Impact of Residual Water Vapor on the Simultaneous Measurements of Trace CH4 and N2O in Air with Cavity Ring-Down Spectroscopy

Abstract

Methane (CH4) and nitrous oxide (N2O) are among the most important atmospheric greenhouse gases. A gas sensor based on a tunable 7.6 μm continuous-wave external-cavity mode-hop-free (EC-MHF) quantum cascade laser (from 1290 to 1350 cm−1) cavity ring-down spectroscopy (CRDS) technique was developed for the simultaneous detection of CH4 and N2O in ambient air with water vapor (H2O) mostly removed via molecular sieve drying to minimize the impact of H2O on the simultaneous measurements. Still, due to the broad and strong absorption spectrum of H2O in the entire mid-infrared (mid-IR) spectral range, residual H2O in the dried ambient air due to incomplete drying and leakage, if not properly accounted for, could cause a significant influence on the measurement accuracy of the simultaneous CH4 and N2O detection. In this paper, the impact of residual H2O on the simultaneous CH4 and N2O measurements were analyzed by comparing the CH4 and N2O concentrations determined from the measured spectrum in the spectral range from 1311 to 1312.1 cm−1 via simultaneous CH4 and N2O measurements and that determined from the measured spectrum in the spectral range from 1311 to 1313 cm−1 via simultaneous CH4, N2O, and H2O measurements. The measured dependence of CH4 and N2O concentration errors on the simultaneously determined H2O concentration indicated that the residual H2O caused an under-estimation of CH4 concentration and over-estimation of N2O concentration. The H2O induced CH4 and N2O concentration errors were approximately linearly proportional to the residual H2O concentration. For the measurement of air flowing at 3 L per min, the residual H2O concentration was stabilized to approximately 14 ppmv, and the corresponding H2O induced errors were −1.3 ppbv for CH4 and 3.7 ppbv for N2O, respectively.