Compact angled multimode interference duplexers for multi-gas sensing applications.

A compact, low-loss 2 × 1 angled-multi-mode-interference-based duplexer is proposed as an optical component for integrating several wavelengths with high coupling efficiency. The self-imaging principle in multimode waveguides is exploited to combine two target wavelengths, corresponding to distinctive absorption lines of important trace gases. The device performance has been numerically enhanced by engineering the geometrical parameters, offering trade-offs in coupling efficiency ratios. The proposed designs are used as versatile duplexers for detecting gas combinations such as ammonia-methane, ammonia-ethane, and ammonia-carbon dioxide, enabling customization for specific sensing applications. The duplexers designed are then fabricated and characterized, with a special focus on assessing the impact of the different target wavelengths on coupling efficiency.

Highly efficient and selective integrated directional couplers for multigas sensing applications.

The design and fabrication of a compact, low-loss, broadband directional coupler (DC) based duplexer operating in the near-infrared (NIR) region are demonstrated. The duplexer exhibits high selectivity and coupling efficiency (CE), for target wavelengths of 1530 nm and 1653.7 nm, making it applicable in systems for the multi-gas detection of ammonia and methane. The measured CE for the duplexer is 73% and 76% at 1530 nm and 1653.7 nm respectively. These results demonstrate the effectiveness of the duplexer as a broadband and scalable power source for highly sensitive sensing techniques, like quartz-enhanced photoacoustic spectroscopy (QEPAS). Its compact size and low-loss characteristics make it highly portable and well-suited for drone-based multi-gas detection applications.

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.

Side-excitation light-induced thermoelastic spectroscopy.

In this Letter, a side-excitation light-induced thermoelastic spectroscopy (SE-LITES) technique was developed for trace gas detection. A novel, to the best of our knowledge, custom quartz tuning fork (QTF) was used as a transducer for photon detection by the thermoelastic effect. The mechanical stress distribution on the QTF surface was analyzed to identify the optimum thermoelastic excitation approach. The electrode film on the QTF surface also works as a partially reflective layer to obtain a long optical absorption path inside the QTF body. With the long optical absorption length and the inner face excitation of the QTF, the thermoelastic effect was greatly enhanced. With an optimized modulation depth, a signal-to-noise ratio (SNR) improvement of more than one order of magnitude was achieved, compared to traditional LITES.

Methane and ethane detection from natural gas level down to trace concentrations using a compact mid-IR LITES sensor based on univariate calibration.

A gas sensor based on light-induced thermo-elastic spectroscopy (LITES) capable to detect methane (C1) and ethane (C2) in a wide concentration range, from percent down to part-per-billion (ppb), is here reported. A novel approach has been implemented, exploiting a compact sensor design that accommodates both a custom 9.8 kHz quartz tuning fork (QTF) used as photodetector and the gas sample in the same housing. The resulting optical pathlength was only 2.5 cm. An interband cascade laser (ICL) with emission wavelength of 3.345 µm was used to target absorption features of C1 and C2. The effects of high concentration analytes on sensor response were firstly investigated. C1 concentration varied from 1% to 10%, while C2 concentration varied from 0.1% to 1%. These ranges were selected to retrace the typical natural gas composition in a 1:10 nitrogen dilution. The LITES sensor was calibrated for both the gas species independently and returned nonlinear but monotonic responses for the two analytes. These univariate calibrations were used to retrieve the composition of C1-C2 binary mixtures with accuracy higher than 98%, without the need for further data analysis. Minimum detection limits of ∼650 ppb and ∼90 ppb were achieved at 10 s of integration time for C1 and C2, respectively, demonstrating the capability of the developed LITES sensor to operate with concentration ranges spanning over 6 orders of magnitude.

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.

Detection of Hydrogen Sulfide in Sewer Using an Erbium-Doped Fiber Amplified Diode Laser and a Gold-Plated Photoacoustic Cell.

A photoacoustic detection module based on a gold-plated photoacoustic cell was reported in this manuscript to measure hydrogen sulfide (H2S) gas in sewers. A 1582 nm distributed feedback (DFB) diode laser was employed as the excitation light source of the photoacoustic sensor. Operating pressure within the photoacoustic cell and laser modulation depth were optimized at room temperature, and the long-term stability of the photoacoustic sensor system was analyzed by an Allan-Werle deviation analysis. Experimental results showed that under atmospheric pressure and room temperature conditions, the photoacoustic detection module exhibits a sensitivity of 11.39 µV/ppm of H2S and can reach a minimum detection limit (1σ) of 140 ppb of H2S with an integration time of 1 s. The sensor was tested for in-field measurements by sampling gas in the sewer near the Shanxi University canteen: levels of H2S of 81.5 ppm were measured, below the 100 ppm limit reported by the Chinese sewer bidding document.

Clamp-type quartz tuning fork enhanced photoacoustic spectroscopy.

In this Letter, clamp-type quartz tuning fork enhanced photoacoustic spectroscopy (Clamp-type QEPAS) is proposed and realized through the design, realization, and testing of clamp-type quartz tuning forks (QTFs) for photoacoustic gas sensing. The clamp-type QTF provides a wavefront-shaped aperture with a diameter up to 1 mm, while keeping Q factors > 104. This novel, to the best of our knowledge, design results in a more than ten times increase in the area available for laser beam focusing for the QEPAS technique with respect to a standard QTF. The wavefront-shaped clamp-type prongs effectively improve the acoustic wave coupling efficiency. The possibility to implement a micro-resonator system for clamp-type QTF is also investigated. A signal-to-noise enhancement of ∼30 times has been obtained with a single-tube acoustic micro resonator length of 8 mm, ∼20% shorter than the dual-tube micro-resonator employed in a conventional QEPAS system.

Multi-gas quartz-enhanced photoacoustic sensor for environmental monitoring exploiting a Vernier effect-based quantum cascade laser.

We report on a gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) able to detect multiple gas species for environmental monitoring applications, by exploiting a Vernier effect-based quantum cascade laser as the excitation source. The device emission spectrum consists of ten separated emission clusters covering the range from 2100 up to 2250 cm-1. Four clusters were selected to detect the absorption features of carbon monoxide (CO), nitrous oxide (N2O), carbon dioxide (CO2), and water vapor (H2O), respectively. The sensor was calibrated with certified concentrations of CO, N2O and CO2 in a wet nitrogen matrix. The H2O absorption feature was used to monitor the water vapor within the gas line during the calibration. Minimum detection limits of 6 ppb, 7 ppb, and 70 ppm were achieved for CO, N2O and CO2, respectively, at 100 ms of integration time. As proof of concept, the QEPAS sensor was tested by continuously sampling indoor laboratory air and monitoring the analytes concentrations.

Quartz-enhanced photoacoustic spectroscopy for multi-gas detection: A review.

Multi-gas detection represents a suitable solution in many applications, such as environmental and atmospheric monitoring, chemical reaction and industrial process control, safety and security, oil&gas and biomedicine. Among optical techniques, Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) has been demonstrated to be a leading-edge technology for addressing multi-gas detection, thanks to the modularity, ruggedness, portability and real time operation of the QEPAS sensors. The detection module consists in a spectrophone, mounted in a vacuum-tight cell and detecting sound waves generated via photoacoustic excitation within the gas sample. As a result, the sound detection is wavelength-independent and the volume of the absorption cell is basically determined by the spectrophone dimensions, typically in the order of few cubic centimeters. In this review paper, the implementation of the QEPAS technique for multi-gas detection will be discussed for three main areas of applications: i) multi-gas trace sensing by exploiting non-interfering absorption features; ii) multi-gas detection dealing with overlapping absorption bands; iii) multi-gas detection in fluctuating backgrounds. The fundamental role of the analysis and statistical tools will be also discussed in detail in relation with the specific applications. This overview on QEPAS technique, highlighting merits and drawbacks, aims at providing ready-to-use guidelines for multi-gas detection in a wide range of applications and operating conditions.

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.

Mid-infrared intracavity quartz-enhanced photoacoustic spectroscopy with pptv - Level sensitivity using a T-shaped custom tuning fork.

Resonant optical power buildup inside a high finesse cavity is exploited to boost the sensitivity in quartz-enhanced photoacoustic spectroscopy (QEPAS) for CO, N2O and H2O detection, operating at a wavelength of 4.59 µm. A quartz tuning fork with T-shaped prongs optimized for QEPAS has been employed. Exploiting the high signal-to-noise ratio attainable with this tuning fork together with an optical power amplification of ~100 enabled by efficient optical feedback locking, limits of detection (3σ, 10 s integration) of 260 ppt and 750 ppt for CO and N2O have been reached.

Ppb-level gas detection using on-beam quartz-enhanced photoacoustic spectroscopy based on a 28 kHz tuning fork.

In this paper, an on-beam quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor based on a custom quartz tuning fork (QTF) acting as a photoacoustic transducer, was realized and tested. The QTF is characterized by a resonance frequency of 28 kHz, ~15% lower than that of a commercially available 32.7 kHz standard QTF. One-dimensional acoustic micro resonator (AmR) was designed and optimized by using stainless-steel capillaries. The 28 kHz QTF and AmRs are assembled in on-beam QEPAS configuration. The AmR geometrical parameters have been optimized in terms of length and internal diameter. The laser beam focus position and the AmR coupling distance were also adjusted to maximize the coupling efficiency. For comparison, QEPAS on-beam configurations based on a standard QTF and on the 28 kHz QTF were compared in terms of H2O and CO2 detection sensitivity. In order to better characterize the performance of the system, H2O, C2H2 and CO2 were detected for a long time and the long-term stability was analyzed by an Allan variance analysis. With the integration time of 1 s, the detection limits for H2O, C2H2 and CO2 are 1.2 ppm, 28.8 ppb and 2.4 ppm, respectively. The detection limits for H2O, C2H2 and CO2 can be further improved to 325 ppb, 10.3 ppb and 318 ppb by increasing the integration time to 521 s, 183 s and 116 s.

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.

H2S quartz-enhanced photoacoustic spectroscopy sensor employing a liquid-nitrogen-cooled THz quantum cascade laser operating in pulsed mode.

In this work, we report on a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor for hydrogen sulfide (H2S) detection, exploiting a liquid-nitrogen-cooled THz quantum cascade laser (QCL) operating in pulsed mode. The spectrophone was designed to accommodate a THz QCL beam and consisted of a custom quartz tuning fork with a large prong spacing, coupled with acoustic resonator tubes. The targeted rotational transition falls at 2.87 THz (95.626 cm-1), with a line-strength of 5.53 ∙ 10-20 cm/mol. A THz QCL peak power of 150 mW was measured at a heat sink temperature of 81 K, pulse width of 1 µs and repetition rate of 15.8 kHz. A QEPAS record sensitivity for H2S detection in the THz range of 360 part-per-billion in volume was achieved at a gas pressure of 60 Torr and 10 s integration time.

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%.

Sub-ppb-level CH4 detection by exploiting a low-noise differential photoacoustic resonator with a room-temperature interband cascade laser.

An ultra-highly sensitive and robust CH4 sensor is reported based on a 3.3 µm interband cascade laser (ICL) and a low-noise differential photoacoustic (PAS) cell. The ICL emission wavelength targeted a fundamental absorption line of CH4 at 2988.795 cm-1 with an intensity of 1.08 × 10-19 cm/molecule. The double-pass and differential design of the PAS cell effectively enhanced the PAS signal amplitude and decreased its background noise. The wavelength modulation depth, operating pressure and V-T relaxation promotion were optimized to maximize the sensor detection limit. With an integration time of 90 s, a detection limit of 0.6 ppb was achieved. No additional water or air laser cooling were required and thereby allowing the realization of a compact and robust CH4 sensor.