CO2 and CH4 due to relative increase of each background gas increased as Ar < O2 < N2, suggesting similar relation for the pressure-broadening effects (PBEs) among the background gas. The pressure-broadening coefficients due to variations in O2 and Ar for CO2 and CH4 are empirically determined from these experimental results. Calculated PBEs using the pressure-broadening coefficients are linearly correlated with the differences between the mole fractions of O2 and Ar and their ambient abundances. Although the PBEs calculation showed that impact of natural variation of O2 is negligible on the CO2 and CH4 measurements, significant bias was inferred for the measurement of synthetic standard gases. For gas standards balanced with purified air, the PBEs were estimated to be marginal (up to 0.05 ppm for CO2 and 0.01 ppb for CH4) although the PBEs were substantial (up to 0.87 ppm for CO2 and 1.4 ppb for CH4) for standards balanced with synthetic air. For isotopic biases on CO2 measurements, we compared experimental results and theoretical calculations, which showed excellent agreement within their uncertainty. We derived instrument-specific water correction functions empirically for three WS-CRDS instruments (Picarro EnviroSense 3000i, G-1301, and G-2301), and evaluated the transferability of the water correction function from G-1301 among these instruments. Although the transferability was not proven, no significant difference was found in the water vapor correction function for the investigated WS-CRDS instruments as well as the instruments reported in the past studies within the typical analytical precision at sufficiently low water concentrations (<0.7% for CO2 and <0.6% for CH4). For accurate measurements of CO2 and CH4 in ambient air, we concluded that WS-CRDS measurements should be performed under complete dehumidification of air samples, or moderate dehumidification followed by application of a water vapor correction function, along with calibration by natural air-based standard gases or purified air-balanced synthetic standard gases with the isotopic correction.
Highlights
Since atmospheric carbon dioxide (CO2) is one of the most important trace gases in controlling the Earth’s climate, much attention has been paid to the understanding of the global distribution of CO2 during the last 50 yr of the twentieth century
Chen et al (2010) examined the analytical performance of a Picarro WS-cavity ring-down spectroscopy (CRDS) instrument in detail. They revealed that CO2 and CH4 measurements were affected by changes in the concentration of water vapor, background gases, and isotopologues of the target gas
In order to achieve high precision and sensitivity, the wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) scanned the intensity of the leaking light over the target gas absorption line using the high-precision wavelength monitor with a wavelength resolution of 0.0003 cm−1: 1603 nm for 12C16O2 and 1651 nm for 12CH4 and H126O in real time using the photodetector during each measurement cycle, allowing to model the absorption peak-shape of the target gas from up to 10 points with a Galatry function (Galatry, 1961)
Summary
Since atmospheric carbon dioxide (CO2) is one of the most important trace gases in controlling the Earth’s climate (e.g. surface temperature), much attention has been paid to the understanding of the global distribution of CO2 during the last 50 yr of the twentieth century. Keeling, 1960; Lowe et al, 1979; Conway et al, 1994; Dlugokencky et al, 1995; Keeling et al, 1995; Matsueda and Inoue, 1996; Prinn et al, 2000; Cunnold et al, 2002; Brenninkmeijer et al, 2007; Machida et al, 2008; Rigby et al, 2008; Terao et al, 2011) These observations have revealed detailed distributions of GHGs, ambient monitoring data are still sparse and less reliable in developing countries where GHG emissions are increasing rapidly due to increasing socioeconomic activities (Marquis and Tans, 2008). Chen et al (2010) examined the analytical performance of a Picarro WS-CRDS instrument in detail They revealed that CO2 and CH4 measurements were affected by changes in the concentration of water vapor, background gases, and isotopologues of the target gas. We investigated (1) the correlations between the pressure-broadening effects (PBEs) and variations in background gases N2, O2, and Ar; (2) the correction for the isotopic bias on the CO2 measurements through comparison between experimental results and theoretical calculations; and (3) the transferability of empirically determined water correction function among different three WS-CRDS models and differences in the water correction values from these functions as well as from past studies
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