Quartz-enhanced Photoacoustic Spectroscopy Sensor Research Articles

Part-per-Billion (Ppb)-Level Acetylene Sensor Employing Optical Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) with an Erbium-Doped Fiber Amplifier (EDFA) and a Fiber-Optic Fabry–Perot Interferometer

An all-optical double-pass quartz enhanced photoacoustic spectroscopy (QEPAS) sensor for the detection of acetylene (C2H2) at part-per-billion (ppb) levels was developed and experimentally validated. By employing an erbium-doped fiber amplifier (EDFA) capable of emitting up to 1 W of optical power, a commercial quartz tuning fork (QTF) resonating at 30.7 kHz, and double-pass acoustic microresonators, the amplitude of the QEPAS signal was significantly enhanced, thereby improving the sensitivity of the C2H2-QEPAS sensor. Instead of using piezoelectric detection in conventional QEPAS, a highly sensitive fiber-optic Fabry–Perot interferometer (FPI) was employed to measure the vibration of the QTF prong. A working point self-stabilizing technique was exploited to improve the demodulation sensitivity and stability. The linear response of the sensor to laser power and C2H2 concentration confirmed that no saturation occurred. With an excitation laser power of 1 W and a C2H2 absorption line of 1532.83 nm, a C2H2 minimum detection limit (MDL) of 19.1 ppb was achieved, corresponding to a normalized noise equivalent absorption coefficient (NNEA) of 1.58 × 10−8 cm−1∙W∙Hz−1/2. Owing to its high sensitivity, long-term stability, and immunity to electromagnetic interferences, the QEPAS sensor provides considerable potential for remote gas sensing in environmental monitoring and other applications.

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.

Acoustic microresonator based in-plane quartz-enhanced photoacoustic spectroscopy sensor with a line interaction mode.

An acoustic microresonator (AmR) based in-plane quartz-enhanced photoacoustic spectroscopy (IP-QEPAS) sensor with a line interaction mode is proposed for what is believed to be the first time. The interaction area for the acoustic wave of the proposed AmR, with a slotted sidewall, is not limited to a point of the quartz tuning fork (QTF) prongs, but extends along the whole plane of the QTF prongs. Sixteen types of AmRs are designed to identify the best parameters. Water vapor (H2O) is chosen as the analyte to verify the reported method. The results indicate that this AmR for IP-QEPAS with a line interaction mode not only provides a high signal level, but also reduces the thermal noise caused by the laser directly illuminating the QTF. Compared with standard IP-QEPAS without an AmR, the minimum detection limit (MDL) is improved by 4.11 times with the use of the technique proposed in this study.

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.

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.

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%.

Two-component gas quartz-enhanced photoacoustic spectroscopy sensor based on time-division multiplexing of distributed-feedback laser driver current.

A two-component gas sensor in quartz-enhanced photoacoustic spectroscopy based on time-division multiplexing (TDM) technology of a distributed-feedback (DFB) laser driver current was proposed and experimentally demonstrated. The quartz tuning-fork-based photoacoustic spectroscopy (PAS) cell configuration with two optical collimators and two acoustic microresonators was designed to detect the second-harmonic (${2}f$2f) PAS signal. The two optical collimators guaranteed that the two laser beams would inject the PAS cell conveniently, providing higher power input than a 3 dB optical fiber coupler. Two-component gas sensing was achieved by the TDM of the DFB laser driver current. We used this two-component gas sensing technique to detect acetylene (${{\rm C}_2}{{\rm H}_2}$C2H2) at 1532.83 nm and methane (${{\rm CH}_4}$CH4) at 1653.722 nm. The ${{\rm C}_2}{{\rm H}_2}$C2H2 and ${{\rm CH}_4}$CH4 detection was achieved at a 2.4 s interval. The minimum detection limits of 1 ppmv for ${{\rm C}_2}{{\rm H}_2}$C2H2 and 13.14 ppmv for ${{\rm CH}_4}$CH4 were obtained, and the linear responses reached were 0.99968 and 0.99652 for ${{\rm C}_2}{{\rm H}_2}$C2H2 and ${{\rm CH}_4}$CH4, respectively. Moreover, the continuous monitoring of ${{\rm CH}_4}$CH4 and ${{\rm C}_2}{{\rm H}_2}$C2H2 for 40 min showed a good stability. The TDM technology of the DFB laser driver current would play an important role on the multi-component detection.

Compact and sensitive mid-infrared all-fiber quartz-enhanced photoacoustic spectroscopy sensor for carbon monoxide detection

A compact and sensitive quartz-enhanced photoacoustic spectroscopy (QEPAS) based sensor for carbon monoxide (CO) detection was demonstrated by using a mid-infrared all-fiber structure as well as a 3D-printed acoustic detection module. An all-fiber configuration has advantages of easier optical alignment, lower insertion loss, improvement in system stability, reduction in sensor size and lower cost. The 3D-printed acoustic detection module was introduced to match the mid-infrared all-fiber structure and further decrease the sensor volume, which resulted in a small size of 3.5 cm3 and a weight of 5 grams. A 2.33 μm distributed feedback fiber-coupled diode laser was used as the laser excitation source. A custom quartz tuning fork (QTF) with a small-gap of 200 μm was used as the acoustic wave transducer in order to improve the signal level of the QEPAS sensor. An acoustic micro resonator was utilized as the acoustic wave enhancer. The gas pressure and laser wavelength modulation depth were optimized, respectively. Water vapor was used to accelerate the vibrational-translational relaxation rate of the targeted CO molecule. Finally, a minimum detection limit (MDL) of 4.2 part per million (ppm) was achieved, corresponding to a normalized noise equivalent absorption (NNEA) coefficient of 7.4 × 10-9 cm-1W/√Hz. An Allan deviation analysis was used to evaluate the long-term stability of the reported CO-QEPAS sensor system. With an integration time of 150 s, the MDL was improved to be 1.3 ppm.

Nitrous oxide quartz-enhanced photoacoustic detection employing a broadband distributed-feedback quantum cascade laser array

We present a gas sensing system based on quartz-enhanced photoacoustic spectroscopy (QEPAS) employing a monolithic distributed-feedback quantum cascade laser (QCL) array operated in a pulsed mode as a light source. The array consists of 32 quantum cascade lasers emitting in a spectral range from 1190 cm−1 to 1340 cm−1. The optoacoustic detection module was composed of a custom quartz tuning fork with a prong spacing of 1 mm, coupled with two micro-resonator tubes to enhance the signal-to-noise ratio. The QEPAS sensor was validated by detecting the absorption of the P- and R-branches of nitrous oxide. The measurements were performed by switching the array QCLs in sequence while tuning their operating temperature to retrieve the fine structure of the two N2O branches. A sensor calibration was performed, demonstrating a linear responsivity for N2O:N2 concentrations from 1000 down to 200 parts-per-million. With a 10 s lock-in integration time, a detection sensitivity of less than 60 parts-per-billion was achieved permitting the monitoring of nitrous oxide at global atmospheric levels.

Review of Recent Advances in QEPAS-Based Trace Gas Sensing

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is an improvement of the conventional microphone-based photoacoustic spectroscopy. In the QEPAS technique, a commercially available millimeter-sized piezoelectric element quartz tuning fork (QTF) is used as an acoustic wave transducer. With the merits of high sensitivity and selectivity, low cost, compactness, and a large dynamic range, QEPAS sensors have been applied widely in gas detection. In this review, recent developments in state-of-the-art QEPAS-based trace gas sensing technique over the past five years are summarized and discussed. The prospect of QEPAS-based gas sensing is also presented.

Quartz-Enhanced Photoacoustic Spectroscopy Sensor with a Small-Gap Quartz Tuning Fork.

A highly sensitive quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor based on a custom quartz tuning fork (QTF) with a small-gap of 200 μm was demonstrated. With the help of the finite element modeling (FEM) simulation software COMSOL, the change tendency of the QEPAS signal under the influence of the laser beam vertical position and the length of the micro-resonator (mR) were calculated theoretically. Water vapor (H2O) was selected as the target analyte. The experimental results agreed well with those of the simulation, which verified the correctness of the theoretical model. An 11-fold signal enhancement was achieved with the addition of an mR with an optimal length of 5 mm in comparison to the bare QTF. Finally, the H2O-QEPAS sensor, which was based on a small-gap QTF, achieved a minimum detection limit (MDL) of 1.3 ppm, indicating an improvement of the sensor performance when compared to the standard QTF that has a gap of 300 μm.

HCN ppt-level detection based on a QEPAS sensor with amplified laser and a miniaturized 3D-printed photoacoustic detection channel.

Ultra-high sensitive and stable detection of hydrogen cyanide (HCN) based on a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor was realized using an erbium-doped fiber amplifier (EDFA) as well as a miniaturized 3D-printed photoacoustic detection channel (PADC) for the first time. A HCN molecule absorption line located at 6536.46 cm-1 was selected which was in the range of the EDFA emission spectrum. The detection sensitivity of the reported EDFA-QEPAS sensor was enhanced significantly due to the high available EDFA excitation laser power. A 3D printing technique was used to develop the compact PADC, resulting in a size of 29 × 15 × 8 mm3 and a mass of ~5 g in order to improve the sensor stability and implement sensor applications requiring a compact size and light weight. At atmospheric pressure, room temperature and a 1 s acquisition time, a minimum detection limit (MDL) of 29 parts per billion (ppb) was achieved, corresponding to a normalized noise equivalent absorption (NNEA) coefficient of 1.08 × 10-8 cm-1W/Hz-1/2. The long-term performance and the stability of the HCN EDFA-QEPAS sensor system were investigated using an Allan deviation analysis. It indicated that the MDL can be improved to 220 parts per trillion (ppt) with an integration time of 300 s, which demonstrated this compact, integrated and miniaturized 3D-printed PADC based sensor had an excellent stability.

Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) Detection of the ν7 Band of Ethylene at Low Pressure with CO2 Interference Analysis.

Ethylene (C2H4) was detected using quartz-enhanced photoacoustic spectroscopy (QEPAS) at 10.5 µm with a continuous wave, distributed-feedback quantum cascade laser as the light source. The QEPAS sensor was operated at low pressures (≤200 torr) to eliminate the cross-talk spectral interference between C2H4 and CO2, a major interfering species in practical applications. The sensor was calibrated to show a good linear response to C2H4 concentration and the Allan deviation analysis demonstrated a minimum detection limit of 8 ppb at an integration time of 90 s. Although no spectral overlap between C2H4 and CO2 was confirmed at the pressure ≤200 torr by the direct absorption measurement using a 28-m multipass cell, we observed the apparent influence of the CO2 addition to the C2H4/N2 mixture on the photoacoustic signal of C2H4. An energy transfer model involving the vibration-vibration (VV) and vibration-translation (VT) transitions in the C2H4-CO2-N2 system was constructed to interpret the experimental data. Additionally, the vibrational relaxation times of C2H4 were obtained based on the QEPAS technique and the energy transfer model, which were in good agreement with the previous studies.

Theoretical analysis of a resonant quartz-enhanced photoacoustic spectroscopy sensor

In this paper, we report the first analytical model for quartz-enhanced photoacoustic spectroscopy in combination with an acoustic resonator. A generalized fundamental equation is proposed to model the photoacoustic effect, taking into account the coupling between the tuning fork and the surrounding fluid. The analytical signal-to-noise ratio is derived, yielding a direct physical insight with respect to the system design. Experimental behaviors are very well reproduced, and numerical finite elements methods are implemented to successfully confirm the relevance of our approach. We also provide a detailed explanation of the coupling dynamics between the quartz tuning fork and the acoustically resonant tube.

HCl ppb-level detection based on QEPAS sensor using a low resonance frequency quartz tuning fork

In this report, a sensitive quartz-enhanced photoacoustic spectroscopy (QEPAS) based hydrogen chloride (HCl) sensor using a quartz tuning fork (QTF) with a resonance frequency of 30.72kHz was demonstrated for the first time. A fiber-coupled, continuous wave (CW), distributed feedback (DFB) diode laser emitting at 1.74μm was employed as the excitation laser source. Wavelength modulation spectroscopy and a 2nd harmonic detection technique were used to reduce the sensor background noise. An acoustic micro-resonator (mR) was added to the QTF sensor architecture to improve the signal amplitude. For the reported HCl sensor system operating at atmospheric pressure, a 550 ppbv (parts per billion by volume) minimum detection limit at 5739.27cm−1 was achieved when the modulation depth and the data acquisition time were set to 0.23cm−1 and 1s, respectively. The ppb-level detection sensitivity and robust design of the QEPAS technique makes it suitable for use in environmental monitoring and other applications.

Compact quantum cascade laser based quartz-enhanced photoacoustic spectroscopy sensor system for detection of carbon disulfide.

A compact gas sensor system based on quartz-enhanced photoacoustic spectroscopy (QEPAS) employing a continuous wave (CW) distributed feedback quantum cascade laser (DFB-QCL) operating at 4.59 µm was developed for detection of carbon disulfide (CS2) in air at trace concentration. The influence of water vapor on monitored QEPAS signal was investigated to enable compensation of this dependence by independent moisture sensing. A 1 σ limit of detection of 28 parts per billion by volume (ppbv) for a 1 s lock-in amplifier time constant was obtained for the CS2 line centered at 2178.69 cm-1 when the gas sample was moisturized with 2.3 vol% H2O. The work reports the suitability of the system for monitoring CS2 with high selectivity and sensitivity, as well as low sample gas volume requirements and fast sensor response for applications such as workplace air and process monitoring at industry.

Compact all-fiber quartz-enhanced photoacoustic spectroscopy sensor with a 30.72 kHz quartz tuning fork and spatially resolved trace gas detection

An ultra compact all-fiber quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor using quartz tuning fork (QTF) with a low resonance frequency of 30.72 kHz was demonstrated. Such a sensor architecture has the advantages of easier optical alignment, lower insertion loss, lower cost, and more compact compared with a conventional QEPAS sensor using discrete optical components for laser delivery and coupling to the QTF. A fiber beam splitter and three QTFs were employed to perform multi-point detection and demonstrated the potential of spatially resolved measurements.

Sensitive detection of carbon monoxide based on a QEPAS sensor with a 2.3 μm fiber-coupled antimonide diode laser

In this paper, a sensitive quartz-enhanced photoacoustic spectroscopy (QEPAS)–based carbon monoxide (CO) sensor using a 2.3 μm continuous wave (CW) distributed feedback (DFB) fiber-coupled antimonide diode laser is demonstrated for the first time. Wavelength modulation spectroscopy and a second-harmonic detection technique are used to reduce the sensor background noise and simplify the data process. Water vapor is added into a 1000 ppm CO:N2 gas mixture to improve the vibrational–translational relaxation rate of the analyzed CO for the purpose of enhancement of the QEPAS signal. After the modulation depth is optimized, a minimum detection limit of 43.3 ppm at the 4294.6 cm−1 absorption line is achieved when the modulation depth is set to 0.32 cm−1.

Quartz-enhanced photoacoustic spectroscopy sensor for ethylene detection with a 3.32 μm distributed feedback laser diode.

An antimonide distributed feedback quantum wells diode laser operating at 3.32 μm at near room temperature in the continuous wave regime has been used to perform ethylene detection based on quartz enhanced photoacoustic spectroscopy. An absorption line centered at 3007.52 cm(-1) was investigated and a normalized noise equivalent absorption coefficient (1σ) of 3.09 10(-7) cm(-1) W Hz(-1/2) was obtained. The linearity and the stability of the detection have been evaluated. Biological samples' respiration has been measured to validate the feasibility of the detection setup in an agronomic environment, especially on ripening apples.