Quartz-enhanced Photoacoustic Research Articles

In Situ High-Precision Measurement of Deep-Sea Dissolved Methane by Quartz-Enhanced Photoacoustic and Light-Induced Thermoelastic Spectroscopy.

Rapid and accurate realization of in situ analysis of deep-sea dissolved gases imperative to the study of ecological geology, oil and gas resource exploration, and global climate change. Herein, we report for the first time the deep-sea dissolved methane (CH4) in situ sensor based on quartz-enhanced photoacoustic and light-induced thermoelastic spectroscopy. The developed sensor system has a volume of φ120 mm × 430 mm and a power consumption of 7.6 W. The sensor, in the manner of frequency division multiplexing, is able to simultaneously measure the photoacoustic signals and light-induced thermoelastic signals, which can accurately correct laser-intensity induced influence on concentration. The spectral response of CH4 concentration varying from 0.01 to 5% is calibrated in detail based on the pressure and temperature in the application environment. The trend of the photoacoustic signal of CH4 at different water molecule (H2O) concentrations is investigated. An Allan variance analysis of several hours demonstrates a minimum detection limit of 0.21 ppm for the CH4 spectrometer. The sensor combined with the gas-liquid separation and enrichment unit is integrated into a compact marine standalone system. Since the specifically designed photoacoustic cell has a volume of only 1.2 mL, the time response for dissolved CH4 detection is reduced to 4 min. Furthermore, the sensor is successfully deployed in the vicinity of the "HaiMa" cold seeps at 1380 m underwater in the South China Sea, completing three consecutive days of measurements of dissolved CH4.

Partial Least-Squares Regression as a Tool to Retrieve Gas Concentrations in Mixtures Detected Using Quartz-Enhanced Photoacoustic Spectroscopy.

We report on a statistical tool based on partial least-squares regression (PLSR) able to retrieve single-component concentrations in a multiple-gas mixture characterized by spectrally overlapping absorption features. Absorption spectra of mixtures of CO–N2O and mixtures of C2H2–CH4–N2O, both diluted in N2, were detected in the mid-IR range by exploiting quartz-enhanced photoacoustic spectroscopy (QEPAS) and using two quantum cascade lasers as light sources. Single-gas reference spectra of each target molecule were acquired and used as PLSR-based algorithm training data set. The concentration range explored in the analysis varies from a few parts-per-million (ppm) to thousands of ppm. Within this concentration range, the influence of the gas matrix on nonradiative relaxation processes can be neglected. Exploiting the ability of PLSR to deal with correlated data, these spectra were used to generate new simulated spectra, i.e., linear combinations of the reference ones. A Gaussian noise distribution was added to the created data set, simulating the real QEPAS signal fluctuations around the peak value. Compared with standard multilinear regression, PLSR predicted gas concentrations with a calibration error up to 5 times better, even with absorption features with spectral overlap greater than 97%.

Anomalous Humidity Dependence in Photoacoustic Spectroscopy of CO Explained by Kinetic Cooling

Water affects the amplitude of photoacoustic signals from many gas phase molecules. In quartz-enhanced photoacoustic (QEPAS) measurements of CO excited at the fundamental vibrational resonance of CO, the photoacoustic signal decreases with increasing humidity, reaches a pronounced minimum at ~0.19%V, and increases with humidity for higher water contents. This peculiar trend is explained by competing endothermal and exothermal pathways of the vibrational relaxation of CO in N2 and H2O. Near-resonant vibrational–vibrational transfer from CO to N2, whose vibrational frequency is 188 cm−1 higher than in CO, consumes thermal energy, yielding a kinetic cooling effect. In contrast, vibrational relaxation via H2O is fast and exothermal, and hence counteracts kinetic cooling, explaining the observed trend. A detailed kinetic model for collisional relaxation of CO in N2 and H2O is presented. Simulations using rate constants obtained from literature were performed and compared to humidity dependent QEPAS experiments at varying pressure. Agreement between the experiments and simulations confirmed the validity of the model. The kinetic model can be used to identify optimized experimental conditions for sensing CO and can be readily adapted to include further collision partners.

Broadband detection of methane and nitrous oxide using a distributed-feedback quantum cascade laser array and quartz-enhanced photoacoustic sensing

Here we report on the broadband detection of nitrous oxide (N2O) and methane (CH4) mixtures in dry nitrogen by using a quartz-enhanced photoacoustic (QEPAS) sensor exploiting an array of 32 distributed-feedback quantum cascade lasers, within a spectral emission range of 1190−1340 cm−1 as the excitation source. Methane detection down to a minimum detection limit of 200 ppb at 10 s lock-in integration time was achieved. The sensor demonstrated a linear response in the range of 200−1000 ppm. Three different mixtures of N2O and CH4 in nitrogen at atmospheric pressure have been analyzed. The capability of the developed QEPAS sensor to selectively determine the N2O and CH4 concentrations was demonstrated, in spite of significant overlap in their respective absorption spectra in the investigated spectral range.

Dual-Gas Quartz-Enhanced Photoacoustic Sensor for Simultaneous Detection of Methane/Nitrous Oxide and Water Vapor.

The development of a dual-gas quartz-enhanced photoacoustic (QEPAS) sensor capable of simultaneous detection of water vapor and alternatively methane or nitrous oxide is reported. A diode laser and a quantum cascade laser (QCL) excited independently and simultaneously both the fundamental and the first overtone flexural mode of the quartz tuning fork (QTF), respectively. The diode laser targeted a water absorption line located at 7181.16 cm-1 (1.392 μm), while the QCL emission wavelength is centered at 7.71 μm and was tuned to target two strong absorption lines of methane and nitrous oxide, located at 1297.47 and 1297.05 cm-1, respectively. Two sets of microresonator tubes were positioned, respectively, at the antinode points of the fundamental and the first overtone flexural modes of the QTF to enhance the QEPAS signal-to-noise ratio. Detection limits of 18 ppb for methane, 5 ppb for nitrous oxide and 20 ppm for water vapor have been achieved at a lock-in integration time of 100 ms.

Sensitive Detection of Ammonia Based on Quartz-Enhanced Photoacoustic Spectroscopy

This letter describes a sensitive quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor for measuring ammonia (NH3) concentrations based on a custom quartz tuning fork (QTF) with a small gap of 200 μm. The signal was enhanced by adding a microresonator (mR) with an optimum length of 5 mm to the bare QTF. Wavelength modulation spectroscopy with second-harmonic detection was adopted to reduce the noise level and simplify the data processing. After optimization of the laser modulation depth, a minimum detection limit of 22.6 ppm was obtained.

Purely wavelength- and amplitude-modulated quartz-enhanced photoacoustic spectroscopy.

We report here on a quartz-enhanced photoacoustic (QEPAS) sensor employing a quantum cascade laser (QCL) structure capable of operating in a pure amplitude or wavelength modulation configuration. The QCL structure is composed of three electrically independent sections: Gain, Phase (PS) and Master Oscillator (MO). Selective current pumping of these three sections allows obtaining laser wavelength tuning without changes in the optical power, and power modulation without emission wavelength shifts. A pure QEPAS amplitude modulation condition is obtained by modulating the PS current, while pure wavelength modulation is achieved by modulating simultaneously the MO and PS QCL sections and slowly scanning the DC current level injected in the PS section.

Highly sensitive gas leak detector based on a quartz-enhanced photoacoustic SF6 sensor.

The implementation, performance validation, and testing of a gas-leak optical sensor based on mid-IR quartz-enhanced photoacoustic (QEPAS) spectroscopic technique is reported. A QEPAS sensor was integrated in a vacuum-sealed test station for mechatronic components. The laser source for the sensor is a quantum cascade laser emitting at 10.56 µm, resonant with a strong absorption band of sulfur hexafluoride (SF6), which was selected as a leak tracer. The minimum detectable concentration of the QEPAS sensor is 2.7 parts per billion with an integration time of 1 s, corresponding to a sensitivity of leak flows in the 10-9 mbar∙l/s range, comparable with state-of-the-art leak detection techniques.

Improved Tuning Fork for Terahertz Quartz-Enhanced Photoacoustic Spectroscopy.

We report on a quartz-enhanced photoacoustic (QEPAS) sensor for methanol (CH3OH) detection employing a novel quartz tuning fork (QTF), specifically designed to enhance the QEPAS sensing performance in the terahertz (THz) spectral range. A discussion of the QTF properties in terms of resonance frequency, quality factor and acousto-electric transduction efficiency as a function of prong sizes and spacing between the QTF prongs is presented. The QTF was employed in a QEPAS sensor system using a 3.93 THz quantum cascade laser as the excitation source in resonance with a CH3OH rotational absorption line located at 131.054 cm−1. A minimum detection limit of 160 ppb in 30 s integration time, corresponding to a normalized noise equivalent absorption NNEA = 3.75 × 10−11 cm−1W/Hz½, was achieved, representing a nearly one-order-of-magnitude improvement with respect to previous reports.

Allan Deviation Plot as a Tool for Quartz-Enhanced Photoacoustic Sensors Noise Analysis.

We report here on the use of the Allan deviation plot to analyze the long-term stability of a quartz-enhanced photoacoustic (QEPAS) gas sensor. The Allan plot provides information about the optimum averaging time for the QEPAS signal and allows the prediction of its ultimate detection limit. The Allan deviation can also be used to determine the main sources of noise coming from the individual components of the sensor. Quartz tuning fork thermal noise dominates for integration times up to 275 s, whereas at longer averaging times, the main contribution to the sensor noise originates from laser power instabilities.

THz quartz-enhanced photoacoustic sensor for H₂S trace gas detection.

We report on a quartz-enhanced photoacoustic (QEPAS) gas sensing system for hydrogen sulphide (H₂S) detection. The system architecture is based on a custom quartz tuning fork (QTF) optoacoustic transducer with a novel geometry and a quantum cascade laser (QCL) emitting 1.1 mW at a frequency of 2.913 THz. The QTF operated on the first flexion resonance frequency of 2871 Hz, with a quality factor Q = 17,900 at 20 Torr. The tuning range of the available QCL allowed the excitation of a H₂S rotational absorption line with a line-strength as small as S = 1.13·10⁻²² cm/mol. The measured detection sensitivity is 30 ppm in 3 seconds and 13 ppm for a 30 seconds integration time, which corresponds to a minimum detectable absorption coefficient α(min) = 2.3·10⁻⁷ cm⁻¹ and a normalized noise-equivalent absorption NNEA = 4.4·10⁻¹⁰ W·cm⁻¹·Hz(-1/2), several times lower than the values previously reported for near-IR and mid-IR H₂S QEPAS sensors.

A quartz-enhanced photoacoustic sensor for H2S trace-gas detection at 2.6 μm

We report on the realization of a quartz-enhanced photoacoustic (QEPAS) sensor for measurement of H2S gas traces. A distributed feedback diode laser working at 2.64 µm wavelength has been coupled to an acoustic detection module composed of a quartz tuning fork and a micro-resonator system, and the QEPAS signal has been optimized in terms of gas sample pressure and laser frequency modulation depth. The sensor shows a very good linearity with respect to the H2S concentration. We performed an Allan–Werle variance analysis to investigate the sensor long-term stability, and we reached a detection limit of four parts per million for 1-s integration time and 500 parts per billion in 60-s integration time. The realized QEPAS sensor represents a good compromise between performance and handiness, in view of a fully portable device.

A quartz enhanced photo-acoustic gas sensor based on a custom tuning fork and a terahertz quantum cascade laser

An innovative quartz enhanced photoacoustic (QEPAS) gas sensing system operating in the THz spectral range and employing a custom quartz tuning fork (QTF) is described. The QTF dimensions are 3.3 cm × 0.4 cm × 0.8 cm, with the two prongs spaced by ∼800 μm. To test our sensor we used a quantum cascade laser as the light source and selected a methanol rotational absorption line at 131.054 cm(-1) (∼3.93 THz), with line-strength S = 4.28 × 10(-21) cm mol(-1). The sensor was operated at 10 Torr pressure on the first flexion QTF resonance frequency of 4245 Hz. The corresponding Q-factor was 74 760. Stepwise concentration measurements were performed to verify the linearity of the QEPAS signal as a function of the methanol concentration. The achieved sensitivity of the system is 7 parts per million in 4 seconds, corresponding to a QEPAS normalized noise-equivalent absorption of 2 × 10(-10) W cm(-1) Hz(-1/2), comparable with the best result of mid-IR QEPAS systems.