Lithium Niobate - Enhanced Photoacoustic Spectroscopy.

In this work, we report on the novel employment of lithium niobate tuning forks as acoustic transducers in photoacoustic spectroscopy for gas sensing. The lithium niobate tuning fork (LiNTF) exhibits a fundamental resonance frequency of 39196.6 Hz and a quality factor Q = 5900 at atmospheric pressure. The possibility to operate the LiNTF as a photoacoustic wave detector was demonstrated targeting a water vapor absorption line falling at 7181.14 cm-1 (1.39 µm). A noise equivalent concentration of 2 ppm was reached with a signal integration time of 20 s. These preliminary results open the path towards integrated photonic devices for gas sensing with LiNTF-based detectors on lithium niobate platforms.

Assessment of vibrational-translational relaxation dynamics of in a wet-nitrogen matrix through QEPAS.

Here we report on a study of the non-radiative relaxation dynamic of 12CH4 and 13CH4 in wet nitrogen-based matrixes by using the quartz-enhanced photoacoustic spectroscopy (QEPAS) technique. The dependence of the QEPAS signal on pressure at fixed matrix composition and on H2O concentration at fixed pressure was investigated. We demonstrated that QEPAS measurements can be used to retrieve both the effective relaxation rate in the matrix, and the V-T relaxation rate associated to collisions with nitrogen and water vapor. No significant differences in measured relaxation rates were observed between the two isotopologues.

Quartz-enhanced photoacoustic spectroscopy (QEPAS) and Beat Frequency-QEPAS techniques for air pollutants detection: A comparison in terms of sensitivity and acquisition time.

In this work, a comparison between Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) and Beat Frequency-QEPAS (BF-QEPAS) techniques for environmental monitoring of pollutants is reported. A spectrophone composed of a T-shaped Quartz Tuning Fork (QTF) coupled with resonator tubes was employed as a detection module. An interband cascade laser has been used as an exciting source, allowing the targeting of two NO absorption features, located at 1900.07 cm-1 and 1900.52 cm-1, and a water vapor absorption feature, located at 1901.76 cm-1. Minimum detection limits of 90 ppb and 180 ppb were achieved with QEPAS and BF-QEPAS techniques, respectively, for NO detection. The capability to detect multiple components in the same gas mixture using BF-QEPAS was also demonstrated.

Signal-to-Noise Ratio Analysis for the Voltage-Mode Read-Out of Quartz Tuning Forks in QEPAS Applications.

Quartz tuning forks (QTFs) are employed as sensitive elements for gas sensing applications implementing quartz-enhanced photoacoustic spectroscopy. Therefore, proper design of the QTF read-out electronics is required to optimize the signal-to-noise ratio (SNR), and in turn, the minimum detection limit of the gas concentration. In this work, we present a theoretical study of the SNR trend in a voltage-mode read-out of QTFs, mainly focusing on the effects of (i) the noise contributions of both the QTF-equivalent resistor and the input bias resistor RL of the preamplifier, (ii) the operating frequency, and (iii) the bandwidth (BW) of the lock-in amplifier low-pass filter. A MATLAB model for the main noise contributions was retrieved and then validated by means of SPICE simulations. When the bandwidth of the lock-in filter is sufficiently narrow (BW = 0.5 Hz), the SNR values do not strongly depend on both the operating frequency and RL values. On the other hand, when a wider low-pass filter bandwidth is employed (BW = 5 Hz), a sharp SNR peak close to the QTF parallel-resonant frequency is found for large values of RL (RL > 2 MΩ), whereas for small values of RL (RL < 2 MΩ), the SNR exhibits a peak around the QTF series-resonant frequency.

Characterization of H2S QEPAS detection in methane-based gas leaks dispersed into environment.

The increase in fatal accidents and chronic illnesses caused by hydrogen sulfide (H2S) exposure occurring in various workplaces is pushing the development of sensing systems for continuous and in-field monitoring of this hazardous gas. We report here on the design and realization of a Near-IR quartz-enhanced photoacoustic sensor (QEPAS) for H2S leaks detection. H2S QEPAS signal was measured in matrixes containing up to 1 % of methane (CH4) and nitrogen (N2) which were chosen as the laboratory model environment for leakages from oil and gas wells or various industrial processes where H2S and CH4 can leak simultaneously. An investigation of the influence of CH4 on H2S relaxation and photoacoustic generation was proposed in this work and the sensor performances were carefully assessed with respect to CH4 content in the mixture. We demonstrated the high selectivity, with no cross talk between H2S, H2O and CH4 absorption lines, high sensitivity, and fast response time of the developed sensor, achieving a minimum detection limit (MDL) of 2.5 ppm for H2S with 2 s lock-in integration time. The employed 2.6 µm laser allowed us to employ the sensor also for CH4 detection, achieving an MDL of 85 ppm. The realized QEPAS sensor lends itself to the development of a portable and compact device for industrial monitoring.

High-concentration methane and ethane QEPAS detection employing partial least squares regression to filter out energy relaxation dependence on gas matrix composition.

A quartz enhanced photoacoustic spectroscopy (QEPAS) sensor capable to detect high concentrations of methane (C1) and ethane (C2) is here reported. The hydrocarbons fingerprint region around 3 µm was exploited using an interband cascade laser (ICL). A standard quartz tuning fork (QTF) coupled with two resonator tubes was used to detect the photoacoustic signal generated by the target molecules. Employing dedicated electronic boards to both control the laser source and collect the QTF signal, a shoe-box sized QEPAS sensor was realized. All the generated mixtures were downstream humidified to remove the influence of water vapor on the target gases. Several natural gas-like samples were generated and subsequently diluted 1:10 in N2. In the concentration ranges under investigation (1%-10% for C1 and 0.1%-1% for C2), both linear and nonlinear responses of the sensor were measured and signal variations due to matrix effects were observed. Partial least squares regression (PLSR) was employed as a multivariate statistical tool to accurately determine the concentrations of C1 and C2 in the mixtures, compensating the matrix relaxation effects. The achieved results extend the range of C1 and C2 concentrations detectable by QEPAS technique up to the percent scale.

Simultaneous Detection of Methane, Ethane, and Propane by QEPAS Sensors for On-Site Hydrocarbon Characterization and Production Monitoring.

Natural gas is sampled and produced throughout the lifespan of a petroleum field. Gas composition and isotope data are critical inputs in the exploration and field development, such as gas show identification, petroleum system analysis, fluid characterization, and production monitoring. On-site gas analysis is usually conducted within a mud gas unit, which is operationally unavailable after drilling. Gas samples need to be taken from the field and shipped back to the laboratory for gas chromatography and isotope-ratio mass spectrometry analyses. Results are usually without sufficient resolution to fully characterize the heterogeneity and dynamics of fluids within the reservoir and the production system. In addition, it often takes a considerable time to obtain the results using the traditional method. A novel QEPAS (quartz-enhanced photoacoustic spectroscopy) sensor system was developed to move gas composition analyses to field for quasi-real-time characterization and monitoring. With respect to previously reported QEPAS prototypes for trace gas detection, the new system realized measuring concentrations of methane (C1), ethane (C2), and propane (C3) in gas phase within the percentage range that is typically encountered in natural gas samples from oil and gas fields. A gas mixing enclosure was used to dilute the natural gas-like mixtures in nitrogen gas (N2) to avoid the saturation of QEPAS signals. An iterative analysis based on multilinear regression of QEPAS spectra was developed to filter out the influence of gas matrix variation from multiple hydrocarbon components. The advance in simultaneous measuring hydrocarbon gases and expanded linearity range of QEPAS, with previously reported detection of H2S, CO2, and gas isotopes (12CO2/13CO2, 13CH4/12CH4), opens a way to use the advanced sensing technology for in situ and real-time gas detection and chemical analysis in the oil industry.

Compact and portable quartz-enhanced photoacoustic spectroscopy sensor for carbon monoxide environmental monitoring in urban areas.

We report on the realization, calibration, and test outdoor of a 19-inches rack 3-units sized Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) trace gas sensor designed for real-time carbon monoxide monitoring in ambient air. Since CO acts as a slow energy relaxer when excited in the mid-infrared spectral region, its QEPAS signal is affected by the presence of relaxation promoters, such as water vapor, or quenchers like molecular oxygen. We analyzed in detail all the CO relaxation processes with typical collisional partners in an ambient air matrix and used this information to evaluate oxygen and humidity-related effects, allowing the real CO concentration to be retrieved. The sensor was tested outdoor in a trafficked urban area for several hours providing results comparable with the daily averages reported by the local air inspection agency, with spikes in CO concentration correlated to the passages of heavy-duty vehicles.

Quartz-enhanced photoacoustic spectroscopy exploiting low-frequency tuning forks as a tool to measure the vibrational relaxation rate in gas species.

We demonstrated that quartz-enhanced photoacoustic spectroscopy (QEPAS) is an efficient tool to measure the vibrational relaxation rate of gas species, employing quartz tuning forks (QTFs) as sound detectors. Based on the dependence of the QTF resonance frequency on the resonator geometry, a wide range of acoustic frequencies with narrow detection bandwidth was probed. By measuring the QEPAS signal of the target analyte as well as the resonance properties of different QTFs as a function of the gas pressure, the relaxation time can be retrieved. This approach has been tested in the near infrared range by measuring the CH4 (nν4 ) vibrational relaxation rate in a mixture of 1% CH4, 0.15 % H2O in N2, and the H2O (ν1 ) relaxation rate in a mixture of 0.5 % H2O in N2. Relaxation times of 3.2 ms Torr and 0.25 ms Torr were estimated for CH4 and H2O, respectively, in excellent agreement with values reported in literature.

Fiber-Coupled Quartz-Enhanced Photoacoustic Spectroscopy System for Methane and Ethane Monitoring in the Near-Infrared Spectral Range.

We report on a fiber-coupled, quartz-enhanced photoacoustic spectroscopy (QEPAS) near-IR sensor for sequential detection of methane (CH4 or C1) and ethane (C2H6 or C2) in air. With the aim of developing a lightweight, compact, low-power-consumption sensor suitable for unmanned aerial vehicles (UAVs)-empowered environmental monitoring, an all-fiber configuration was designed and realized. Two laser diodes emitting at 1653.7 nm and 1684 nm for CH4 and C2H6 detection, respectively, were fiber-combined and fiber-coupled to the collimator port of the acoustic detection module. No cross talk between methane and ethane QEPAS signal was observed, and the related peak signals were well resolved. The QEPAS sensor was calibrated using gas samples generated from certified concentrations of 1% CH4 in N2 and 1% C2H6 in N2. At a lock-in integration time of 100 ms, minimum detection limits of 0.76 ppm and 34 ppm for methane and ethane were achieved, respectively. The relaxation rate of CH4 in standard air has been investigated considering the effects of H2O, N2 and O2 molecules. No influence on the CH4 QEPAS signal is expected when the water vapor concentration level present in air varies in the range 0.6-3%.

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%.

Environmental Monitoring of Methane with Quartz-Enhanced Photoacoustic Spectroscopy Exploiting an Electronic Hygrometer to Compensate the H2O Influence on the Sensor Signal.

A dual-gas sensor based on the combination of a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor and an electronic hygrometer was realized for the simultaneous detection of methane (CH4) and water vapor (H2O) in air. The QEPAS sensor employed an interband cascade laser operating at 3.34 µm capable of targeting a CH4 absorption line at 2988.8 cm-1 and a water line at 2988.6 cm-1. Water vapor was measured with both the electronic hygrometer and the QEPAS sensor for comparison. The measurement accuracy provided by the hygrometer enabled the adjustment of methane QEPAS signal with respect to the water vapor concentration to retrieve the actual CH4 concentration. The sensor was tested by performing prolonged measurements of CH4 and H2O over 60 h to demonstrate the effectiveness of this approach for environmental monitoring applications.

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.

Acoustic Coupling between Resonator Tubes in Quartz-Enhanced Photoacoustic Spectrophones Employing a Large Prong Spacing Tuning Fork.

A theoretical model describing the acoustic coupling between two resonator tubes in spectrophones exploiting custom-made quartz tuning forks (QTFs) is proposed. The model is based on an open-end correction to predict the optimal tube length. A calculation of the sound field distribution from one tube exit allowed for the estimation of the optimal radius as a function of the QTF prong spacing and the sound wavelength. The theoretical predictions have been confirmed using experimental studies employing a custom QTF with a fundamental flexural mode resonance frequency of 15.8 kHz and a quality factor of 15,000 at atmospheric pressure. The spacing between the two prongs was 1.5 mm. Spectrophones mounting this QTF were implemented for the quartz-enhanced photoacoustic detection of water vapor in air in the mid-infrared 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.