Simultaneous Monitoring of Atmospheric CH4, N2O, and H2O Using a Single Gas Sensor Based on Mid-IR Quartz-Enhanced Photoacoustic Spectroscopy

Abstract

An optical sensor based on external-cavity quantum cascade laser (EC-QCL) was developed for simultaneous triple-species monitoring of CH₄, N₂O, and H₂O vapor using off-beam quartz-enhanced photoacoustic spectroscopy (OB-QEPAS). The EC-QCL wavelength was scanned over three neighboring absorption lines of CH₄ (1260.81 cm^-1), N₂O (1261.06 cm^-1), and H₂O vapor (1261.58 cm^-1) by tuning the grating of the EC-QCL with a piezoelectric actuator. Molecular relaxation effects impacting the generation of the QEPAS signals resulting from light absorption by CH₄ and N₂O molecules were investigated in the mid-infrared region near 8 μm. A theoretical model was introduced for the mid-infrared region, including the beneficial influence of water vapor. An enhancement of the QEPAS signals by a factor of 3 for CH₄ in air and of 20% for N₂O in air was observed in humidified samples compared to that in dry samples. The QEPAS measurement was scaled by the calibrated reference spectrometers; detection limits of 98 ppbv for CH₄, 12 ppbv for N₂O, and 750 ppmv for H₂O vapor were obtained with a 1σ signal-to-noise ratio (SNR = 1) in humidified gas mixtures. Real-time Kalman filtering was applied to improve the measurement precision by a factor of approximately 4 while keeping the same temporal resolution, leading to measurement precisions of 60 ppbv for CH₄, 10 ppbv for N₂O, and 0.07% for H₂O in the measurements of 1.99 ppmv CH₄ and 312 ppbv N₂O humidified with 2.8% H₂O vapor, with a 1 s lock-in amplifier time constant and an equivalent bandwidth of 0.1 Hz.