Simultaneous Detection of Major Greenhouse Gases with Multiresonator Photoacoustic Spectroscopy.

Greenhouse gas (GHG) detection plays an important role in climate change research and industry applications. A novel photoacoustic spectroscopy (PAS) sensor based on multiple resonators has been developed for the detection of GHGs. The major GHGs CO2, CH4, and N2O were measured simultaneously using only one acoustic sensor by coupling three acoustic resonators into a photoacoustic cell. A sinusoidal voltage signal-driven noise source was integrated into a multiresonator photoacoustic cell, allowing convenient calibration of the resonant frequency of the photoacoustic cell. The performance of the sensor was further enhanced by reflecting a laser beam four times in the photoacoustic cell. Allan deviation analysis showed that the minimum detection limits of 2.7 ppm, 90 ppb, and 1 ppb could be achieved for CO2, CH4, and N2O, respectively, over a 300 s integration time. The feasibility of the system was confirmed by continuous measurements of the three major GHGs from different sources for up to 10 h.

Neural Network Based Aliasing Spectral Decoupling Algorithm for Precise Mid-Infrared Multicomponent Gases Sensing.

Owing to the overlapping and cross-interference of absorption lines in multicomponent gases, the simultaneous measurement of such gases via laser absorption spectroscopy frequently necessitates the use of supplementary pressure sensors to distinguish the spectral lines. Alternatively, it requires multiple lasers combined with time-division multiplexing to independently scan the absorption peaks of each gas, thereby preventing interference from other gases. This inevitably escalates both the cost of the system and the complexity of the gas pathway. In response to these challenges, a mid-infrared sensor employing a neural network-based decoupling algorithm for aliasing spectral is developed, enabling the simultaneous detection of methane(CH4), water vapor(H2O), and ethane(C2H6). The sensor system underwent evaluation in a controlled laboratory environment. Allan deviation analysis revealed that the minimum detection limits for CH4,H2O, and C2H6 were 6.04, 118.44, and 1 ppb, respectively, with an averaging time of 3 s. The performance of the proposed sensor demonstrates that the aliasing spectral decoupling algorithm based on neural network combined with wavelength-modulated spectroscopy technology has the advantages of high sensitivity, low cost and low complexity, showing its potential for simultaneous detection of multicomponent trace gases in various fields.

Pressure sensing with two-color laser absorption spectroscopy for combustion diagnostics.

Pressure is an important parameter in assessing combustion performance that is typically measured using contact sensors. However, contact sensors usually disturb combustion flows and suffer from the temperature tolerance limit of sensor materials. In this Letter, an innovative noncontact two-color pressure sensing method based on tunable diode laser absorption spectroscopy (TDLAS) is proposed. This makes it possible to measure pressure at high temperature environments for combustion diagnostics. The proposed method uses the linear combination of the collision-broadened linewidths of two H2O absorption lines near 1343 and 1392 nm to measure the pressure. The feasibility and performance of such method have been demonstrated by measuring pressures from 1 to 5 bars at temperatures up to 1300 K with a laser wavelength scanning rate of 20 kHz. Measurement errors were found to be within 3%. Compared to previously reported TDLAS pressure sensors, this method is free from the influence of concentration and can also be combined with the existing two-color TDLAS thermometry to realize a fast, on line, and multi-parameter measurement in combustion diagnostics.

Tumor-derived GABA promotes lung cancer progression by influencing TAMs polarization and neovascularization.

BACKGROUND: Gamma-aminobutyric acid (GABA), a common neurotransmitter, has been found in various cancers but its origin and its role in the tumor immune microenvironment remains unclear. METHODS: Here, we reported the expression of glutamate decarboxylase 1 (GAD1, converting glutamate into GABA) in lung cancer tissues based on the publicly available database, and explored the effects and underlying mechanism of GABA on lung cancer progression. RESULTS: Compared with normal tissues, GAD1 was aberrantly overexpressed in lung adenocarcinoma (LUAD) based on TCGA database. Furthermore, the LUAD patients' overall survival was negatively correlated with the GAD1 expression levels. Our work found that a GABAa receptor inhibitor had a therapeutic effect on mouse tumors and significantly reduced tumor size and weight. Further experiments showed that GABA derived from tumor cells promoted tumor progression not by directly affecting cancer cells but by affecting macrophages polarization in the tumor microenvironment. We found that GABA inhibited the NF-κB pathway and STAT3 pathway to prevent macrophages from polarizing towards M1 type, while promoting macrophage M2 polarization by activating the STAT6 pathway. GABA was also found to promote tumor neovascularization by increasing the expression of FGF2 in macrophages. CONCLUSIONS: These results suggest that GABA affects tumor progression by regulating macrophage polarization, and targeting GABA and its signaling pathway may represent a potential therapy for lung cancer.

Erbium-doped fiber amplifier (EDFA)-assisted laser heterodyne radiometer (LHR) working in the shot-noise-dominated regime.

A near-infrared (NIR) laser heterodyne radiometer (LHR) using a 1603 nm distributed feedback (DFB) laser, associated with an erbium-doped fiber amplifier (EDFA), used as a local oscillator (LO) was developed. The EDFA was customized for automatic power control to amplify and stabilize the LO DFB laser power, which allowed to reduce baseline fluctuation and thus make the processed atmospheric transmission spectrum with higher precision. The operation of the EDFA-assisted LHR with a shot-noise-dominated performance was analyzed and experimentally achieved by optimizing the LO power. The performance of the developed LHR was evaluated and verified by measuring an atmospheric CO2 absorption spectrum, and the atmospheric CO2 column abundances were then retrieved based on the optimal estimation method (OEM). The results were in good agreement with the Greenhouse Gas Observation Satellite (GOSAT) data. The EDFA-assisted LHR firstly reported in this Letter has a potential to further improve the measurement precision of atmospheric greenhouse gases using ground-based LHR remote sensing.

High-resolution oxygen-corrected laser heterodyne radiometer (LHR) for stratospheric and tropospheric wind field detection.

We developed a near-infrared (NIR) dual-channel oxygen-corrected laser heterodyne radiometer (LHR) in the ground-based solar occultation mode for measuring vertical profile of wind field in the troposphere and low stratosphere. Two distributed feedback (DFB) lasers centered at 1.27 µm and 1.603 µm were used as local oscillators (LO) to probe absorption of oxygen (O2) and carbon dioxide (CO2), respectively. High-resolution atmospheric O2 and CO2 transmission spectra were measured simultaneously. The atmospheric O2 transmission spectrum was used to correct the temperature and pressure profiles based on a constrained Nelder-Mead's simplex method. Vertical profiles of atmospheric wind field with an accuracy of ∼5 m/s were retrieved based on the optimal estimation method (OEM). The results reveal that the dual-channel oxygen-corrected LHR has high development potential in portable and miniaturized wind field measurement.

Portable TDLAS Sensor for Online Monitoring of CO2 and H2O Using a Miniaturized Multi-Pass Cell.

We designed a tunable diode laser absorption spectroscopy (TDLAS) sensor for the online monitoring of CO2 and H2O concentrations. It comprised a small self-design multi-pass cell, home-made laser drive circuits, and a data acquisition circuit. The optical and electrical parts and the gas circuit were integrated into a portable carrying case (height = 134 mm, length = 388 mm, and width = 290 mm). A TDLAS drive module (size: 90 mm × 45 mm) was designed to realize the function of laser current and temperature control with a temperature control accuracy of ±1.4 mK and a current control accuracy of ±0.5 µA, and signal acquisition and demodulation. The weight and power consumption of the TDLAS system were only 5 kg and 10 W, respectively. Distributed feedback lasers (2004 nm and 1392 nm) were employed to target CO2 and H2O absorption lines, respectively. According to Allan analysis, the detection limits of CO2 and H2O were 0.13 ppm and 3.7 ppm at an average time of 18 s and 35 s, respectively. The system response time was approximately 10 s. Sensor performance was verified by measuring atmospheric CO2 and H2O concentrations for 240 h. Experimental results were compared with those obtained using a commercial instrument LI-7500, which uses non-dispersive infrared technology. Measurements of the developed gas analyzer were in good agreement with those of the commercial instrument, and its accuracy was comparable. Therefore, the TDLAS sensor has strong application prospects in atmospheric CO2 and H2O concentration detection and ecological soil flux monitoring.

Double-enhanced multipass cell-based wavelength modulation spectroscopy CH4 sensor for ecological applications.

A novel CH4 sensor based on wavelength modulation spectroscopy with a multipass cell was developed for the soil respiration measurement of CH4. A home-made double-enhanced Herriot-type multipass cell with an effective absorption length of 73.926 m and a fiber-coupled distributed feedback diode laser emission at 1653.74 nm were used to design the sensor. The double enhancement of the effective optical pathlength of the multipass cell, absorption line locking, laser intensity normalization, and temperature control of the multipass cell were used to improve cell performance and achieve a minimum detection limit of 10 ppbv and a measurement precision of 6.4 ppbv. Finally, the potential of the developed CH4 sensor for ecological applications was verified by measuring the soil respiration of CH4 and monitoring of CH4 in the atmosphere over a long period.

Standoff sub-ppb level measurement of atmospheric ammonia with calibration-free wavelength modulation spectroscopy.

Ammonia (NH3) plays a significant role in the formation of atmospheric particulate matter, and influences on environmental and public health as well as climate change. Thus, it is important to sensitive measurement of atmospheric NH3. In the present work, a sub-ppb level standoff open-path NH3 sensor was developed for on line, sensitive measurement of atmospheric NH3. A 9.06 µm distributed feedback quantum cascade laser was employed to probe the ammonia absorption lines located on fundamental rotational-vibrational absorption band and calibration-free wavelength modulation spectroscopy technique was employed to retrieve NH3 concentration directly. The standoff open-path NH3 sensor performance was investigated in laboratory corridor with 80 m open path length (Hefei, China) and a minimum detection limit of 0.46 ppb (3σ) was obtained. Finally, field campaign measurement was carried out in a winter wheat farmland (Changshu, China). Field measurement shown that the concentration of NH3 varies from 7 ppb to 30 ppb with an average of 14 ppb. The developed standoff sensor has high potential to be a robust tool for monitoring atmospheric NH3 or study of regional ammonia emissions in farmland or feedlot scale.

Open-path anti-pollution multi-pass cell-based TDLAS sensor for the online measurement of atmospheric H2O and CO2 fluxes.

We report an open-path and anti-pollution multi-pass cell based tunable diode laser absorption spectroscopy (TDLAS) sensor, which was designed for online measurement of atmospheric H2O and CO2 fluxes. It is mainly composed of two plano-convex mirrors coated on a convex surface, which makes it different from traditional multi-pass cells. This design does not allow a direct contact between the coating layer of the lens and air, thereby realizing the anti-pollution effect of the coating layer. Two DFB lasers operating at 1392 nm and 2004 nm were employed to target H2O and CO2 absorption lines, respectively. Allan analysis of variance indicated that detection limits of H2O and CO2 were 5.98 ppm and 0.68 ppm, respectively, at an average time of 0.1 s. The sensor performance was demonstrated by measuring CO2 and H2O flux emissions at Jiangdu Agricultural Monitoring Station in Jiangsu Province. The results were compared with those obtained using the commercial instrument LI-7500, which is based on non-dispersive infrared technology. The developed gas analysis instrument exhibited good consistency with commercial instruments, and its accuracy was comparable; thus, it has strong application prospects for flux measurements in any ecosystem.

A MEMS modulator-based dual-channel mid-infrared laser heterodyne radiometer for simultaneous remote sensing of atmospheric CH4, H2O and N2O.

The performance of a micro-electro-mechanical system (MEMS) modulator-based dual-channel mid-infrared laser heterodyne radiometer (MIR-LHR) was demonstrated in ground-based solar occultation mode for the first time. A MEMS mirror was employed as an alternative modulator to the traditional mechanical chopper, which makes the system more stable and compact. Two inter-band cascade lasers (ICL) centered at 3.53 µm and 3.93 µm, were employed as local oscillators (LO) to probe absorption lines of methane (CH4), water vapor (H2O) and nitrous oxide (N2O). The system stability greater than 1000 s was evaluated by Allan variance. The experimental MIR-LHR spectra (acquired at Hefei, China, on February 24th 2022) of two channels were compared and were in good agreement with simulation spectra from atmospheric transmission modeling. The mixing ratio of CH4, H2O and N2O were determined to be ∼1.906 ppm, 3069 ppm and ∼338 ppb, respectively. The reported MEMS modulator-based dual-channel MIR-LHR in this manuscript has great potential to be a portable and high spectral resolution instrument for remote sensing of multi-component gases in the atmospheric column.

Simultaneous Sensitive Determination of δ13C, δ18O, and δ17O in Human Breath CO2 Based on ICL Direct Absorption Spectroscopy.

Previous research revealed that isotopes 13C and 18O of exhaled CO2 have the potential link with Helicobacter pylori; however, the 17O isotope has received very little attention. We developed a sensitive spectroscopic sensor for simultaneous δ13C, δ18O, and δ17O analysis of human breath CO2 based on mid-infrared laser direct absorption spectroscopy with an interband cascade laser (ICL) at 4.33 µm. There was a gas cell with a small volume of less than 5 mL, and the pressure in the gas cell was precisely controlled with a standard deviation of 0.0035 Torr. Moreover, real-time breath sampling and batch operation were achieved in gas inlets. The theoretical drifts for δ13C, δ18O, and δ17O measurement caused by temperature were minimized to 0.017‱, 0.024‱, and 0.021‱, respectively, thanks to the precise temperature control with a standard deviation of 0.0013 °C. After absolute temperature correction, the error between the system responded δ-value and the reference is less than 0.3‱. According to Allan variance analysis, the system precisions for δ13C, δ18O, and δ17O were 0.12‱, 0.18‱, and 0.47‱, respectively, at 1 s integration time, which were close to the real-time measurement errors of six repeated exhalations.

Humidity enhanced N2O photoacoustic sensor with a 4.53 µm quantum cascade laser and Kalman filter.

A high-sensitivity N2O photoacoustic sensor using a 4.53 µm quantum cascade laser was developed. Sharply enhancement of photoacoustic signal of N2O with the increasing of humidity was investigated experimentally. Finally, 2.3 % water vapor was added to the analyzed sample to improve the vibrational-translational (V-T) relaxation rate of N2O molecule transition, and therefore enhance the N2O photoacoustic signal. High performance with a minimum detection limit of 28 ppbv in 1 s and a measurement precision of 34 ppbv have been achieved, respectively. Kalman adaptive filtering was used to remove the shot-to-shot variability related to the real-time noise in the measurement data and further improve the measurement precision. Without sacrificing the time resolution of the system, the Kalman adaptive filtering improves the measurement precision of the system by 2.3 times. The ability of the N2O photoacoustic sensor was demonstrated by continuous measurement of atmospheric N2O concentration for a period of 7 h.

Transportable mid-infrared laser heterodyne radiometer operating in the shot-noise dominated regime.

A transportable laser heterodyne radiometer (LHR) based on an external cavity quantum cascade laser, operating in the mid-infrared (mid-IR) around 8 µm, was developed for ground-based remote sensing of multiple greenhouse gases. A newly available novel flexible mid-IR polycrystalline fiber was first exploited to couple solar radiation, real-time captured using a portable sun-tracker, to the LHR receiver. Compared to free space coupling of sunlight, the technique usually used nowadays in the mid-IR, such fiber coupling configuration makes the LHR system readily more stable, simpler, and robust. Operation of the LHR with quasi-shot-noise limited performance was analyzed and experimentally achieved by optimizing local oscillator power. To the best of our knowledge, no such performance approaching the fundamental limit has been reported for a transportable LHR operating at a long mid-IR wavelength around 8 µm. CH4 and N2O were simultaneously measured in the atmospheric column using the developed mid-IR LHR. The experimental LHR spectrum of CH4 and N2O was compared and is in good agreement with a referenced Fourier-transform infrared spectrum from the Total Carbon Column Observing Network observation site and with a simulation spectrum from atmospheric transmission modeling.

Development of a 443 nm diode laser-based differential photoacoustic spectrometer for simultaneous measurements of aerosol absorption and NO2.

Measurement of ambient aerosol and nitrogen dioxide (NO2) is important as they are major pollutants from the burning of fossil fuel and biomass. In the present work, a differential photoacoustic spectrometer (D-PAS) was developed for simultaneous, online measurements of aerosol optical absorption and NO2 concentration. A novel photoacoustic resonator was designed and employed in the D-PAS for controlling a large flow rate, improving response time, and keeping the flow noise at a low level. The detection limits of 1.0 Mm-1 and 0.87 ppb for aerosol absorption and NO2 concentration measurements were achieved with a lock-in amplifier time constant of 1 s. The D-PAS accuracy was demonstrated by performing a long-time, continuous measurement of aerosol, and NO2 in ambient air. The measured results of NO2 are consistent with the NOx analyzer and environmental monitoring station results.

A Dual-Laser Sensor Based on Off-Axis Integrated Cavity Output Spectroscopy and Time-Division Multiplexing Method.

In this article, a compact dual-laser sensor based on an off-axis integrated-cavity output spectroscopy and time-division multiplexing method is reported. A complete dual-channel optical structure is developed and integrated on an optical cavity, which allows two distributed feedback (DFB) lasers operating at wavelengths of 1603 nm and 1651 nm to measure the concentration of CO2 and CH4, simultaneously. Performances of the dual-laser sensor are experimentally evaluated by using standard air (with a mixture of CO2 and CH4). The limit of detection (LoD) is 0.271 ppm and 1.743 ppb at a 20 s for CO2 and CH4, respectively, and the noise equivalent absorption sensitivities are 2.68 × 10-10 cm-1 Hz-1/2 and 3.88 × 10-10 cm-1 Hz-1/2, respectively. Together with a commercial instrument, the dual-laser sensor is used to measure CO2 and CH4 concentration over 120 h and verify the regular operation of the sensor for the detection of ambient air. Furthermore, a first-order exponential moving average algorithm is implemented as an effective digital filtering method to estimate the gas concentration.

Compact dual-gas sensor for simultaneous measurement of atmospheric methane, and water vapor using a 3.38 µm antimonide-distributed feedback laser diode.

A simple, compact sensor involving a continuous-wave 3.38 µm distributed feedback laser in combination with a novel compact dense-pattern multipass cell was demonstrated for simultaneous measurement of atmospheric methane and water vapor. The calibration-free direct absorption spectroscopy approach was adopted for data generation and processing. Allan deviation analysis indicates that minimum detection limits (1σ) of 11.0 ppb for CH4 and 100 ppm for H2O were achieved with a 1-s integration time at an optimum pressure of 50 Torr. Atmospheric environmental mixing ratios of these two gases were recorded and analyzed. This newly developed mid-infrared dual-gas sensor is very suitable for trace gas sensing in weight-limited unmanned aerial vehicle- or balloon-embedded field observations.

Laser frequency locking and intensity normalization in wavelength modulation spectroscopy for sensitive gas sensing.

A novel method for laser frequency locking and intensity normalization in wavelength modulation spectroscopy (WMS)-based gas sensor system is reported. The center spacing between two second harmonic peaks demodulated from the rising and falling edges of a scanning triangular wave (for wavelength scan) is employed as a frequency locking reference. Amplitude of the directly acquired sine signal (for wavelength modulation) in the spectral region far away from the absorption feature is employed as an intensity normalization reference. A 50 ppm CH4:N2 sample sealed in a multi-pass cell at 1 atm was employed as the target analyte for demonstration. The frequency locking significantly improves measurement accuracy, and the introduced intensity normalization method realized a ~3 times SNR improvement as compared to the commonly used 1f normalization method under frequency locking conditions. A minimum measurement precision of ~2.5 ppbv was achieved with a normalized noise equivalent absorption coefficient of 1.8 × 10-9 cm-1Hz-1/2.

Dual-Gas Sensor of CH4/C2H6 Based on Wavelength Modulation Spectroscopy Coupled to a Home-Made Compact Dense-Pattern Multipass Cell.

A sensitive dual-gas sensor for the detection of CH4 and C2H6 is demonstrated. Two tunable semiconductor lasers operating at 1.653 µm (for CH4 monitoring) and 1.684 µm (for C2H6) were used as the light source for spectroscopic measurements of CH4 and C2H6. Long-path absorption in a home-made compact dense-pattern multipass cell (Leff = 29.37 m) was employed, combined with wavelength modulation and second harmonic detection. Simultaneous detection of CH4 and C2H6 was achieved by separated wavelength modulations of the two lasers. Modulation frequencies and amplitudes were optimized for sensitivity detection of CH4 and C2H6 simultaneously. The dual-gas sensor exhibits 1σ detection limits of 1.5 ppbv for CH4 in 140 s averaging time and 100 ppbv for C2H6 in 200 s.

Sensing atmospheric reactive species using light emitting diode by incoherent broadband cavity enhanced absorption spectroscopy.

We overview our recent progress in the developments and applications of light emitting diode-based incoherent broadband cavity enhanced absorption spectroscopy (LED-IBBCEAS) techniques for real-time optical sensing chemically reactive atmospheric species (HONO, NO3, NO2) in intensive campaigns and in atmospheric simulation chamber. New application of optical monitoring of NO3 concentration-time profile for study of the NO3-initiated oxidation process of isoprene in a smog chamber is reported.