Off-plane quartz-enhanced photoacoustic spectroscopy.

In this work, we developed off-plane quartz-enhanced photoacoustic spectroscopy (OP-QEPAS). In the OP-QEPAS the light beam went neither through the prong spacing of the quartz tuning fork (QTF) nor in the QTF plane. The light beam is in parallel with the QTF with an optimal distance, resulting in low background noise. A radial-cavity (RC) resonator was coupled with the QTF to enhance the photoacoustic signal by the radial resonance mode. By offsetting both the QTF and the laser position from the central axis, we enhance the effect of the acoustic radial resonance and prevent the noise generated by direct laser irradiation of the QTF. Compared to IP-QEPAS based on a bare QTF, the developed OP-QEPAS with a RC resonator showed a >10× signal-to-noise ratio (SNR) enhancement. The OP-QEPAS system has great advantages in the use of light emitting devices (LEDs), long-wavelength laser sources such as mid-infrared quantum cascade lasers, and terahertz sources. When employing a LED as the excitation source, the noise level was suppressed by ∼2 orders of magnitude. Furthermore, the radial and longitudinal resonance modes can be combined to further improve the sensor performance.

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.

Ppbv-level mid-infrared photoacoustic sensor for mouth alcohol test after consuming lychee fruits.

A ppbv-level mid-infrared photoacoustic spectroscopy sensor was developed for mouth alcohol tests. A compact CO2 laser with a sealed waveguide and integrated radio frequency (RF) power supply was used. The emission wavelength is ∼9.3 µm with a power of 10 W. A detection limit of ∼18 ppbv (1σ) for ethanol gas with an integration of 1 s was achieved. The sensor performed a linear dynamic range with an R square value of ∼0.999. A breath measurement experiment after consuming lychees was conducted. The photoacoustic signal amplitude decreased with the quality of lychee consumed, confirming the existence of residual alcohol in the mouth. During continuous measurement, the photoacoustic signal decreased in < 10 min when consuming 30 g lychee fruits, proving that the alcohol detected in exhaled breath originated from the oral cavity rather than the bloodstream. This work provided valuable information on the distinction of alcoholism and crime.

Helmholtz-resonator quartz-enhanced photoacoustic spectroscopy.

In this work, Helmholtz-resonator quartz-enhanced photoacoustic spectroscopy (HR-QEPAS) was developed for trace gas sensing. A pair of Helmholtz resonators with high-order resonance frequency was designed and coupled with a quartz tuning fork (QTF). Detailed theoretical analysis and experimental research were carried out to optimize the HR-QEPAS performance. As a proof-of-concept experiment, the water vapor in the ambient air was detected using a 1.39 µm near-infrared laser diode. Benefiting from the acoustic filtering of the Helmholtz resonance, the noise level of QEPAS was reduced by >30%, making the QEPAS sensor immune to environmental noise. In addition, the photoacoustic signal amplitude was improved significantly by >1 order of magnitude. As a result, the detection signal-to-noise ratio was enhanced by >20 times, compared with a bare QTF.

Quartz-Enhanced Photoacoustic Spectroscopy-Conductance Spectroscopy for Gas Mixture Analysis.

A novel spectroscopic method, named quartz-enhanced photoacoustic spectroscopy-conductance spectroscopy (QEPAS-CS), was first developed for gas mixture analysis. In QEPAS-CS, the advantage of photoacoustic detection and conductance analysis was realized by a quartz tuning fork (QTF). Two-component gas analysis was done by photoacoustic detection and conductance detection. For an explicit application, natural spider silk was used as a water vapor transducer to modify the QTF, making a conductance sensing channel. A 2004 nm laser diode was used as an excitation source for a photoacoustic sensing channel. Such a QEPAS-CS sensor was used for H2O/CO2 gas mixture analysis in a cell incubator. This provides a solution to calibrate an infrared photoacoustic spectroscopy gas sensor. This example effectively confirms the capacity of multigas analysis by the QEPAS-CS sensor.

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.

Optical amplification enables a huge sensitivity improvement to laser heterodyne radiometers for high-resolution measurements of atmospheric gases.

A novel, to the best of our knowledge, performance-enhanced laser heterodyne radiometer has been developed by utilizing a semiconductor optical amplifier to amplify the collected weak solar radiation in an optical fiber. High-spectral-resolution measurements of atmospheric carbon dioxide column absorption are used to validate the technique and performance of the developed instrument. The implementation of optical amplification led to a 9-times improvement in sensitivity according to the Allan variance analysis for noise fluctuations, and resulted in a 7.7-times enhancement in measurement precision for atmospheric carbon dioxide. The promising results showed the great potential of employing this type of compact fiber-optics-based spectral radiometer for applications such as atmospheric greenhouse gas sensing.

Frequency-Domain Detection for Frequency-Division Multiplexing QEPAS.

To achieve multi-gas measurements of quartz-enhanced photoacoustic spectroscopy (QEPAS) sensors under a frequency-division multiplexing mode with a narrow modulation frequency interval, we report a frequency-domain detection method. A CH4 absorption line at 1653.72 nm and a CO2 absorption line at 2004.02 nm were investigated in this experiment. A modulation frequency interval of as narrow as 0.6 Hz for CH4 and CO2 detection was achieved. Frequency-domain 2f signals were obtained with a resolution of 0.125 Hz using a real-time frequency analyzer. With the multiple linear regressions of the frequency-domain 2f signals of various gas mixtures, small deviations within 2.5% and good linear relationships for gas detection were observed under the frequency-division multiplexing mode. Detection limits of 0.6 ppm for CH4 and 2.9 ppm for CO2 were simultaneously obtained. With the 0.6-Hz interval, the amplitudes of QEPAS signals will increase substantially since the modulation frequencies are closer to the resonant frequency of a QTF. Furthermore, the frequency-domain detection method with a narrow interval can realize precise gas measurements of more species with more lasers operating under the frequency-division multiplexing mode. Additionally, this method, with a narrow interval of modulation frequencies, can also realize frequency-division multiplexing detection for QEPAS sensors under low pressure despite the ultra-narrow bandwidth of the QTF.

Integrated near-infrared QEPAS sensor based on a 28 kHz quartz tuning fork for online monitoring of CO2 in the greenhouse.

In this paper, a highly sensitive and integrated near-infrared CO2 sensor was developed based on quartz-enhanced photoacoustic spectroscopy (QEPAS). Unlike traditional QEPAS, a novel pilot line manufactured quartz tuning fork (QTF) with a resonance frequency f 0 of 28 kHz was employed as an acoustic wave transducer. A near-infrared DFB laser diode emitting at 2004 nm was employed as the excitation light source for CO2 detection. An integrated near-infrared QEPAS module was designed and manufactured. The QTF, acoustic micro resonator (AmR), gas cell, and laser fiber are integrated, resulting in a super compact acoustic detection module (ADM). Compared to a traditional 32 kHz QTF, the QEPAS signal amplitude increased by > 2 times by the integrated QEPAS module based on a 28 kHz QTF. At atmospheric pressure, a 5.4 ppm detection limit at a CO2 absorption line of 4991.25 cm-1 was achieved with an integration time of 1 s. The long-term performance and stability of the CO2 sensor system were investigated using Allan variance analysis. Finally, the minimum detection limit (MDL) was improved to 0.7 ppm when the integration time was 125 s. A portable CO2 sensor system based on QEPAS was developed for 24 h continuous monitoring of CO2 in the greenhouse located in Guangzhou city. The CO2 concentration variations were clearly observed during day and night. Photosynthesis and respiration plants can be further researched by the portable CO2 sensor system.

High-power near-infrared QEPAS sensor for ppb-level acetylene detection using a 28 kHz quartz tuning fork and 10 W EDFA.

A high-power near-infrared (NIR) quartz enhanced photoacoustic spectroscopy (QEPAS) sensor for part per billion (ppb) level acetylene (C2H2) detection was reported. A 1536 nm distributed feedback (DFB) diode laser was used as the excitation light source. Cooperated with the laser, a C-band 10 W erbium-doped fiber amplifier (EDFA) was employed to boost the optical excitation power to improve QEPAS detection sensitivity. A pilot line manufactured quartz tuning fork (QTF) with a resonance frequency of 28 kHz was used as the photoacoustic transducer. In the case of high excitation power, gas flow effect and temperature effect were found and studied. Benefitting from the low QTF resonance frequency, high excitation power, and vibrational-translational (V-T) relaxation promoter, a detection limit of ∼7 ppb was achieved for C2H2 detection, corresponding to a normalized noise equivalent absorption coefficient of 4.4×10-8cm-1 · W · Hz-1/2.

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.

Quasi-Simultaneous Sensitive Detection of Two Gas Species by Cavity-Ringdown Spectroscopy with Two Lasers.

We developed a cavity ringdown spectrometer by utilizing a step-scanning and dithering method for matching laser wavelengths to optical resonances of an optical cavity. Our approach is capable of working with two and more lasers for quasi-simultaneous measurements of multiple gas species. The developed system was tested with two lasers operating around 1654 nm and 1658 nm for spectral detections of 12CH4 and its isotope 13CH4 in air, respectively. The ringdown time of the empty cavity was about 340 µs. The achieved high detection sensitivity of a noise-equivalent absorption coefficient was 2.8 × 10-11 cm-1 Hz-1/2 or 1 × 10-11 cm-1 by averaging for 30 s. The uncertainty of the high precision determination of δ13CH4 in air is about 1.3‰. Such a system will be useful for future applications such as environmental monitoring.

A Fiber-Integrated CRDS Sensor for In-Situ Measurement of Dissolved Carbon Dioxide in Seawater.

Research on carbon dioxide (CO2) geological and biogeochemical cycles in the ocean is important to support the geoscience study. Continuous in-situ measurement of dissolved CO2 is critically needed. However, the time and spatial resolution are being restricted due to the challenges of very high submarine pressure and quite low efficiency in water-gas separation, which, therefore, are emerging the main barriers to deep sea investigation. We develop a fiber-integrated sensor based on cavity ring-down spectroscopy for in-situ CO2 measurement. Furthermore, a fast concentration retrieval model using exponential fit is proposed at non-equilibrium condition. The in-situ dissolved CO2 measurement achieves 10 times faster than conventional methods, where an equilibrium condition is needed. As a proof of principle, near-coast in-situ CO2 measurement was implemented in Sanya City, Haina, China, obtaining an effective dissolved CO2 concentration of ~950 ppm. The experimental results prove the feasibly for fast dissolved gas measurement, which would benefit the ocean investigation with more detailed scientific data.

Radial-cavity quartz-enhanced photoacoustic spectroscopy.

Radial-cavity quartz-enhanced photoacoustic spectroscopy (RC-QEPAS) was proposed for trace gas analysis. A radial cavity with (0,0,1) resonance mode was coupled with the quartz tuning fork (QTF) to greatly enhance the QEPAS signal and facilitate the optical alignment. The coupled resonance enhancement effects of the radial cavity and QTF were analyzed theoretically and researched experimentally. With an optimized radial cavity, the detection sensitivity of QEPAS was enhanced by >1 order of magnitude. The RC-QEPAS makes the acoustic detection module more compact and optical alignment comparable with a bare QFT, benefiting the usage of light sources with poor beam quality.

Development of a Laser Gas Analyzer for Fast CO2 and H2O Flux Measurements Utilizing Derivative Absorption Spectroscopy at a 100 Hz Data Rate.

We report the development of a laser gas analyzer that measures gas concentrations at a data rate of 100 Hz. This fast data rate helps eddy covariance calculations for gas fluxes in turbulent high wind speed environments. The laser gas analyzer is based on derivative laser absorption spectroscopy and set for measurements of water vapor (H2O, at wavelength ~1392 nm) and carbon dioxide (CO2, at ~2004 nm). This instrument, in combination with an ultrasonic anemometer, has been tested experimentally in both marine and terrestrial environments. First, we compared the accuracy of results between the laser gas analyzer and a high-quality commercial instrument with a max data rate of 20 Hz. We then analyzed and compared the correlation of H2O flux results at data rates of 100 Hz and 20 Hz in both high and low wind speeds to verify the contribution of high frequency components. The measurement results show that the contribution of 100 Hz data rate to flux calculations is about 11% compared to that measured with 20 Hz data rate, in an environment with wind speed of ~10 m/s. Therefore, it shows that the laser gas analyzer with high detection frequency is more suitable for measurements in high wind speed environments.

Development of a laser heterodyne spectroradiometer for high-resolution measurements of CO2, CH4, H2O and O2 in the atmospheric column.

We have developed a portable near-infrared laser heterodyne radiometer (LHR) for quasi-simultaneous measurements of atmospheric carbon dioxide (CO2), methane (CH4), water vapor (H2O) and oxygen (O2) column absorption by using three distributed-feedback diode lasers as the local oscillators of the heterodyne detection. The developed system shows good performance in terms of its high spectral resolution of 0.066 cm-1 and a low solar power detection noise which was about 2 times the theoretical quantum limit. Its measurement precision of the column-averaged mole fraction for CO2 and CH4 is within 1.1%, based on the standard deviation from the mean value of the retrieved results for a clean sky. The column abundance information of the O2 is used to correct for the variations and uncertainties of atmosphere pressure, the solar altitude angle, and the prior profiles of pressure and temperature. Comparison measurements of daily column-averaged atmospheric mole fractions of CO2, CH4 and H2O, between our developed LHR and a greenhouse gas observing satellite, show a good agreement, which proves the reliability of our developed system.

A Robust Optical Sensor for Remote Multi-Species Detection Combining Frequency-Division Multiplexing and Normalized Wavelength Modulation Spectroscopy.

By combining frequency-division multiplexing and normalized wavelength modulation spectroscopy, a robust remote multi-species sensor was developed and demonstrated for practical hydrocarbon monitoring. Independently modulated laser beams are combined to simultaneously interrogate different gas samples using an open-ended centimeter-size multipass cell. Gas species of interest are demodulated with the second harmonics to enhance sensitivity, and high immunity to laser power variation is achieved by normalizing to the corresponding first harmonics. Performance of the optical sensor was experimentally evaluated using methane (CH4) and acetylene (C2H2) samples, which were separated by a 3-km fiber cable from the laser source. Sub-ppm sensitivity with 1-s time resolution was achieved for both gas species. Moreover, even with large laser intensity fluctuations ranging from 0 to 6 dB, the noise can be kept within 1.38 times as much as that of a stable intensity case. The reported spectroscopic technique would provide a promising optical sensor for remote monitoring of multi hazardous gases with high robustness.

A novel strategy for creating a new system of third-generation hybrid rice technology using a cytoplasmic sterility gene and a genic male-sterile gene.

Heterosis utilization is the most effective way to improve rice yields. The cytoplasmic male-sterility (CMS) and photoperiod/thermosensitive genic male-sterility (PTGMS) systems have been widely used in rice production. However, the rate of resource utilization for the CMS system hybrid rice is low, and the hybrid seed production for the PTGMS system is affected by the environment. The technical limitations of these two breeding methods restrict the rapid development of hybrid rice. The advantages of the genic male-sterility (GMS) rice, such as stable sterility and free combination, can fill the gaps of the first two generations of hybrid rice technology. At present, the third-generation hybrid rice breeding technology is being used to realize the application of GMS materials in hybrid rice. This study aimed to use an artificial CMS gene as a pollen killer to create a smart sterile line for hybrid rice production. The clustered regularly interspaced short palindromic repeats/CRISPR-associated 9 (CRISPR/Cas9) technology was used to successfully obtain a CYP703A3-deficient male-sterile mutant containing no genetically modified component in the genetic background of indica 9311. Through young ear callus transformation, this mutant was transformed with three sets of element-linked expression vectors, including pollen fertility restoration gene CYP703A3, pollen-lethality gene orfH79 and selection marker gene DsRed2. The maintainer 9311-3B with stable inheritance was obtained, which could realize the batch breeding of GMS materials. Further, the sterile line 9311-3A and restorer lines were used for hybridization, and a batch of superior combinations of hybrid rice was obtained.

Implementation of the toroidal absorption cell with multi-layer patterns by a single ring surface.

We developed a type of toroidal multi-pass cell with multi-layer patterns based on the off-axis model. The effective path length of the original toroidal multi-pass cell is extended several roundtrips in comparison with the single-layer pattern, since the inner surface of the toroidal multi-pass cell is more efficiently utilized. The light pattern has been achieved by using the simple ring surface, which is easy to fabricate. The exact analytical equations for the design of the toroidal multi-pass cell were derived based on analytical vector calculations. A series of numerical ray tracing simulations is presented, and the maximum theoretical optical path length that can be reached is 30 m with a setup of 5 cm column radius. Furthermore, two practical spot patterns are demonstrated with a path length of 8.3 m for a two-layer pattern and 10 m for a three-layer pattern, with respective effective volumes of 63 mL and 94 mL. Furthermore, the fringe effect is substantially reduced to less than 0.5% by the usage of our designed mask.

Development of an in situ analysis system for methane dissolved in seawater based on cavity ringdown spectroscopy.

This paper reports the development of a compact in situ real-time concentration analysis system for methane dissolved in seawater by using a continuous-wave cavity ringdown spectroscopy (CRDS) technique. The miniaturized design of the system, including optical resonance cavity and control and data acquisition-analysis electronics, has a cylindrical dimension of 550 mm in length and 100 mm in diameter. Ringdown signal generation, data acquisition and storage, current driver, and temperature controller of the diode laser are all integrated in the miniaturized system circuits, with an electrical power consumption of less than 12 W. Fitting algorithms of the ringdown signal and spectral line are implemented in a digital signal processor, which is the main control chip of the system circuit. The detection sensitivity for methane concentration can reach 0.4 ppbv with an approximate averaging time of 240 s (or 4 min). Comparing the system's measurement of ambient air against a high-quality commercial CRDS instrument has demonstrated a good agreement in results. In addition, as a "proof of concept" for measuring dissolved methane, the developed instrument was tested in an actual underwater environment. The results showed the potential of this miniaturized portable instrument for in situ gas sensing applications.