光声光谱气体传感技术研究进展

光声光谱是通过光声效应把样品吸收光谱转换成声波探测,实现样品成分、浓度分析检测的一种光谱传感技术,是光谱学的一个重要分支。光声光谱除了具有吸收光谱的高选择性、高灵敏度外,还具有信号只跟样品光吸收有关,不受散射光影响,零背景, 信号与光功率成正比以及信号探测器不受光波长影响等诸多优点。在环境监测、工业过程控制与检测、医学诊断和国防危化品检测等领域得到了越来越多的应用,呈现出快速发展的趋势。除了传统的共振光声光谱技术,近年来先后出现了悬臂增强型光声光谱、石英音叉谐振增强型光声光谱、多通道光声光谱等各具特色的新技术。对光声光谱气体传感技术的研究进展进行了介绍,并分析了其应用前景和未来发展趋势。     

Effect of buffer gases on the performance of SO2 trace measurement based on photoacoustic spectroscopy

In this experimental work a laser photoacoustic spectrometer designed and fabricated. System sensitivity for detection of SO₂ and NO₂ was measured. Resonance frequency variation versus pressure increase of Nitrogen, Argon, Helium and Air buffer gases was studied. Results show that, sensitivity of system for SO₂ and NO₂ are 353 ppb and 963 ppb respectively. It was shown that resonance frequency for Nitrogen, Argon, and Air buffer gases was not noticeably varied by buffer gas pressure increasing, but for Helium, resonance frequency not only is not in range of three other gases, but also grows by pressure increasing. The system noises were damped preparing two buffer chambers.     

NO trace gas sensor based on quartz-enhanced photoacoustic spectroscopy and external cavity quantum cascade laser

A gas sensor based on quartz-enhanced photoacoustic detection and an external cavity quantum cascade laser was realized and characterized for trace nitric oxide monitoring using the NO R(6.5) absorption doublet at 1900.075 cm⁻¹. Signal and noise dependence on gas pressure were studied to optimize sensor performance. The NO concentration resulting in a noise-equivalent signal was found to be 15 parts per billion by volume, with 100 mW optical excitation power and a data acquisition time of 5 s.     

Resonance photoacoustic spectroscopy and gas analysis of gaseous flow at reduced pressure

The results of theoretical and experimental studies of sensitivity of a resonant photoacoustic Helmholtz resonator detector for gas flowing through a photoacoustic cell under reduced pressure are presented. The measurements of the sensitivity and ultimate sensitivity of the differential photoacoustic cell were performed with a near-IR room-temperature diode laser using the well-known H₂O absorption line (12496.1056 cm^-1) as a reference. The measured value of the sensitivity (6–17 Pa W m^-1) is in satisfactory agreement with the calculated one, which equals 6–35 Pa W m^-1. The obtained value of the ultimate sensitivity ((3–5)×10^-7 W m^-1 Hz^-1/2) provides measurements of the concentration of molecules at the ppb–ppm level. Received: 19 April 2001 / Revised version: 18 September 2001 / Published online: 7 November 2001     

Differential Helmholtz resonant photoacoustic cell for spectroscopy and gas analysis with room-temperature diode lasers

The results of theoretical and experimental studies and the design of a multi-purpose differential Helmholtz resonant photoacoustic detector (DHRD) and its applications to high-resolution spectroscopy of molecular gases and gas analysis with a room-temperature diode laser in the near-IR region are summarized. The series of experiments and numerical analysis of the DHRD sensitivity were performed for both types (single-pass and multi-pass) of DHRDs within a wide pressure range 0.1–101 kPa, including the regime of a gas flowing through a DHRD cell. The hardware and electronic arrangement of DHRDs for diode laser spectrometers and gas analyzers providing a limiting absorption sensitivity better than 10^-7 Wm^-1 are described. The results of measurements of spectral line parameters of H₂O near 800 and 1390 nm and CH₄ near 1650 nm (intensities, line broadening and shifting by atomic and molecular gases) are presented and discussed. The problems and the ways of perfection of the methodology and accuracy of DHRD techniques with tunable diode lasers of near-IR and visible spectral ranges are discussed. Received: 1 April 2002 / Revised version: 20 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +7/382-225-8026, E-mail: kvan@asd.iao.ru     

Open-path measurement of ozone and methane gases using quartz-enhanced photoacoustic spectroscopy

We demonstrate a standoff system based on quartz-enhanced photoacoustic spectroscopy technique for the concentration measurements of atmospheric ozone and methane. The technique is a modified version of Photoacoustic spectroscopy. Two primary features of this technique are the employment of a tunable quantum cascade laser and a resonant quartz-crystal tuning fork detector. Both of these features facilitate simultaneous sensing of multiple molecular species. External-cavity quantum cascade laser having a spectral range from 7 to 10 micron is used. Diurnal concentration variations of methane and ozone are estimated for open-path up to 25 m. The ambient methane and ozone concentration maxima were observed to have values of 3.5 parts per million by volume and 140 parts per billion by volume, respectively. Finite-element mesh-based software is used to simulate the Eigen frequency of the tuning fork sensor. High-resolution transmission molecular spectroscopic database of atmospheric gases and the real-time gas concentration data from the Delhi Pollution Control Committee have been used as references.     

Continuous wave optical parametric oscillator for quartz-enhanced photoacoustic trace gas sensing

A continuous wave optical parametric oscillator, generating up to 300 mW idler output in the 3–4 μm wavelength region, and pumped by a fiber-amplified DBR diode laser is used for trace gas detection by means of quartz-enhanced photoacoustic spectroscopy (QEPAS). Mode-hop-free tuning of the OPO output over 5.2 cm^-1 and continuous spectral coverage exceeding 16.5 cm^-1 were achieved via electronic pump source tuning alone. Online monitoring of the idler wavelength, with feedback to the DBR diode laser, provided an automated closed-loop control allowing arbitrary idler wavelength selection within the pump tuning range and locking of the idler wavelength with a stability of 1.7×10^-3 cm^-1 over at least 30 min. Using this approach, we locked the idler wavelength at an ethane absorption peak and obtained QEPAS data to verify the linear response of the QEPAS signal at different ethane concentrations (100 ppbv-20 ppmv) and different power levels. The detection limit for ethane was determined to be 13 ppbv (20 s averaging), corresponding to a normalized noise equivalent absorption coefficient of 4.4×10^-7 cm^-1  W/Hz^1/2. PACS 42.55.Wd; 42.65.Yj; 42.62.Fi     

Resonant photoacoustic detection of trace gas with DFB diode laser

A resonant photoacoustic detection system based on a low-power distributed feedback diode laser is developed. This sensor has been applied to the detection of acetylene (C₂H₂) using a specifically designed photoacoustic cell operating on its second longitudinal mode. The minimum detectable limit of about 10 parts-per-million volume (SNR=1) is achieved with an average laser power of 3.5 mW at atmospheric pressure, and an integration time constant of 3 ms; thus, the minimum detectable absorption coefficient normalised by power and bandwidth is 4.0×10⁻⁸ W cm⁻¹/√Hz. The optimum operating pressure buffered with N₂ is also investigated. The realisation of our system is described and experimental results are compared with different modulation techniques and other results reported in the literature. A number of issues arising from the conventional use of mechanical chopping of the beam can be effectively suppressed in wavelength modulation PA spectroscopy (WM-PAS) and second harmonic detection.     

Optical parametric oscillator based difference frequency laser source for photoacoustic trace gas spectroscopy in the 3 μm mid-IR range

We report on the extension of the emission wavelength range of a nanosecond pulsed commercial optical parametric oscillator (OPO) towards the infrared. By difference frequency mixing the idler of the OPO with the fundamental of its Nd:YAG pump laser the wavelength range from 2.5–4.5 μm is covered at considerable pulse energies. This laser source is then applied for the first time to photoacoustic trace gas spectroscopy in the fundamental C---H stretch band located around 3.3 μm. Spectra of single- and multi-component gas mixtures of volatile organic compounds are recorded and analyzed with respect to composition and concentration. The detection limits for the individual substances within the gas mixtures are found in the lower parts per million (ppm) range.     

Micromechanical photothermal spectroscopy of trace gases using functionalized polymers

We demonstrate a novel method to spectroscopically detect and identify trace gases. Micromechanical photothermal spectroscopy (MPS) with functionalized sorbent materials provides trace gas spectra in an optical interaction length of only a few micrometers. We use microcavity interferometry to read out displacements as low as 25 fm/√Hz, heating as low as 200 pW/√Hz, and analyte concentrations as low as 65 parts-per-billion for the nerve agent simulant DMMP. MPS integrated with functional materials represents an important new tool in chip-scale optical sensing.     

Design, simulation and structural optimization of a longitudinal acoustic resonator for trace gas detection using laser photoacoustic spectroscopy (LPAS)

The design of the acoustic resonator is critical for the optimization of the sensitivity of laser photoacoustic spectroscopy (LPAS) in trace gas detection applications. In this paper, an LC circuit model is used for the simulation of a 1D acoustic resonator. This acoustic resonator is designed for CO photoacoustic spectroscopy. The effects of the structural parameters, quality factor and resonant frequency on the performance of the device are theoretically analyzed. The role of the buffer volume as an acoustic filter is investigated and optimized dimensions of the buffer volume, to achieve minimum noise transmission coefficient, are calculated. The effects of the ambient temperature, variety of pressure and gas flow velocity on the resonant frequency of photoacoustic resonator and PA signal are simulated. The temperature dependence of the microphone sensitivity is also introduced.     

Ammonia trace measurements at ppb level based on near-IR photoacoustic spectroscopy

A photoacoustic sensor using a laser diode emitting near 1532 nm in combination with an erbium-doped fibre amplifier has been developed for ammonia trace gas analysis at atmospheric pressure. NH₃ concentration measurements down to 6 ppb and a noise-equivalent detection limit below 3 ppb in dry air are demonstrated. Two wavelength-modulation schemes with 1f and 2f detection using a lock-in amplifier were investigated and compared to maximise the signal-to-noise ratio. A quantitative analysis of CO₂ and H₂O interference with NH₃ is presented. Typical concentrations present in ambient air of 400 ppm CO₂ and 1.15% H₂O (50% relative humidity at 20 °C) result in a NH₃ equivalent concentration of 36 ppb and 100 ppb, respectively. PACS 42.62.Fi; 43.35.Ud; 42.55.Px     

基于中红外分布反馈量子级联激光器的光声光谱技术用于痕量甲烷气体检测

由于工业监控和环境检测的需要,甲烷气体检测日益得到人们的关注。研究了基于中红外分布反馈量子级联激光器(DFB-QCL)的光声光谱技术,并应用于痕量甲烷的检测。自主研发的DFB-QCL室温工作时的激射波长在7.6μm附近,覆盖了甲烷的特征吸收谱线1 316.83cm-1。待测甲烷气体充入亥姆霍兹光声谐振腔中,DFB-QCL的工作频率为234Hz、室温脉冲工作时峰值功率为80mW。中红外光经过甲烷吸收后,产生的声波信号经麦克风检测,由锁相放大器对信号进行采集并输入计算机进行处理。按信噪比为1计算,得到甲烷的探测极限为189nmol.mol-1。     

Laser photoacoustic spectroscopy of biosystems gas exchange with the atmosphere

2 evolution by some plants exposed to elevated concentration of pollutants and pressure decrease is studied using a photoacoustic spectrometer with a CO₂ laser. The measurements show a considerable CO₂ evolution by all kinds of the test plants. The quantity of CO₂ emitted by pea seedlings at 8 kPa, for example, exceeds the control one by about 20 times (24 h after the exposure start). The exposure of pea seedlings to C₂H₄ and O₃ at various concentrations also increases CO₂ evolution: the 48-h exposure of test plants to C₂H₄ (at 0.01 ppm) increases CO₂ evolution by approximately 100% with respect to the control plants. Received: 09 April 1998     

光声光谱气体检测系统中气体湿度的影响研究

工作环境是光声光谱气体检测系统在工业现场应用的重要影响因素.实验发现,待测气体湿度对电容式微音器灵敏度影响显著,导致现有光声光谱气体榆测系统测试结果漂移.文章提出一种气体湿度影响消除方法,在光声腔中安装扬声器,以扬声器信号幅值作为声感应器件灵敏度的自适应表征,对光声信号幅值作自行修正,有效克服电容式微音器声信号榆测中灵...     

Theoretical analysis of a quartz-enhanced photoacoustic spectroscopy sensor

Quartz-enhanced photoacoustic spectroscopy (QEPAS) sensors are based on a recent approach to photoacoustic detection which employs a quartz tuning fork as an acoustic transducer. These sensors enable detection of trace gases for air quality monitoring, industrial process control, and medical diagnostics. To detect a trace gas, modulated laser radiation is directed between the tines of a tuning fork. The optical energy absorbed by the gas results in a periodic thermal expansion which gives rise to a weak acoustic pressure wave. This pressure wave excites a resonant vibration of the tuning fork thereby generating an electrical signal via the piezoelectric effect. This paper describes a theoretical model of a QEPAS sensor. By deriving analytical solutions for the partial differential equations in the model, we obtain a formula for the piezoelectric current in terms of the optical, mechanical, and electrical parameters of the system. We use the model to calculate the optimal position of the laser beam with respect to the tuning fork and the phase of the piezoelectric current. We also show that a QEPAS transducer with a particular 32.8 kHz tuning fork is 2–3 times as sensitive as one with a 4.25 kHz tuning fork. These simulation results closely match experimental data.     

Environmental trace gas detection using laser spectroscopy

This special issue of Applied Physics B – Lasers and Optics attempts to document the current status and trends of environmental trace gas detection through a collection of 32 invited papers motivated in part by the need for and importance of a detailed understanding of our environment. Although numerous traditional optical methods, gas chromatography, and mass spectrometry have served us extremely well in atmospheric and environmental trace gas detection, promising new sensing and precise measurement techniques based on laser spectroscopy have emerged and been successfully used in numerous applications. The concept and timing of this special issue has been stimulated to some extent by recent exciting developments of several novel technologies, such as diode and fiber lasers for the optical communications industry, diode-pumped solid-state lasers, and novel bulk and waveguide infrared nonlinear materials. These can be applied to the ultra-sensitive, highly selective detection and real-time analysis of a large number of trace gas species by means of absorption spectroscopy in the mid-infrared fingerprint region, which contains virtually all the fundamental vibrational modes of molecules. Reduction of cost and complexity makes such spectroscopic sources more universally available and user friendly to both established and new fields that include air quality, atmospheric chemistry, industrial, traffic, and rural emissions, chemical analysis and process control, and medical applications.This issue, consisting of two parts, chronicles some of the most significant and representative current research trends. It is hoped that this issue will inspire new directions to both specialists and newcomers in which to drive this exciting field and envision future applications of environmental sensing.Part I: Spectroscopic air monitoring techniques and instrumentation

宽带腔增强吸收光谱技术应用于痕量气体探测及气溶胶消光系数测量

基于氙灯的非相干宽带腔增强吸收光谱系统, 并将其应用于痕量气体及气溶胶消光系数的测量. 该系统的探测灵敏度通过测量NO₂在520—560 nm波长范围内的吸收得到验证, 最小可探测灵敏度为1.8× 10^-7cm^-1 (1σ, 0.12 s积分时间, 50次平均), 对应的NO₂探测极限～33 nmol/mol. 结合标准气溶胶粒子发生系统, 测量了不同浓度的单分散硫酸铵气溶胶粒子在532 nm波长处的消光系数, 得到粒径为600 nm的硫酸铵气溶胶的消光截面为1.12× 10^-8cm², 与文献报道值1.167× 10^-8cm²相一致, 验证了气溶胶测量的可行性和准确性.