End-to-end methane gas detection algorithm based on transformer and multi-layer perceptron.

In this paper, an end-to-end methane gas detection algorithm based on transformer and multi-layer perceptron (MLP) for tunable diode laser absorption spectroscopy (TDLAS) is presented. It consists of a Transformer-based U-shaped Neural Network (TUNN) filtering algorithm and a concentration prediction network (CPN) based on MLP. This algorithm employs an end-to-end architectural design to extract information from noisy transmission spectra of methane and derive the CH4 concentrations from denoised spectra, without intermediate steps. The results demonstrate the superiority of the proposed TUNN filtering algorithm over other typically employed digital filters. For concentration prediction, the determination coefficient (R2) reached 99.7%. Even at low concentrations, R2 remained notably high, reaching up to 89%. The proposed algorithm results in a more efficient, convenient, and accurate spectral data processing for TDLAS-based gas sensors.

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.

Quartz-Enhanced Photoacoustic Sensor Based on a Multi-Laser Source for In-Sequence Detection of NO2, SO2, and NH3.

In this work, we report on the implementation of a multi-quantum cascade laser (QCL) module as an innovative light source for quartz-enhanced photoacoustic spectroscopy (QEPAS) sensing. The source is composed of three different QCLs coupled with a dichroitic beam combiner module that provides an overlapping collimated beam output for all three QCLs. The 3λ-QCL QEPAS sensor was tested for detection of NO2, SO2, and NH3 in sequence in a laboratory environment. Sensitivities of 19.99 mV/ppm, 19.39 mV/ppm, and 73.99 mV/ppm were reached for NO2, SO2, and NH3 gas detection, respectively, with ultimate detection limits of 9 ppb, 9.3 ppb, and 2.4 ppb for these three gases, respectively, at an integration time of 100 ms. The detection limits were well below the values of typical natural abundance of NO2, SO2, and NH3 in air.

Commercial and Custom Quartz Tuning Forks for Quartz Enhanced Photoacoustic Spectroscopy: Stability under Humidity Variation.

This work investigates the behavior of commercial and custom Quartz tuning forkss (QTF) under humidity variations. The QTFs were placed inside a humidity chamber and the parameters were studied with a setup to record the resonance frequency and quality factor by resonance tracking. The variations of these parameters that led to a 1% theoretical error on the Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) signal were defined. At a controlled level of humidity, the commercial and custom QTFs present similar results. Therefore, commercial QTFs appear to be a very good candidates for QEPAS as they are also affordable and small. When the humidity increases from 30 to 90 %RH, the variations in the custom QTFs' parameters remain suitable, while commercial QTFs show unpredictable behavior.

Evaluation of greenhouse gas emissions from aerobic and anaerobic wastewater treatment plants in Southeast of Italy.

An evaluation of the operative functioning data of 183 Wastewater Treatment Plants (WWTPs) in Apulia (Southeast of Italy) has been carried out aimed to assess their Green House Gases (GHGs) emissions and the level for which the use of anaerobic sludge treatment should be more convenient in terms of electricity consumption and of GHGs emissions. Out of the 183 studies WWTPs, 140 are practicing aerobic digestion of sludge, while the remaining 43 are practicing anaerobic digestion of sludge. WWTPs in Apulia are serving about 4,81 million PE (Population Equivalent), yielding approximately 600,000-ton equivalent CO2 per annum. The production of GHGs emissions has been estimated by evaluating the contribution of CO2 deriving from: a) electric energy consumption (fossil CO2), b) biogenic CO2, c) N2O and d) CH4 emissions. The present study investigates a number of technical measures for upgrading the existing WWTPs, so to reduce GHGs emissions through the amelioration of CH4 production and capture in the anaerobic step, and through reducing the production of biogenic N2O and CO2 emissions in the aerated basin. The methodology employees artificial intelligence-based control for upgrading the aerobic oxidation of the organic carbon and the nitrification-denitrification steps. As a result, GHGs emissions are expected to be reduced by approximately: 71% for CH4, 57% for N2O, 20% for biogenic CO2 and 15% for fossil derived CO2.

Threshold fluence and incubation during multi-pulse ultrafast laser ablation of quartz.

In this work, the incubation effect on the laser ablation threshold of quartz, after multi-shot irradiation with femtosecond pulses at 1030-nm-wavelength with different repetition rates, was investigated. A strong decrease of the multi-pulse ablation threshold with the number of pulses N was found due to incubation. Moreover, the influence of the repetition rate was negligible in the investigated frequency range which went from 0.06 to 200 kHz. A saturation of the threshold fluence value was observed at number of pulses N > 100 which has been found to be well fitted by an exponential incubation model. Using such model, we estimated the single-pulse ablation threshold value and the incubation coefficient for quartz, which were found equal to Fth,1 = 6.23 ± 0.23 J/cm2 and k = 0.058 ± 0.004.

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.

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.

Ppt level carbon monoxide detection based on light-induced thermoelastic spectroscopy exploring custom quartz tuning forks and a mid-infrared QCL.

In this paper, we report on an ultra-highly sensitive light-induced thermoelastic spectroscopy (LITES)-based carbon monoxide (CO) sensor exploiting custom quartz tuning forks (QTFs) as a photodetector, a multi-pass cell and a mid-infrared quantum cascade laser (QCL) for the first time. The QCL emitting at 4.58 µm with output power of 145 mW was employed as exciting source and the multi-pass cell was employed to increase the gas absorption pathlength. To reduce the noise level, wavelength modulation spectroscopy (WMS) and second harmonic demodulation techniques were exploited. Three QTFs including two custom QTFs (#1 and #2) with different geometries and a commercial standard QTF (#3) were tested as photodetector in the gas sensor. When the integration time of the system was set at 200 ms, minimum detection limits (MDLs) of 750 part-per-trillion (ppt), 4.6 part-per-billion (ppb) and 5.8 ppb were achieved employing QTF #1 #2, and #3, respectively. A full sensor calibration was achieved using the most sensitive QTF#1, demonstrating an excellent linear response with CO concentration.

Multi-pass quartz-enhanced photoacoustic spectroscopy-based trace gas sensing.

A multi-pass quartz-enhanced photoacoustic spectroscopy (MP-QEPAS)-based trace gas sensor is reported. In MP-QEPAS, a multi-pass laser beam pattern through the prong spacing of a quartz tuning fork (QTF) is obtained by means of two right-angle prisms. A large QTF with the prong length of 17 mm and prong spacing of 0.8 mm was employed to increase the passage of multi-pass time and ease the alignment of the beam reflection pattern through the QTF. This multi-pass configuration allows the laser beam to pass through the QTF prong spacing six times. Water vapor (H2O) was chosen as target gas to investigate the performance of the MP-QEPAS sensor. Compared to a conventional QEPAS measurement, the MP-QEPAS technique provided an enhancement of signal level of ∼3.2 times.

Mid-Infrared Quartz-Enhanced Photoacoustic Sensor for ppb-Level CO Detection in a SF6 Gas Matrix Exploiting a T-Grooved Quartz Tuning Fork.

An optical sensor for highly sensitive detection of carbon monoxide (CO) in sulfur hexafluoride (SF6) was demonstrated by using the quartz-enhanced photoacoustic spectroscopy technique. A spectrophone composed of a custom 8 kHz T-shaped quartz tuning fork with grooved prongs and a pair of resonator tubes, to amplify the laser-induced acoustic waves, was designed aiming to maximize the CO photoacoustic response in SF6. A theoretical analysis and an experimental investigation of the influence of SF6 gas matrix on spectrophone resonance properties for CO detection have been provided, and the performances were compared with the standard air matrix. A mid-infrared quantum cascade laser with a central wavelength at 4.61 µm, resonant with the fundamental band of CO, and an optical power of 20 mW was employed as the light excitation source. A minimum detection limit of 10 ppb at 10 s of integration time was achieved, and a sensor response time of ∼3 min was measured.

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%.

Light-induced thermo-elastic effect in quartz tuning forks exploited as a photodetector in gas absorption spectroscopy.

We report on a study of light-induced thermo-elastic effects occurring in quartz tuning forks (QTFs) when exploited as near-infrared light detectors in a tunable diode laser absorption spectroscopy sensor setup. Our analysis showed that when the residual laser beam transmitted by the absorption cell is focused on the QTF surface area where the maximum strain field occurs, the QTF signal-to-noise ratio (SNR) is proportional to the strain itself and to the QTF accumulation time. The SNR was also evaluated when the pressure surrounding the QTF was lowered from 700 Torr to 5 Torr, resulting in an enhancement factor of ∽4 at the lowest pressure. At 5 torr, the QTF employed as light detector showed an SNR ∽6.5 times higher than that obtained by using a commercially available amplified photodetector.

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.

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.

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%.

Ppb-Level Quartz-Enhanced Photoacoustic Detection of Carbon Monoxide Exploiting a Surface Grooved Tuning Fork.

A compact and sensitive carbon monoxide (CO) sensor was demonstrated by using quartz enhanced photoacoustic spectroscopy (QEPAS) exploiting a novel 15.2 kHz quartz tuning fork (QTF) with grooved surfaces. The custom QTF was designed to provide a quality factor as high as 15 000 at atmospheric pressure, which offers a high detection sensitivity. A large QTF prong spacing of 800 µm was selected, allowing one to avoid the use of any spatial filters when employing a quantum cascade laser as the excitation source. Four rectangular grooves were carved on two prong surfaces of the QTF to decrease the electrical resistance and hence enhance the signal amplitude. With water vapor as the catalyst for vibrational energy transfer, the sensor system using the novel surface grooved QTF achieved a CO minimum detection limit of 7 ppb for a 300 ms averaging time, which corresponds to a normalized noise equivalent absorption coefficient of 8.74 × 10-9 cm-1W /√Hz. Continuous measurements covering a seven-day period for atmospheric CO were implemented to verify the reliability and validity of the developed CO sensor system.

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.

Piezo-enhanced acoustic detection module for mid-infrared trace gas sensing using a grooved quartz tuning fork.

A grooved quartz tuning fork (QTF) with a prong spacing of 800 µm for QEPAS application is reported. The prongs spacing is large enough to facilitate optical alignments when a degraded laser beam is used for QEPAS-based trace gas sensors. The grooved QTF has a resonance frequency of 15.2 kHz at atmospheric pressure and is characterized by four rectangular grooves carved on the QTF prong surfaces. With a grooved-prong, the electrical resistance R of the QTF is reduced resulting in an enhanced piezoelectric signal, while the Q factor is not affected, remaining as high as 15000 at atmospheric pressure. The geometric parameters of the acoustic micro resonators (AmRs) for on-beam QEPAS were optimized to match the grooved QTF, and a signal-to-noise gain factor of ∼ 30 was obtained with an optimum configuration. The performance of the QEPAS-based sensor was demonstrated exploiting an interband cascade laser (ICL) for CH4 detection and a 1σ normalized noise equivalent absorption (NNEA) coefficient of 4.1×10-9 cm-1 W/√Hz was obtained at atmospheric pressure.

Tuning forks with optimized geometries for quartz-enhanced photoacoustic spectroscopy.

We report on the design, realization, and performance of novel quartz tuning forks (QTFs) optimized for quartz-enhanced photoacoustic spectroscopy (QEPAS). Starting from a QTF geometry designed to provide a fundamental flexural in-plane vibrational mode resonance frequency of ~16 kHz, with a quality factor of 15,000 at atmospheric pressure, two novel geometries have been realized: a QTF with T-shaped prongs and a QTF with prongs having rectangular grooves carved on both surface sides. The QTF with grooves showed the lowest electrical resistance, while the T-shaped prongs QTF provided the best photoacoustic response in terms of signal-to-noise ratio (SNR). When acoustically coupled with a pair of micro-resonator tubes, the T-shaped QTF provides a SNR enhancement of a factor of 60 with respect to the bare QTF, which represents a record value for mid-infrared QEPAS sensing.