Absorption spectroscopy with quantum cascade lasers

Novel pulsed and cw quantum cascade distributed feedback (QC-DFB) lasers operating near lambda=8 micrometers were used for detection and quantification of trace gases in ambient air by means of sensitive absorption spectroscopy. N2O, 12CH4, 13CH4, and different isotopic species of H2O were detected. Also, a highly selective detection of ethanol vapor in air with a sensitivity of 125 parts per billion by volume (ppb) was demonstrated.     

基于可调谐激光吸收光谱的大气甲烷监测仪

可调谐二极管激光吸收光谱(TDLAS)技术利用二极管激光器波长调谐特性,获得被测气体的特征吸收光谱范围内的吸收光谱,从而对污染气体进行定性或者定量分析,这种方法不仅精度较高,选择性强而且响应速度快,已经被用于大气痕量气体监测以及工业控制。在对空气中的痕量气体进行检测中,由于气体浓度较低,需要和长吸收光程技术相结合。将可调谐二极管激光吸收光谱与经过108次反射后达到27 m光程的多次反射池相结合研制了用于地面环境空气中甲烷含量监测的便携式吸收光谱仪,并结合了用于微弱信号检测的二次谐波检测技术,从而达到了体积分数低于1×10-7的检测限,并利用不同体积分数的甲烷气体对系统进行了测试,得到了很好的测试结果。     

Rapid formaldehyde monitoring in ambient air by means of mid-infrared cavity leak-out spectroscopy

We report the spectroscopic detection of formaldehyde in ambient air using cavity leak-out spectroscopy, a cw variant of cavity ring-down spectroscopy. This technique proved to be suitable for a real-time quantitative analysis of polluted air without any preprocessing of the air sample. Using a tunable CO-overtone sideband laser for the λ=3 μm spectral region and a ring-down cell with R=99.95% mirrors, we achieved a detection limit of 2 parts per billion formaldehyde in ambient air, corresponding to a minimum detectable absorption coefficient of 7×10^-9/cm (sampling time: 2 s). Calibration problems arising from the polarity of the molecule and due to HITRAN database uncertainties are discussed. Received: 28 March 2002 / Revised version: 7 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-211/811-3121, E-mail: muertz@uni-duesseldorf.de     

Mid-infrared cavity leak-out spectroscopy for ultrasensitive detection of carbonyl sulfide

We present a ringdown absorption spectrometer based on a continuous-wave CO laser in the mid-infrared spectral region near lambda = 5 microm. Using a linear ringdown cavity (length, 0.5 m) with R > = 99.99% mirrors, we observed a noise-equivalent absorption coefficient of 7 x 10(-11) cm(-1) Hz(-1/2). This is 2 orders of magnitude improved compared with previous values. With this setup we studied the spectroscopic detection of carbonyl sulfide (here abbreviated OCS) traces in ambient air and in exhaled breath. We achieved a detection limit of 7 parts in 10(12) (parts per trillion) OCS in ambient air, which is unprecedented and shows great promise for environmental and biomedical applications.     

基于TDLAS-WMS的中红外痕量CH_4检测仪

为了对痕量甲烷(CH4)进行非接触式检测,采用可调谐二极管激光吸收光谱(TDLAS)与波长调制光谱(WMS)的检测技术,利用CH4位于中红外波段1 332.8cm-1吸收谱线,设计并研制出痕量CH4检测仪。该仪器使用中心波长为7.5μm的中红外量子级联激光器(QCL),通过调谐系数-0.2cm-1·A-1,采用固定工作温度调节其注入电流(0.6~1.6 A)的方式使其发光光谱扫描CH4气体吸收谱线(1 332.8cm-1)。在光学结构方面,该仪器采用光程为76m的herriott长光程密闭气体吸收气室,配合差分检测光路,降低了由激光光源波动引起的噪声,确保对痕量CH4进行检测。实验中,实现了40×10-9最低检测下限,检测结果的相对误差为0.09%,稳定度优于2.8%,验证了该仪器的可行性。     

高灵敏度激光吸收光谱中的微弱信号处理

可调谐二极管激光频率调制吸收光谱（FM-TDLAS）技术是一种高灵敏度的痕量气体检测方法。为改善以CH₄为目标气体检测系统的信噪比,提高系统的检测灵敏度,以双平衡混频器（double balanced mixer）为核心,设计了一套用于提取被噪声淹没的微弱信号的调制解调高频相敏探测器。在对高频相敏探测器进行具体设计和分析的基础上, 结合实验,利用CH₄气体在1653nm附近的近红外吸收光谱,对整体电路的性能进行了测试,获得了具有较高信噪比的二次和一次谐波信号,检测灵敏度可达10×10^-6。     

Performance characteristics of narrow linewidth fiber laser pumped mid-IR difference frequency mixing light source for methane detection.

A high-power, narrow-linewidth Yb fiber laser with a fiber Bragg grating (FBG) pumped difference frequency generation (DFG) in a periodically poled lithium niobate (PPLN) crystal was investigated in detail. A mid-IR power of approximately 2.3 microW at 3.3 micrometers with a slope efficiency of 0.85 mW/W2 was achieved. A Doppler-broadened absorption spectrum of CH4 at 3038.497 cm-1 (3.2911 micrometers) was obtained with a 0.1-m long-gas cell at a pressure of 133 Pa. The linewidth of the DFG source was evaluated to be less than 96 MHz from the observed spectral linewidth. Real-time monitoring of CH4 (approximately 1.78 ppm) in ambient air in a multipass cell which has an optical path length of 10 m was also demonstrated.     

基于可调谐二极管激光吸收光谱波长调制技术在线测量燃烧场温度

 介绍了可调谐二极管激光吸收光谱（TDLAS）波长调制技术的测温原理。通过选择水在1 397.75 nm和1 397.87 nm处两条邻近的吸收线,运用多功能数据采集卡对二极管激光器进行控制和信号采集,实现了TDLAS波长调制技术对标定燃烧炉甲烷/空气预混火焰温度的实时在线测量,测量重复频率为250 Hz。分析了温度测量数据抖动的原因,结果表明燃烧过程中火焰本身温度的抖动是测量结果波动的主要原因,测量系统的A类标准不确定度小于53 K。     

Isotopic ratio measurement of methane in ambient air using mid-infrared cavity leak-out spectroscopy

We report on infrared laser spectroscopic measurements of the isotopic composition of methane (¹²CH₄, ¹³CH₄) in natural air samples with a cavity ring-down technique. A CO overtone sideband laser is utilized to excite a high-finesse cavity which provides an effective optical absorption path length of 3.6 km. We achieved a detection limit of 105 ppt methane in ambient air using an integration time of 20 s. This corresponds to a minimum detectable absorption of 1.9×10^-9 /cm. Rapid determination of the ¹³C/¹²Cisotopic ratio of methane in ambient air without sample preconcentration or gas processing is realized. The present system requires only few minutes for an isotopic ratio measurement with a precision of 11%o . Received: 14 July 2000 / Revised version: 25 October 2000 / Published online: 6 December 2000     

An approach of open-path gas sensor based on tunable diode laser absorption spectroscopy

Tunable diode laser absorption spectroscopy (TDLAS) is a new method to detect trace-gas qualitatively or quantificationally based on the scan characteristic of the diode laser to obtain the absorption spectroscopy in the characteristic absorption region. A time-sharing scanning open-path TDLAS system using two near infrared distributed feedback (DFB) tunable diode lasers is designed to detect CH4 and H2S in leakage of natural gas. A low-cost Fresnel lens is used in this system as receiving optics which receives the laser beam reflected by a solid corner cube reflector with a distance of up to about 60 m. High sensitivity is achieved by means of wavelength-modulation spectroscopy with second-harmonic detection. The minimum detection limits of 1.1 ppm·m for CH4 and 15 ppm·m for H2S are demonstrated with a total optical path of 120 m. The simulation monitoring experiment of nature gas leakage was carried out with this system. According to the receiving light efficiency of optical system and detectable minimum light intensity of detection, the detectable optical path of the system can achieve 1 - 2 km. The sensor is suitable for natural gas leakage monitoring application.     

基于可调谐二极管激光吸收光谱遥测CH4浓度

文章对可调谐二极管激光的直接吸收和波长调制光谱进行了理论分析,设计了一套用于研究甲烷吸收特性的测量系统.近红外二极管激光工作在室温下,选用波长为1.65 μm,利用甲烷的2v3带R(3)线实现对甲烷气体的吸收测量,对测量的信噪比和系统的基本噪声源进行了分析,为实现甲烷浓度的在线遥测打下基础.     

可调谐半导体激光吸收光谱法对高温甲烷的测量研究

可调谐半导体激光吸收光谱(TDLAS)是一种具有高灵敏度、高分辨率、快速检测特点的气体检测技术,已广泛用于大气中多种痕量气体的检测以及地面的痕量气体和气体泄漏的检测。研究了利用TDLAS技术测量高温下甲烷浓度的实验方法,使用可加热的静态吸收池对在1653.72nm波长附近R(3)支转动跃迁的吸收线进行了测量,并计算了吸收线强。分别在相同温度不同浓度和相同浓度不同温度的两种条件下进行了实验。结果表明,利用直接吸收的方法,在实验室可以得到370K时的最小可探测限为100×10-6,500K时的最小可探测限为245×10-6(吸收池长度为10cm),可以应用在燃烧控制及喷焰气体浓度测量等多个领域。     

基于可调谐激光吸收光谱技术的脱硝过程中微量逃逸氨气检测实验研究

为了对电厂脱硝过程中逃逸的微量氨气进行在线检测,实验室采用可调谐激光吸收光谱技术对常温常压下以及不同温度下的低浓度氨气进行了测量试验,其中电厂逃逸氨气检测处温度约为650 K。通过分析近红外波段的氨气吸收谱线,并考虑实际测量环境H₂O和CO₂等浓度很大的气体吸收谱线的干扰,实验选取2.25 μm附近的ν₂+ν₃谱线作为浓度检测谱线。为了验证所选谱线对低浓度NH₃的测量能力,实验对H₂O,CO₂和NH₃的吸收谱线进行模拟,发现低浓度NH₃受较大浓度的H₂O和CO₂谱线的干扰较小,尤其是CO₂谱线的干扰可以忽略不计,且2.25 μm处谱线强度远远大于通讯波段1.53 μm处的谱线。基于新型Herriott池以及高温管式炉,结合可调谐激光吸收光谱中的直接吸收技术和波长调制技术,实现了对不同温度下超低浓度NH₃的高分辨率快速检测。常温常压下其线型函数可以利用洛伦兹线型来近似描述,直接吸收测量技术可以使探测极限降低到0.225×10-6。通过采用简单降噪处理技术如多次平均、简单小波分析等,得到不同温度下的谐波信号与浓度具有良好的线性关系,为采用可调谐激光吸收光谱技术进行现场低浓度逃逸氨气检测提供了很好的依据。     

Impact of water table depth on forest soil methane turnover in laboratory soil cores deduced from natural abundance and tracer 13C stable isotope experiments

We investigated turnover of methane (CH4) in soils from a poorly drained UK forest. In situ, this forest exhibited a negligible soil-atmosphere CH4 flux, whereas adjacent grassland plots were sources of CH4. We hypothesised that the forest plots exhibited reduced anaerobic CH4 production through water-table draw down. Consequently, we exposed soil cores from under oak to high and low water-table conditions in the laboratory. Methane fluxes increased significantly in the high water-table (1925+/-1702 mug CH4 m(-2) h(-1)) compared to the low one (-3.5+/-6.8 microg CH4 m(-2) h(-1)). Natural abundance delta13C values of CH4 showed a strong depletion in high water-table cores (-56.7+/-2.9 per thousand) compared to methane in ambient air (-46.0 per thousand) indicative of methanogenic processes. The delta13C values of CH4 from low water-table cores (delta13C-46.8+/-0.2 per thousand) was similar to ambient air and suggested little alteration of headspace CH4 by the soil microbial community. In order to assess the CH4 oxidizing activity of the two treatments conclusively, a 13CH4 spike was added to the cores and 13CO2 production was measured as the by-product of CH4 oxidation. 13CH4 oxidation rates were 57.5 (+/-12.7) and 0.5 (+/-0.1) microg CH4 m(-2) h(-1) for high and low water-tables, respectively. These data show that the lower water-table hydrology treatment impacted methanogenic processes without stimulating methanotrophy.     

可调谐二极管激光吸收光谱法监测大气痕量气体中的浓度标定方法研究

可调谐二极管激光吸收光谱(TDLAS)技术是利用二极管激光器波长调谐特性,获得被测气体的特征吸收光谱范围内的吸收光谱,从而对污染气体进行定性或者定量分析。在空气痕量气体检测中,一般需要和长光程吸收池相结合使用。可调谐二极管激光吸收光谱法就是在可调谐二极管激光器与长光程吸收池技术相结合的基础上发展起来的一种新的痕量气体检测方法。这种方法不仅精度较高,选择性强而且响应速度快。已经广泛用于大气中多种痕量气体的检测以及地面的痕量气体和气体泄漏的检测。在大部分痕量气体检测仪器中需要精确地对检测气体进行在线的浓度标定,文章介绍了一个简单而精确的浓度标定方法,从理论上进行了分析,然后通过实验证明了这种方法的可行性。     

Laser spectroscopic instrumentation and techniques: long-path monitoring by resonance absorption

Tunable laser spectroscopy has necessitated the introduction of new measurement techniques, particularly with regard to the wavelength calibration. This paper highlights some of these requirements and surveys laser spectroscopic measurements which have already been performed in the infrared. The rather unique properties of tunable infrared lasers also make them useful for air pollution monitoring. In particular, several tunable laser techniques have been used for long-path monitoring of ambient gases in the atmosphere by resonance absorption. The results of these measurements and prospects for the future will be discussed.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

Development of improved PLIF CH detection using an Alexandrite laser for single-shot investigation of turbulent and lean flames

We report on the development of planar laser-induced fluorescence (PLIF) for CH imaging with improved detection sensitivity for single-shot investigations of turbulent, lean, premixed flames. A ring-cavity, pulsed Alexandrite laser was frequency-doubled to excite the lines in the R-branch band-head of the B-X (0,0) band and broadband fluorescence from the B-X (0,1), A-X (1,1) and (0,0) bands, overlapping in the spectral range around 431 nm, was collected. The employed Alexandrite laser, which is characterized by its long pulse duration (150 ns), gives a tunable laser beam around 775 nm with a pulse energy for the second harmonic at the CH absorption wavelength of about 70 mJ. Moreover, the laser has the possibility to be operated in narrow bandwidth (100 MHz) or broad bandwidth (8 cm⁻¹). An introductory high resolution excitation scan over the R-branch band-head was performed and, in addition, saturated excitation with the broadband option of the laser was investigated. By simultaneous excitation of several rotational transitions and to bring these transitions close to saturation, high signal-to-noise ratios were reached over a wide range of equivalence ratios. A sharp and thin CH layer was observed in single-shot PLIF images from laminar premixed methane/air flames from Φ = 0.6 to Φ = 1.5. Finally, the impact of the developed CH PLIF technique is demonstrated in a highly turbulent, lean, partially premixed methane/air flame established on a co-axial jet flame burner.     

CO2分子的近红外二极管激光吸收光谱灵敏探测

利用近红外二极管激光波长调制技术与二次谐波探测结合初步观测了CO2 分子在波长 1.5 7μm附近的吸收 ,获得了最小可探测吸收为 8.6× 10 -5(信噪比为 2 ) ,对应 5 0 0× 10 -6m-1的探测灵敏度。