High-sensitivity methane detection based on QEPAS and H-QEPAS technologies combined with a self-designed 8.7 kHz quartz tuning fork

Abstract

Methane (CH₄) is a greenhouse gas as well as being flammable and explosive. In this manuscript, quartz-enhanced photoacoustic spectroscopy (QEPAS) and heterodyne QEPAS (H-QEPAS) exploring a self-designed quartz tuning fork (QTF) with resonance frequency (f₀) of ∼8.7 kHz was utilized to achieve sensitive CH₄ detection. Compared with the standard commercial 32.768 kHz QTF, this self-designed QTF with a low f₀ and large prong gap has the merits of long energy accumulation time and low optical noise. The strongest line located at 6057.08 cm⁻¹ in the 2v₃ overtone band of CH₄ was chosen as the target absorption line. A diode laser with a high output power of > 30 mW was utilized as the excitation source. Acoustic micro-resonators (AmRs) were added to the sensor architecture to amplify the intensity of acoustic waves. Compared to the bare QTF, after the addition of AmRs, a signal enhancement of 149-fold and 165-fold were obtained for QEPAS and H-QEPAS systems, respectively. The corresponding minimum detection limits (MDLs) were 711 ppb and 1.06 ppm for QEPAS and H-QEPAS sensors. Furthermore, based on Allan variance analysis the MDLs can be improved to 19 ppb and 27 ppb correspondingly. Compared to the QEPAS sensor, the H-QEPAS sensor shows significantly shorter measurement timeframes, allowing for measuring the gas concentration quickly while simultaneously obtaining f₀ of QTF.