Research on carbon dioxide (CO₂) geological and biogeochemical cycles in the ocean is important to support the geoscience study. Continuous in-situ measurement of dissolved CO₂ is critically needed. However, the time and spatial resolution are being restricted due to the challenges of very high submarine pressure and quite low efficiency in water-gas separation, which, therefore, are emerging the main barriers to deep sea investigation. We develop a fiber-integrated sensor based on cavity ring-down spectroscopy for in-situ CO₂ measurement. Furthermore, a fast concentration retrieval model using exponential fit is proposed at non-equilibrium condition. The in-situ dissolved CO₂ measurement achieves 10 times faster than conventional methods, where an equilibrium condition is needed. As a proof of principle, near-coast in-situ CO₂ measurement was implemented in Sanya City, Haina, China, obtaining an effective dissolved CO₂ concentration of ~950 ppm. The experimental results prove the feasibly for fast dissolved gas measurement, which would benefit the ocean investigation with more detailed scientific data.

To achieve multi-gas measurements of quartz-enhanced photoacoustic spectroscopy (QEPAS) sensors under a frequency-division multiplexing mode with a narrow modulation frequency interval, we report a frequency-domain detection method. A CH₄ absorption line at 1653.72 nm and a CO₂ absorption line at 2004.02 nm were investigated in this experiment. A modulation frequency interval of as narrow as 0.6 Hz for CH₄ and CO₂ detection was achieved. Frequency-domain 2f signals were obtained with a resolution of 0.125 Hz using a real-time frequency analyzer. With the multiple linear regressions of the frequency-domain 2f signals of various gas mixtures, small deviations within 2.5% and good linear relationships for gas detection were observed under the frequency-division multiplexing mode. Detection limits of 0.6 ppm for CH₄ and 2.9 ppm for CO₂ were simultaneously obtained. With the 0.6-Hz interval, the amplitudes of QEPAS signals will increase substantially since the modulation frequencies are closer to the resonant frequency of a QTF. Furthermore, the frequency-domain detection method with a narrow interval can realize precise gas measurements of more species with more lasers operating under the frequency-division multiplexing mode. Additionally, this method, with a narrow interval of modulation frequencies, can also realize frequency-division multiplexing detection for QEPAS sensors under low pressure despite the ultra-narrow bandwidth of the QTF.

This research proposes a method for the simultaneous acquisition of the second harmonic (2f) signal of quartz-enhanced photoacoustic spectroscopy (QEPAS) and the first harmonic (1f) signal of quartz-enhanced photothermal spectroscopy (QEPTS) based on the dual-quartz-enhanced photoacoustic–photothermal spectroscopy. The laser beam is first wavelength-modulated by the injection current and then intensity-modulated by an acoustic-optic modulator. The frequency of the wavelength modulation is half of the QTF1 resonant frequency, and the frequency of the intensity modulation is equal to the QTF2 resonant frequency. A modulated laser beam traveled through the two arms of the QTF1 and converged on the root of the QTF2. The 2f photoacoustic and 1f photothermal signals are concurrently obtained using the frequency division multiplexing technology and lock-in amplifiers, which allows the simultaneous detection of the gas concentration and laser light intensity. CH₄ is chosen as the target gas, and the variations of the 2f photoacoustic and 1f photothermal signals are evaluated at various gas concentrations and light intensities. According to the experiments, the amplitude of the 1f photothermal signal has a good linear connection with light intensity (R² = 0.998), which can be utilized to accurately revise the 2f photoacoustic signal while light intensity fluctuates. Over a wide range of concentrations, the normalized 2f photoacoustic signals exhibit an excellent linear response (R² = 0.996). According to the Allan deviation analysis, the minimum detection limit for CH₄ is 0.39 ppm when the integration time is 430 s. Compared with the light intensity correction using a photodetector for the QEPAS system, this approach offers a novel and effective light intensity correction method for concentration measurements employing 2f analysis. It also has the advantages of low cost and compact volume, especially for mid-infrared and terahertz systems.