Real-time detection of 13CH4 in ambient air by use of mid-infrared cavity leak-out spectroscopy

We report on spectroscopic real-time detection of (13)CH(4) in ambient air. Our measurements were carried out by means of cavity leak-out absorption spectroscopy employing a tunable cw laser in the mid-infrared spectral region near lambda = 3 mum. A CO laser in combination with tunable microwave sideband generation was used as the light source. Using a 50-cm-long ringdown cell with R = 99.98% mirrors, we achieved a detection limit of 290 parts in 10(12) (ppt) (13)CH(4) in ambient air (integration time, 100 s). The corresponding noise-equivalent absorption coefficient was 5 x 10(-9)/cm.     

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     

Ba原子6s6p1P1←6s6s1S0跃迁的光腔衰荡光谱

建立了一套光腔衰荡原子束吸收光谱测量装置,并对Ba原子的6s6p¹P₁←6s6s¹S₀吸收谱线用光腔衰荡光谱方法进行了测量,得到了Ba原子在553.548nm不同温度下的吸收谱线线型.实验结果表明,该装置测量吸收灵敏度达到6×10^-7. 关键词： 光腔衰荡 吸收光谱 Ba原子     

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.     

Application of a broadband blue laser diode to trace NO2 detection using off-beam quartz-enhanced photoacoustic spectroscopy

We applied for the first time, to our knowledge, broadband off-beam quartz-enhanced photoacoustic spectroscopy (BB-OB-QEPAS) to trace NO2 detection using a broadband blue laser diode centered at 450?nm. A detection limit of 18?ppbv (parts in 10(9) by volume) for NO2 in N2 at atmospheric pressure was achieved with an average laser power of 7?mW at a 1?s integration time, which corresponds to a 1?σ normalized noise equivalent absorption coefficient of 4.1×10(-9) cm(-1)?W=Hz(1=2). An Allan variance analysis was performed to investigate the long-term stability of the BB-OB-QEPAS-based NO2 sensor.     

基于光腔衰荡光谱的便携式呼气异戊二烯分析仪性能评估

呼气异戊二烯是一种内源性代谢产物,其含量与人体血液中的胆固醇水平存在关联。但人体呼气影响因素众多,寻找其与胆固醇水平诊断参数的定量相关性,需要对选取的特定人群进行有效的呼吸气体分析（实时、在线、高灵敏度、高选择性、高精度的大量呼气数据获取）。光腔衰荡光谱（CRDS）是一种具有极高灵敏度、稳定性和选择性的光谱技术。采用目前市场在售的单波长紧凑型半导体紫外激光器,搭建了一套基于CRDS的呼气异戊二烯分析仪,该分析仪主要由激光系统、真空腔体、光电探测模块以及数据采集模块构成。线性拟合的结果显示所获得的衰荡信号接近单指数衰减（R2=0.998 39）,符合朗伯-比尔定律。探究了不同信号平均次数对衰荡信号稳定性的影响,综合考虑衰荡信号的稳定性和分析仪的响应时间,采用128次作为实验过程中的信号平均次数。对呼气异戊二烯分析仪的性能进行了测试,为了表征分析仪的稳定性,持续测量了分析仪16 min的真空衰荡时间。使用氮气、空气和呼吸样本,测量了呼气异戊二烯分析仪的重复性和响应速度。为了测试分析仪的线性度,测量了不同粒子数密度的异戊二烯标准气体（10×10-9,30×10-9,50×10-9,100×10-9,200×10-9）的衰荡时间。最后分析了在224 nm测量异戊二烯存在的光谱干扰问题（NO,N₂O和丙酮）。实验表明：分析仪具有高的灵敏度（检测极限为0.49×10-9）、良好的重复性、稳定性（0.48%）、近实时的响应速度（1秒测量一个数据）和良好的线性度（R2=0.993 13）,将检测极限提高至现有水平的1/1 000。研究证明基于CRDS的便携式呼气异戊二烯分析仪可实现对人体呼气异戊二烯的有效分析。     

Cavity ringdown spectroscopy using mid-infrared quantum-cascade lasers

Cavity ringdown spectra of ammonia at 10 parts in 10(9) by volume (ppbv) and higher concentrations were recorded by use of a 16-mW continuous-wave quantum-casacde distributed-feedback laser at 8.5 mum whose wavelength was continuously temperature tuned over 15 nm. A sensitivity (noise-equivalent absorbance) of 3.4x10(-9) cm(-1) Hz(-1/2) was achieved for ammonia in nitrogen at standard temperature and pressure, which corresponds to a detection limit of 0.25 ppbv.     

Time resolved simultaneous detection of 14NO and 15NO via mid-infrared cavity leak-out spectroscopy

We present a ring-down absorption spectrometer based on a continuous-wave CO laser in the mid-infrared spectral region near lambda = 5 microm. Using a linear ring-down cavity (length: 0.5 m) with high reflective mirrors (R = 99.988 %), we observed a noise-equivalent absorption coefficient of 3 x 10(-10) cm(-1)Hz(-1/2). This corresponds to a noise-equivalent concentration of 800 parts per trillion (ppt) for (14)NO and 40 ppt for (15)NO in 1 s averaging time. We achieve a time resolution of 1 s which allows time resolved simultaneous detection of the two N isotopes. The delta(15)N value was obtained with a precision of +/-1.2 per thousand in a sample with a NO fraction of 11 ppm. The simultaneous detection enables the use of (15)NO as a tracer molecule for endogenous biomedical processes.     

VCSEL-based oxygen spectroscopy for structural analysis of pharmaceutical solids

We present a minimalistic and flexible single-beam instrumentation based on sensitive tunable diode laser absorption spectroscopy (TDLAS) and its use in structural analysis of highly scattering pharmaceutical solids. By utilising a vertical cavity surface emitting laser (VCSEL) for sensing of molecular oxygen dispersed in tablets, we address structural properties such as porosity. Experiments involve working with unknown path lengths, severe backscattering and diffuse light. These unusual experimental conditions has led to the use of the term gas in scattering media absorption spectroscopy (GASMAS). By employing fully digital wavelength modulation spectroscopy and coherent sampling, system sensitivity in ambient air experiments reaches the 10^-7 range. Oxygen absorption exhibited by our tablets, being influenced by both sample porosity and scattering, was in the range 8×10^-5 to 2×10^-3, and corresponds to 2–50 mm of path length through ambient air (L_eq). The day-to-day reproducibility was on average 1.8% (0.3 mm L_eq), being limited by mechanical positioning. This is the first time sub-millimetre sensitivity is reached in GASMAS. We also demonstrate measurements on gas transport on a 1-s time scale. By employing pulsed illumination and time-correlated single-photon counting, we reveal that GASMAS exhibits excellent correlation with time-domain photon migration. In addition, we introduce an optical measure of porosity by relating oxygen absorption to average photon time-of-flight. Finally, the simplicity, robustness and low cost of this novel TDLAS instrumentation provide industrial potential. PACS 42.62.Fi; 39.30.+w; 78.55.Mb; 42.62.Cf; 87.64.Cc     

Wavelength modulated off-axis integrated cavity output spectroscopy in the near infrared

A novel instrument based on an improved off-axis alignment of integrated cavity output spectroscopy (OA-ICOS) in conjunction with a wavelength modulation (WM) technique, was developed using a DFB diode laser operating in the near infrared at 1.573 μm (6357.3 cm^-1). The laser-based sensor employed a 44 cm optical cavity that provided an effective absorption path length of ∼68 m. A minimum detectable absorption of approximately 3.6 ppmv Hz^-1/2 or 2.3×10^-7 Hz^-1/2 per optical pass was obtained using second harmonic detection. We demonstrated that by implementation of the WM technique to OA-ICOS in the near infrared, the detection sensitivity was improved by a factor of 14 compared to that obtained with OA-ICOS. Measurements of CO₂ mixing ratios in ambient air have been performed by using both OA-ICOS and WM-OA-ICOS techniques for performance comparison. PACS 42.62.Fi; 07.07.Df; 33.20.Ea     

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。     

NO2分子高灵敏度痕量探测技术研究

 搭建了一台基于蓝光LED的非相干宽带腔增强吸收光谱系统,并将其应用于NO2分子的高灵敏度痕量探测研究。在3 s采样时间下, 系统探测灵敏度为3.2×10-9 cm-1（1 σ）,对应NO2的探测极限约为187 pmol/mol。利用Allan方差对系统最佳采样时间及系统稳定性进行分析,当采样时间延长至30 s时,系统的探测极限可提高至44 pmol/mol。将该系统应用于实际大气中NO2的连续测量,其测量结果与商业化NOx分析仪（Thermo 42i）进行了比对测试。     

Rapidly swept, continuous-wave cavity ringdown spectroscopy with optical heterodyne detection: single- and multi-wavelength sensing of gases

Spectroscopic sensing of gases can be performed with high sensitivity and photometric precision by cavity ringdown (CRD) absorption spectroscopy. Our cavity ringdown spectrometer incorporates continuous-wave (cw) tunable diode lasers, fibre-optic coupling and standard photonics and optical telecommunications components. It comprises a rapidly swept optical cavity in a single-ended optical heterodyne transmitter–receiver configuration, enabling optical absorption of gases to be recorded either as single-frequency scanned spectra or as simultaneous, multi-wavelength tailored spectra. By measuring weak near-infrared rovibrational spectra of carbon dioxide gas (CO₂), with high resolution in the vicinity of 1.53 μm, we have realised a noise-limited absorption sensitivity of 2.5×10^-9 cm^-1 Hz^-1/2. Analytical sensitivity limits (both actual and projected) and prospective gas-diagnostic applications are discussed. Our approach to cw-CRD spectroscopy offers high performance in a relatively simple, low-cost, compact instrument that is amenable to chemical analysis of trace gases in medical, agricultural, industrial and environmental situations. Received: 16 May 2002 / Revised version: 3 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +61-2/9850-8313, E-mail: brian.orr@mq.edu.au     

Mode-by-mode optical feedback: cavity ringdown spectroscopy

We describe a new continuous wave cavity ringdown spectroscopy (cw-CRDS) approach using an extended cavity diode laser (ECDL) optically self-locked to a high finesse cavity including an intracavity glass plate under the Brewster angle. Low noise, mode-by-mode absorption spectra are recorded at a high acquisition rate (laser frequency scan greater than 400 GHz/s) and covering four orders of magnitude in absorption coefficient. Sampling spectra with the fixed high finesse cavity frequency comb provides high precision frequency markers. An original scheme for the laser beam shut-down, based on signal shape analysis and the diode laser injection current control, is presented. This scheme avoids any supplementary switching device. To retrieve ringdown processing at a kilohertz rate several exponential decay fit algorithms are compared. Performances of this new scheme are demonstrated with the observation of very weak lines of the oxygen B-band around 680 nm. Atmospheric spectra of isolated lines averaged for less than 10 s show a baseline noise of 5×10^-10 cm^-1 and a single point minimum detectable absorption loss over a one-second measurement interval of 2×10^-10 cm/ is obtained. PACS 07.88.+y; 42.55.Px; 42.62.Fi     

Development of a cw-laser-based cavity-ringdown sensor aboard a spacecraft for trace air constituents

The progress in the development of a sensor for the detection of trace air constituents to monitor spacecraft air quality is reported. A continuous-wave (cw), external-cavity tunable diode laser centered at 1.55 μm is used to pump an optical cavity absorption cell in cw-cavity ringdown spectroscopy (cw-CRDS). Preliminary results are presented that demonstrate the sensitivity, selectivity and reproducibility of this method. Detection limits of 2.0 ppm for CO, 2.5 ppm for CO₂, 1.8 ppm for H₂O, 19.4 ppb for NH₃, 7.9 ppb for HCN and 4.0 ppb for C₂H₂ are calculated. Received: 3 April 2002 / Revised version: 3 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-202/994-5873, E-mail: Houston@gwu.edu     

Detection of trace gases by rapidly-swept continuous-wave cavity ringdown spectroscopy: pushing the limits of sensitivity

Cavity ringdown (CRD) absorption spectroscopy enables spectroscopic sensing of gases with a high sensitivity and accuracy. Instrumental improvements result in a new high-performance continuous-wave (cw) CRD spectrometer using a rapidly-swept cavity of simple design. It employs efficient data-acquisition procedures, high-reflectivity mirrors, a low-adsorption flow cell, and various compact fibre-optical components in a single-ended transmitter-receiver configuration suitable for remote sensing. Baseline noise levels in our latest cw-CRD experiments yield a competitive noise-equivalent absorption limit of ∼5×10^-10 cm^-1Hz^-1/2, independent of whatever molecules are to be detected. Measurements in the near-infrared wavelength range of 1.51–1.56 μm yield sub-ppmv (i.e., ppbv or better) sensitivity in the gas phase for several representative molecules (notably CO₂, CO, H₂O, NH₃, C₂H₂, and other hydrocarbons). By measuring spectroscopic features in the 1.525 μm band of C₂H₂ gas, we realise detection limits of 19 nTorr (2.5×10^-11 atm) of neat C₂H₂ (Doppler-limited at low pressure) and 0.37 ppbv of C₂H₂ in air (pressure-broadened at 1 atm). Our cw-CRD spectrometer is a high-performance sensor in a relatively simple, low-cost, compact instrument that is amenable to chemical analysis of trace gases in medicine, agriculture, industry, and the environment. PACS 07.07.Df; 07.57.Ty; 42.62.Fi     

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum cascade laser

Optical-feedback cavity-enhanced absorption spectroscopy is demonstrated in the mid-IR by using a quantum cascade laser (emitting at 4.46 μm). The laser linewidth reduction and frequency locking by selective optical feedback from the resonant cavity field turns out to be particularly advantageous in this spectral range: It allows strong cavity transmission, which compensates for low light sensitivity, especially when using room-temperature detectors. We obtain a noise equivalent absorption coefficient of 3 × 10(-9)/cm for 1 s averaging of spectra composed by 100 independent points. At 4.46 μm, this yields a detection limit of 35 parts in 10(12) by volume for N(2)O at 50 mbar, corresponding to 4 × 10(7) molecules/cm(3), or still to 1 fmol in the sample volume.     

Absorption spectroscopy: technique provides extremely high sensitivity

Technology associated with cavity ringdown laser absorption spectroscopy is reviewed. The technique is used to study general trace analysis, free radicals in flames and chemical reactors, molecular ions in electrical discharges, biological molecules and water clusters in supersonic jets, and vibrational overtones of stable molecules. Its specific enough to detect about 1-ppm fractional absorption by a gaseous sample in about 10 microseconds. The use of mirrors in ringdown sepctroscopy is explained. Other topics include the generation of pulsed infrared rays and the adaptation of ringdown spectroscopy for use with narrow-bandwidth continuous-wave lasers.     

More Sub-Doppler Heterodyne Frequency Measurements on OCS between 56 and 63 THz

By using tunable microwave sidebands added to CO-laser lines, we have made more sub-Doppler heterodyne frequency measurements on OCS. Three new rotational transitions have been measured for each of three absorption bands, 10(0)0-00(0)0, 02(0)1-00(0)0, and 03(1)1-01(1)0. The absolute uncertainties of the measurements are on the order of +/-25 kHz. New calibration tables are given for the region 1860-1925 and 2020-2085 cm(-1) based on the most recent OCS measurements. Copyright 2000 Academic Press.