Development of a Sub-ppb Resolution Methane Sensor Using a GaSb-Based DFB Diode Laser near 3270 nm for Fugitive Emission Measurement

Abstract

A challenge for mobile measurement of fugitive methane emissions is the availability of portable sensors that feature high sensitivity and fast response times, simultaneously. A methane gas sensor to measure fugitive emissions was developed using a continuous-wave, thermoelectrically cooled, GaSb-based distributed feedback diode laser emitting at a wavelength of 3.27 μm to probe methane in its strong ν₃ vibrational band. Direct absorption spectra (DAS) as well as wavelength-modulated spectra (WMS) of pressure-broadened R(3) manifold lines of methane were recorded through a custom-developed open-path multipass cell with an effective optical path length of 6.8 m. A novel metrological approach was taken to characterize the sensor response in terms of the linearity of different WMS metrics, namely, the peak-to-peak amplitude of the X_2f component and the peak and/or the integrated area of the background-subtracted quadrature signal (i.e., Q(2f - 2f₀)) and the background-subtracted 1f-normalized quadrature signal (i.e., Q(2f/1f - 2f₀/1f₀)). Comparison with calibration gas concentrations spanning 1.5 to 40 ppm_v indicated that the latter WMS metric showed the most linear response, while fitting DAS provides a traceable reference. In the WMS mode, a sensitivity better than 1 ppb_v was achieved at a 1 s integration time. The sensitivity and response time are well-suited to measure enhancements in ambient methane levels caused by fugitive emissions.

Keywords: fugitive emissions; methane; mid-infrared; multipass cell; wavelength modulation spectroscopy.