Precision continuous-wave cavity ringdown spectroscopy of CO<Subscript>2</Subscript> at 1064 nm

A high performance continuous-wave cavity ringdown spectrometer using a rapidly swept cavity has been applied to investigate weak absorption of CO₂ line near 1064 nm. In the experimental setup, offset locking of the Nd:YAG laser to other iodine-stabilized Nd:YAG laser provides a frequency accuracy better than 20 kHz. The ringdown time was obtained by fitting the experimental ringdown data to a theoretically obtained ringdown curve. The absorption coefficient and absolute center wavelength are determined with accuracy better than two orders of magnitude with respect to the previous observations. Our experimental setup yields high performance in a relatively simple, low cost, and compact system that is amenable to chemical analysis of trace gases in medicine, agriculture, industry, and the environment.     

High-sensitivity methane monitoring based on quasi-fundamental mode matched continuous-wave cavity ring-down spectroscopy

Continuous-wave cavity ring-down spectroscopy (CW-CRDS) is an important technical means to monitor greenhouse gases in atmospheric environment. In this paper, a CW-CRDS system is built to meet the needs of atmospheric methane monitoring. The problem of mode matching is explained from the perspective of transverse mode and longitudinal mode, and the influence of laser injection efficiency on measurement precision is further analyzed. The results of cavity ring-down time measurement show that the measurement precision is higher when the laser is coupled with the fundamental mode. In the experiment, DFB laser is used to calibrate the system with standard methane concentration, and the measurement residual is less than ±4×10^-4 μs^-1. The methane concentration in the air is monitored in real time for two days. The results show the consistency of the concentration changes over the two days, which further demonstrates the reliability of the system for the measurement of trace methane. By analyzing the influence of mode matching, it not only assists the adjustment of the optical path, but also further improves the sensitivity of the system measurement.     

Flexible laser diode trace gas sensor based on cavity ringdown spectroscopy with an optical fiber-coupled high-finesse external-cavity diode laser

A flexible and portable trace nitrogen dioxide sensor based on cavity ringdown spectroscopy using an optical fiber-coupled high-finesse cavity was successfully demonstrated. Tailoring the spatial mode matching condition of the core of an optical fiber and high-finesse external cavity allows for effective optical feedback into an antireflection-coated laser diode for stable resonant enhancement of the external cavity. The external cavity, which works as a ringdown cavity, could be remotely located from the light source and receiver section by only a single mode optical fiber. The sensitivity was found to be 1.0×10⁻⁷ cm⁻¹ in a compact 1-cm³ ringdown cavity volume.     

Continuous-wave cavity-ringdown detection of stimulated Raman gain spectra

Cavity ringdown (CRD) spectroscopy, with its high sensitivity, provides a novel way to perform continuous-wave (cw) stimulated Raman gain (SRG) spectroscopy, rather than by conventional optically detected coherent Raman techniques. Tunable cw laser light at ∼1544 nm is used to probe ringdown decay from a rapidly-swept, high-finesse optical cavity containing a gas-phase sample of interest and itself located inside the cavity of a cw single-longitudinal-mode Nd:YAG ring laser operating at ∼1064.4 nm. This approach is used to measure cw SRG spectra of the ν ₁ fundamental rovibrational Raman band of methane gas at ∼2916.5 cm⁻¹. The resulting SRG-CRD resonances have ringdown times longer than in the off-resonance case, in contrast to the usual shorter ringdown times arising from absorption and other loss processes. Previously reported noise-equivalent sensitivities have been substantially improved, by using a second ringdown cavity to facilitate subtraction of infrared-absorption background signals. Moreover, by employing a ringdown cavity in the form of a ring, the SRG-pump and CRD-detected Stokes beams can co-propagate uni-directionally, which significantly reduces Doppler broadening.     

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     

波长调制-直接吸收方法在线监测大气中CH4和CO2浓度

波长调制-直接吸收光谱(WM-DAS),同时具有直接吸收光谱(DAS)的免标定、可测量吸收率函数的优点和波长调制光谱(WMS)高信噪比、抗干扰能力强的优点.本文利用免标定、高信噪比的WM-DAS方法结合长光程Herriott池,在常压常温条件下,对大气中CH4(6046.952 cm^-1)和CO2(6330.821 cm^-1)分子两条近红外吸收谱线的吸收率函数进行了测量,其光谱拟合残差标准差可达到5.6×10^-5.随后,采取WM-DAS方法结合Herriott池,对大气中CO2和CH4浓度进行了连续监测,并将其与高灵敏度的连续波腔衰荡光谱(CW-CRDS)测量结果进行比较.实验结果表明:本文采用的长光程WM-DAS与CW-CRDS方法测量结果一致,两组数据线性拟合相关性达到0.99,其中基于WM-DAS方法的CO2和CH4的检测限分别达到170 ppb和1.5 ppb,略高于CW-CRDS检测限,但其测量速度远高于CW-CRDS,并且具有系统简单、对环境要求低、可长期稳定运行等优点.     

Near-infrared laser based cavity ringdown spectroscopy for applications in petrochemical industry

A simple, economic diode laser based cavity ringdown system for trace-gas applications in the petrochemical industry is presented. As acetylene (C₂H₂) is sometimes present as an interfering contaminant in the gas flow of ethylene (ethene, C₂H₄) in a polyethylene production process, an on-line monitoring of such traces is essential. We investigated C₂H₂–C₂H₄ mixtures in a gas-flow configuration in real time. The experimental setup consists of a near-infrared external cavity diode laser with an output power of a few mW, standard telecommunication fibers and a home-made gas cell providing a user-friendly cavity alignment. A noise-equivalent detection sensitivity of 4.5×10^-8 cm^-1 Hz^-1/2 was achieved, corresponding to a detection limit of 20 ppbV C₂H₂ in synthetic air at 100 mbar. In an actual C₂H₂–C₂H₄ gas-flow measurement the minimum detectable concentration of C₂H₂ added to the C₂H₄ gas stream (which may already contain an unknown C₂H₂ contamination) increased to 160 ppbV. Moreover, stepwise C₂H₂ concentration increments of 500 ppbV were resolved with a 1-min time resolution and an excellent linear relationship between the absorption coefficient and the concentration was found. PACS 07.07.Df; 42.62.Fi; 82.80.Gk     

Three-level depletion by cavity ringdown absorption spectroscopy: proof of concept

Theoretical quantitative considerations as well as experimental data are presented based on absorption population depletion coupled with cavity ringdown spectroscopy. The absorbing number densities inside the cavity are determined by numerical integration of the coupled rate equations. The number of photons involved in absorption, cavity losses due to mirror reflectivity and stimulated emission are taken into account. The principle is to monitor a first transition by cavity ringdown spectroscopy while a second transition, with a state in common, is resonantly excited by the decaying radiation of different frequency also trapped inside the optical cavity. A numerical example is given for atomic lines of neon and the measurements carried out in a supersonic slit-jet expansion discharge demonstrate the feasibility of the technique. The technique is also proven to work with two resonant transitions of C₂. Translational velocity of the jet modifying the rate equations is included in the model.     

Quantitative gas measurements using a versatile OPO-based cavity ringdown spectrometer and the comparison with spectroscopic databases

A versatile OPO-based cavity ringdown spectrometer is reported for quantitative and sensitive gas measurement down to nmol/mol levels. The system is based on cavity ringdown spectroscopy (CRDS) in combination with a continuous wave optical parametric oscillator tunable from 2693 to 3505 nm. Using a single set of CRDS mirrors, spectra were recorded of methane, ethane, benzene, propane, water, acetone and formaldehyde. Gas mixtures were gravimetrically prepared in cylinders or via dynamic generation using diffusion tubes (formaldehyde). Results were compared with data from the Hitran, PNNL and NIST databases. Good agreement was found with PNNL and NIST data for most molecules while agreement with Hitran was less for ethane and formaldehyde.     

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     

Optimization of the mode matching in pulsed cavity ringdown spectroscopy by monitoring non-degenerate transverse mode beating

A simple and reliable method is presented for optimizing the mode matching of a laser beam to the high-finesse cavity used in pulsed cavity ringdown spectroscopy (CRDS). The method is based on minimizing the excitation of higher-order transverse cavity modes through monitoring the non-degenerate transverse mode beating which becomes visible with induced cavity asymmetry caused by slight misalignment. No additional instrument is required other than a pinhole aperture, thus this method can be applied for CRDS experiments in the whole wavelength range. Measurements of the CRDS absorption spectrum of acetylene (C₂H₂) near 571 nm demonstrate that the mode-matching optimization improves the sensitivity of pulsed CRDS. Received: 22 October 2001 / Revised version: 16 January 2002 / Published online: 14 March 2002     

A novel multiple species ringdown spectrometer for in situ measurements of methane,carbon dioxide,and carbon isotope

We have developed a standalone, user-friendly, multi-species ringdown spectrometer for in situ measurements of methane (CH₄), carbon dioxide (CO₂), and a carbon dioxide isotope (¹³CO₂). The instrument is based on near-infrared continuous-wave cavity ringdown spectroscopy (NIR cw-CRDS) and engineered to be of approximately 16 kg with dimensions of 50 cm × 40 cm × 15 cm. The instrument design, optical configuration, electronic control, and performance are described. CH₄, CO₂, and ¹³CO₂ are measured at different wavelengths that are obtained through multiplexing two distributed feedback laser diodes with central wavelengths at 1597 and 1650 nm. The spectrometer has low power consumption and runs for 4–6 h when powered by a standard car battery. The instrument is operated either locally by interacting with a 7-inch touch screen or remotely via an Internet connection. The 1-σ detection limits for CH₄ and CO₂ are 0.2 and 120 ppmv, respectively. The measurement uncertainty is better than ±4% of full-scale reading for CH₄ and CO₂ and ±1.5‰ for δ¹³C (part per thousand relative to the Pee Dee Belemnite scale). Measurement of each species is near real-time; switching from measuring one species to another takes less than one minute. This work demonstrates a novel multiple-species CRDS-instrumentation platform, which can be adopted for development of an array of ringdown spectrometers for portable, user-friendly, field analysis of a variety of gases in environmental and industrial applications. Discussion of a future version of the spectrometer with better detection sensitivity, higher accuracy, and a smaller geometry is also presented. PACS  42.62.Fi; 42.55.Px; 33.20.Ea; 07.88.+y; 07.57.Ty     

Fast, low-noise, mode-by-mode, cavity-enhanced absorption spectroscopy by diode-laser self-locking

A new technique of cavity enhanced absorption spectroscopy is described. Molecular absorption spectra are obtained by recording the transmission maxima of the successive TEM_oo resonances of a high-finesse optical cavity when a Distributed Feedback Diode Laser is tuned across them. A noisy cavity output is usually observed in such a measurement since the resonances are spectrally narrower than the laser. We show that a folded (V-shaped) cavity can be used to obtain selective optical feedback from the intracavity field which builds up at resonance. This induces laser linewidth reduction and frequency locking. The linewidth narrowing eliminates the noisy cavity output, and allows measuring the maximum mode transmissions accurately. The frequency locking permits the laser to scan stepwise through the successive cavity modes. Frequency tuning is thus tightly optimized for cavity mode injection. Our setup for this technique of Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) includes a 50 cm folded cavity with finesse ∼20 000 (ringdown time ∼20 μs) and allows recording spectra of up to 200 cavity modes (2 cm⁻¹) using 100 ms laser scans. We obtain a noise equivalent absorption coefficient of ∼5×10⁻¹⁰ cm⁻¹ for 1 s averaging over scans, with a dynamic range of four orders of magnitude.     

Signal processing system in cavity enhanced spectroscopy

The paper presents a signal processing system used for nitrogen dioxide detection employing cavity enhanced absorption spectroscopy. In this system, the absorbing gas concentration is determined by the measurement of a decay time of a light pulse trapped in a cavity. The setup includes a resonance optical cavity, which was equipped with spherical and high reflectance mirrors, the pulsed diode laser (414 nm) and electronic signal processing system. In order to ensure registration of low-level signals and accurate decay time measurements, special preamplifier and digital signal processing circuit were developed. Theoretical analyses of main parameters of optical cavity and signal processing system were presented and especially signal-to-noise ratio was taken into consideration. Furthermore, investigation of S/N signal processing system and influence of preamplifier feedback resistance on the useful signal distortion were described. The aim of the experiment was to study potential application of cavity enhanced absorption spectroscopy for construction of fully optoelectronic NO₂ sensor which could replace, e.g., commonly used chemical detectors. Thanks to the developed signal processing system, detection limit of NO₂ sensor reaches the value of 0.2 ppb (absorption coefficient equivalent = 2.8 × 10⁻⁹ cm⁻¹).     

Influence of ethylene spectral lines on methane concentration measurements with a diode laser methane sensor in the 1.65 μm region

Spectra measurements around 1.65 μm have revealed that spectral lines of ethylene are present in this range along with methane spectral lines. Furthermore, the HITRAN database has no parameters of these ethylene lines. In particular, it was found that several ethylene absorption lines are located near the methane feature often used for quantitative spectroscopy (R3 triplet of the 2ν₃ band). Ethylene can be present together with methane in the samples under study, perturbing the recorded spectrum of CH₄. This perturbation by an interfering species can produce systematic errors in the derived CH₄ concentration. We have found in this work by numerical modelling that when measuring the methane concentration by a diode laser methane sensor operating in the 6046–6048 cm^-1 range, the systematic error on the retrieved CH₄ concentration decreases, as a rule, when decreasing the width of the fitted spectral window. At equal concentrations of ethylene and methane in the sample under study, the error on the concentration of CH₄ determined by the correlation technique can reach 15%. When using the technique based on the 2nd or 3rd derivative of the spectrum, interfering or impurity lines induce a systematic error on the derived CH₄ concentration, which is less than 2%. PACS 07.07.Df; 07.88.+y; 42.62.-b     

Study of gas detection based on integrated cavity output spectroscopy

A trace gases detection system based on integrated cavity output spectroscopy (ICOS) was developed, where a NIR tunable diode laser (TDL) was used as light source, an optical cavity composed by two plan-concave mirrors with reflection near 99.7% was used as the absorption cell. Trace water vapour (H₂O), carbon dioxide (CO₂), methane (CH₄), carbon monoxide (CO) and mixture of CO₂ and CO were tested by ICOS based on the characteristics absorption. The wavelength calibration, cavity transmission characteristics, quantitative measurement ability and sensitivity of the TDL-ICOS were also studied, and a evaluated minimum detectable sensitivity of 1.15 × 10^?7 cm^?1 was obtained when the system was used to CH₄ detection. The experiment results show that TDL-ICOS is expected to be a reliable and promising system for the detection of trace gases since it has some advantages such as real-time monitoring, simple device, easy operation, high sensitivity, good stability and quantitative ability.     

CO2 sensor for mainstream capnography based on TDLAS

The setup and signal processing for a mainstream capnography sensor is presented in this paper. The probe exhibits an optical path length of 2.5 cm and is equipped with a vertical-cavity surface-emitting laser at 2 μm. The sensor does not need any calibration, since the CO₂ absorption line as well as the laser background is measured using direct tunable diode laser absorption spectroscopy. Unavoidable optical fringes are reduced with a self-developed fringe rejection method. The sensor achieves a concentration resolution <300 ppmv at 4 vol% and a measurement rate >30 Hz.     

High-resolution cavity-tuned ringdown spectrometer using a narrow-bandwidth pulsed laser source

A novel method of cavity ringdown spectroscopy is proposed to achieve high spectral resolution with tunable narrow bandwidth pulsed lasers. We demonstrate a cavity-tuned ringdown configuration in which only a single cavity mode is kept excited near the carrier frequency of a narrow bandwidth pulse laser. This is done simply by making a cavity resonance actively track the frequency reference served by the cw injection seed of the pulsed laser source. We present the servo mechanism used in the cavity resonance tracking, reliable procedures for transverse mode matching, and the evidence of single longitudinal mode excitation. The spectrometer performance is tested to record weak molecular overtone features of acetylene around the wavelength of 570 nm, showing cavity tracking stability within 5-MHz uncertainty which overcomes the bandwidth limit of pulsed laser sources itself. PACS 42.62.Fi; 42.60.Da; 33.20.Kf     

双重频率锁定的腔衰荡吸收光谱技术及信号处理

针对传统腔衰荡光谱技术浓度获取率低,提出基于双重锁定的连续波腔衰荡吸收光谱技术.通过波长调制一次谐波信号将激光器的频率锁定到C_2H_2吸收线上,同时使用PDH锁频技术将衰荡腔锁定到激光器上,从而避免了测量过程中激光器的频率漂移和腔长的抖动,使测量结果更加精确;并且,由于双重锁定,单次衰荡事件的发生率,也就是浓度信息的获取率只受衰荡时间以及重新锁定时间限制,在本试验系统中采集速率可以达到30 k Hz,可以实现对气体浓度的快速测量.为了提高信噪比,采用Kalman滤波技术,对浓度信息进行实时处理,有效抑制了噪声,根据阿伦方差分析,探测灵敏度可以达到4×10~(-9)cm~(-1)(2 s平均).     

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。