Detection of chemical warfare agents based on quantum cascade laser cavity ring-down spectroscopy

Chemical warfare agents(CWAs) are recognized as serious threats of terrorist acts against the civilian population.Minimizing the impact of these threats requires early detection of the presence of CWAs.Cavity ring-down spectroscopy(CRDS) is an exquisitely sensitive technique for the detection of trace gaseous species.In this letter,the CRDS technique is employed using a pulsed quantum cascade laser for the detection of dimethyl methylphosphonate(DMMP).A limit of DMMP detection of approximately 77 ppb is achieved.The best achievable sensitivity that corresponds to noise-equivalent absorption is approximately 2×10-7cm 1.     

Liquid-contents verification for explosives, other hazards, and contraband by magnetic resonance

An increasingly important need today is to guard against terrorist attacks at key locations such as airports and public buildings. Liquid explosives can avoid detection at security checkpoints by being concealed as beverages or other benign liquids. Magnetic resonance (MR) offers a safe, noninvasive technology for probing and classifying the liquid contents inside sealed nonmetallic containers or packages. MR parameters such as relaxation times and signal amplitudes can be used to verify if the container actually has the liquid that is claimed. This verification, which can be done quickly, will allow for the detection of containers whose contents have been tampered with and possibly replaced or mixed with liquid explosives. The development of MR technology for the detection of liquid explosives has been funded by the Federal Aviation Administration. MR can also be potentially used for the detection of hazards such as chemical warfare agents and contraband such as dissolved narcotics.     

Photoacoustic spectroscopy for trace gas detection with cryogenic and room-temperature continuous-wave quantum cascade lasers

The main characteristics that a sensor must possess for trace gas detection and pollution monitoring are high sensitivity, high selectivity and the capability to perform in situ measurements. The photacoustic Helmholtz sensor developed in Reims, used in conjunction with powerful Quantum Cascade Lasers (QCLs), fulfils all these requirements. The best cell response is # 1200 V W⁻¹ cm and the corresponding ultimate sensitivity is j 3.3 × 10⁻¹⁰ W cm⁻¹¹ Hz^−11/2. This efficient sensor is used with mid-infrared QCLs from Alpes Lasers to reach the strong fundamental absorption bands of some atmospheric gases. A first cryogenic QCL emitting at 7.9 μm demonstrates the detection of methane in air with a detection limit of 3 ppb. A detection limit of 20 ppb of NO in air is demonstrated using another cryogenic QCL emitting in the 5.4 μm region. Real in-situ measurements can be achieved only with room-temperature QCLs. A room-temperature QCL emitting in the 7.9 μm region demonstrates the simultaneous detection of methane and nitrous oxide in air (17 and 7 ppb detection limit, respectively). All these reliable measurements allow the estimated detection limit for various atmospheric gases using quantum cascade lasers to be obtained. Each gas absorbing in the infrared may be detected at a detection limit in the ppb or low-ppb range.     

Application of mid-infrared cavity-ringdown spectroscopy to trace explosives vapor detection using a broadly tunable (6–8 μm) optical parametric oscillator

A novel instrument, based on cavity-ringdown spectroscopy (CRDS), has been developed for trace gas detection. The new instrument utilizes a widely tunable optical parametric oscillator (OPO), which incorporates a zinc–germanium–phosphide (ZGP) crystal that is pumped at 2.8 μm by a 25-Hz Er,Cr:YSGG laser. The resultant mid-IR beam profile is nearly Gaussian, with energies exceeding 200 μJ/pulse between 6 and 8 μm, corresponding to a quantum conversion efficiency of approximately 35%. Vapor-phase mid-infrared spectra of common explosives (TNT, TATP, RDX, PETN and Tetryl) were acquired using the CRDS technique. Parts-per-billion concentration levels were readily detected with no sample preconcentration. A collection/flash-heating sequence was implemented in order to enhance detection limits for ambient air sampling. Detection limits as low as 75 ppt for TNT are expected, with similar concentration levels for the other explosives. Received: 1 April 2002 / Revised version: 13 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-408/524-0551, E-mail: mtodd@picarro.com     

Open-path trace gas detection of ammonia based on cavity-enhanced absorption spectroscopy

A compact open-path optical ammonia detector is developed. A tunable external-cavity diode laser operating at 1.5 μm is used to probe absorptions of ammonia via the cavity-enhanced absorption (CEA) technique. The detector is tested in a climate chamber. The sensitivity and linearity of this system are studied for ammonia and water at atmospheric pressure. A cluster of closely spaced rovibrational overtone and combination band transitions, observed as one broad absorption feature, is used for the detection of ammonia. On these molecular transitions a detection limit of 100 ppb (1 s) is determined. The ammonia measurements are calibrated independently with a chemiluminescence monitor. Compared to other optical open-path detection methods in the 1–2 μm region, the present result shows an improved sensitivity for contactless ammonia detection by over one order of magnitude. Using the same set-up, a detection limit of 100 ppm (1 s) is determined for the detection of water at atmospheric pressure. Received: 19 January 2000 / Revised version: 6 March 2000 / Published online: 7 June 2000     

Near-infrared trace-gas sensors based on room-temperature diode lasers

2 monitor designed for field applications using room-temperature diode lasers are presented. Near-infrared DFB lasers operating at 1.57 μm and around 2.0 μm have been used for CO₂ measurements. At ambient concentration levels a resolution of more than two orders of magnitude has been demonstrated at 1.57 μm, at 2 μm the precision is in the order of 0.1 ppm CO₂, and for trace analysis a detection limit of 10 ppb has been obtained. The measurements demonstrate the capability of near-infrared DFB diode lasers for the precise determination of CO₂ concentrations as required for climatological, medical, or industrial applications. Received: 24 February 1998/Revised version: 27 April 1998     

Photoacoustic trace-gas detection using a cw single-frequency parametric oscillator

2 H₆) at 3.34 μm using a widely tunable cw single-frequency optical parametric oscillator. The high frequency and power stability and the continuous tunability of the parametric oscillator make it ideally suited for this application. Detection sensitivities of 0.5 ppb for ethane are obtained, which is comparable to the best results previously obtained with intracavity detection using line-tunable CO overtone lasers. The flexibility and compact size of cw single-frequency parametric oscillators can lead to portable photoacoustic trace-gas detection systems for environmental monitoring and process control. Received: 28 January 1998/Revised version: 9 April 1998     

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     

Telecom-grade fiber laser-based difference-frequency generation and ppb-level detection of benzene vapor in air around 3 μm

We report on the development of a field deployable compact laser instrument tunable over ∼232 cm⁻¹ from 3.16 to 3.41 μm (2932.5–3164.5 cm⁻¹) for chemical species monitoring at the ppb-level. The laser instrument is based on widely tunable continuous-wave difference-frequency generation (DFG), pumped by two telecom-grade fiber lasers. DFG power of ∼0.3 mW near 3.3 μm with a spectral purity of ∼3.3 MHz was achieved by using moderate pumping powers: 408 mW at 1062 nm and 636 mW at 1570 nm. Spectroscopic performance of the developed DFG-based instrument was evaluated with direct absorption spectra of ethylene at 3.23 μm (∼3094.31 cm⁻¹). Absorption spectra of vapor-phase benzene near 3.28 μm (∼3043.82 cm⁻¹) were recorded with Doppler-limited resolution. Line intensities of the most intense absorption lines of the ν ₁₂ band near 3043.8 cm⁻¹ were determined to support development of sensitive mid-infrared trace gas detection of benzene vapor in the atmosphere. Detection of benzene vapor in air at different concentration levels has been performed for the first time using multi-pass cell enhanced direct absorption spectroscopy at ∼3.28 μm with a minimum detectable concentration of 50 ppb (1σ).     

Continuous-wave quantum cascade lasers absorption spectrometers for trace gas detection in the atmosphere

Mid infra-red absorption spectrometry based on continuous-wave distributed feedback (DFB) quantum cascade laser (QCL) is more and more widely used for trace gas detection and pollution monitoring. The main advantages of this technique are high sensitivity, high selectivity and a potential for extreme compactness. Various examples of trace gas detection for atmospheric detection will be presented in this paper. Commercial QCLs available on the shelves were first implemented. A cryogenic QCL emitting at 6.7 μm was used to demonstrate the detection of water vapor and its isotopes. A room-temperature QCL was then used to simultaneously detect methane and nitrous oxide at 7.9 μm. Recently, we have developed a room-temperature top grating DFB QCL designed around 4.5 μm for the demonstration of N₂O detection in the ppb range. Atmospheric applications of these spectrometers will be presented. The improvements of QCL performances make it now possible to develop instruments that are more and more compact and therefore compatible with in situ applications.     

Potentials and limits of mid-infrared laser spectroscopy for the detection of explosives

Optical methods are well-established for trace gas detection in many applications, such as industrial process control or environmental sensing. Consequently, they gain much interest in the discussion of sensing methods for counterterrorism, e.g., the detection of explosives. Explosives as well as their decomposition products possess strong absorption features in the mid-infrared (MIR) spectral region between λ=5 and 11 μm. In this report we present two different laser spectroscopic approaches based on quantum cascade lasers (QCLs) operating at wavelengths around λ=5 and 8 μm, respectively. Stand-off configuration for the remote detection of nitro-based explosives (e.g., trinitrotoluene, TNT) and a fiber coupled sensor device for the detection of triacetone triperoxide (TATP) are discussed. PACS  42.62.Fi; 07.07.Df     

Pulsed laser surface fragmentation and mid-infrared laser spectroscopy for remote detection of explosives

Stand-off technology for the remote detection of explosives and their traces on contaminated surfaces is a field of research that has recently gained much interest. Optical methods are well established in applications for counterterrorism because they facilitate analysis without contact between human being and hazardous materials. In this paper, to our knowledge for the first time, a remote stand-off detection system is developed by combination of pulsed laser fragmentation and pulsed mid-infrared laser absorption spectroscopy. Since the absorption of explosives is more efficient for infrared wavelengths laser radiation in the eye safe region around λ=1.47 μm rather than the conventional Nd:YAG laser line at λ=1.06 μm is preferred for the fragmentation. Generated product gases such as nitric oxide are probed by a synchronized distributed feedback quantum cascade laser (DFB-QCL) at λ≈5.3 μm. The ratio of NO and NO₂ is a measure to distinguish between energetic and non-energetic materials. PACS 42.62.Fi; 07.07.DF; 42.55.Px     

表面增强拉曼光谱检测爆炸物研究进展

近年来,恐怖袭击、刑事犯罪等爆炸事件频发,对社会的公共安全构成了严峻挑战。炸药是各种爆炸物的核心成分,因此对炸药的分析检测与识别是公共安全领域研究的热点之一。表面增强拉曼光谱可以对爆炸物分子实现指纹谱性、超痕量、实时高效的探测和识别,在安全检测和法庭科学等公共安全领域展现了极具诱惑力的应用前景。最近几年,国际上针对表面增强拉曼光谱检测爆炸物的研究十分活跃,取得了丰富的成果,文章综述了爆炸物表面增强拉曼基底,包括表面修饰改性和复合功能结构基底;有机和无机爆炸物的检测;以及爆炸物光谱识别的研究进展。分析了需要面对的问题,并总结展望了未来的发展趋势。相信随着纳米科学与技术、表面科学、仪器科学以及深度学习等新兴科技的快速发展,表面增强拉曼光谱一定能在爆炸物检测和识别方面取得更大进展。     

Cavity ring down spectroscopy: detection of trace amounts of substance

We describe several applications of cavity ring-down spectroscopy (CRDS) for trace matter detection. NO₂ sensor was constructed in our team using this technique and blue-violet lasers (395–440 nm). Its sensitivity is better than single ppb. CRDS at 627 nm was used for detection of NO₃. Successful monitoring of N₂O in air requires high precision mid-infrared spectroscopy. These sensors might be used for atmospheric purity monitoring as well as for explosives detection. Here, the spectroscopy on sharp vibronic molecular resonances is performed. Therefore the single mode lasers which can be tuned to selected molecular lines are used. Similarly, the spectroscopy at 936 nm was used for sensitive water vapour detection. The opportunity of construction of H₂O sensor reaching the sensitivity about 10 ppb is also discussed.     

Planar laser-induced fluorescence imaging of carbon monoxide using vibrational (infrared) transitions

We report a new imaging diagnostic suitable for measurements of infrared-active molecules, namely infrared planar laser-induced fluorescence (IR PLIF), in which a tunable infrared source is used to excite vibrational transitions in molecules and vibrational fluorescence is collected by an infrared camera. A nanosecond-pulse Nd:YAG-pumped KTP/KTA OPO/OPA system is used to generate 12 mJ of tunable output near 2.35 μm which excites the 2ν band of carbon monoxide (CO); fluorescence resulting from excited CO is collected at 4.7 μm by using an InSb focal plane array. Quantitative, high-SNR PLIF imaging of gas-phase CO is demonstrated at a 10-Hz acquisition rate with a minimum detection limit of 1350 ppm at 300 K. Received: 30 July 1999 / Published online: 16 September 1999     

一种热光可调谐级联微环滤波器的理论分析

根据Vernier效应可大幅度提高滤波器自由光谱范围和调谐范围,设计了一种热光可调谐级联微环滤波器. 利用传输矩阵方法和有限元方法从理论上计算了对于第一级微环半径为48 μm,第二级半径为50 μm的级联微环滤波器的自由光谱范围和调谐范围可以达到75.6 nm,而功耗仅为103.1 mW,这是目前为止我们 所知的基于微环谐振腔的硅基热光可调谐滤波器中最大的自由光谱范围和在如此低功耗下最大的调谐范围. 利用有限元方法,还计算了半径为50 μm微环的热光调谐响应时间,上升沿时间为3.5 μs,下降沿时间仅为0.8 μs.     

Faraday rotation spectrometer with sub-second response time for?detection of nitric oxide using a cw DFB quantum cascade laser at?5.33 μm

A Faraday modulation spectrometer for sensitive and fast detection of nitric oxide at 5.33 μm utilizing a room temperature continuous wave distributed feedback quantum cascade laser and a Peltier cooled MCT detector is presented. The magnetic field was modulated at 7.4 kHz whereas the laser wavelength was scanned at 20 Hz across the most favorable rotational-vibrational transition for FAMOS, Q _3/2(3/2), at 5.33 μm. Using a 15 cm optical path and lineshape fitting, the spectrometer provides a detection limit of 4.5 ppb for a response time of 1 s. An Allan variance analysis demonstrates that the system has an excellent stability, up to several hours of operation.     

An all-diode-laser-based, dual-cavity AgGaS2 cw difference-frequency source for the 9–11 μm range

2 ) nonlinear crystal is reported. The device uses a standing-wave dual-resonator scheme to enhance both near-infrared lasers. For 7 mW of 778.2-nm and 275 mW of 842.5-nm input powers, 40 nW of 10.2-μm radiation is generated by a preliminary setup. A μW-level range output power is expected after optimization of the device optical components. This compact tunable source will allow Fabry–Pérot high-resolution Doppler-free spectroscopy of spherical molecules, such as OsO₄ or SF₆, in the 9–11 μm range as an alternative source to frequency-stabilized CO₂ lasers. Received: 17 March 1998     

Spectroscopic detection of biological NO with a quantum cascade laser

Two configurations of a continuous wave quantum cascade distributed feedback laser-based gas sensor for the detection of NO at a parts per billion (ppb) concentration level, typical of biomedical applications, have been investigated. The laser was operated at liquid nitrogen temperature near λ=5.2 μm. In the first configuration, a 100 m optical path length multi-pass cell was employed to enhance the NO absorption. In the second configuration, a technique based on cavity-enhanced spectroscopy (CES) was utilized, with an effective path length of 670 m. Both sensors enabled simultaneous analysis of NO and CO₂ concentrations in exhaled air. The minimum detectable NO concentration was found to be 3 ppb with a multi-pass cell and 16 ppb when using CES. The two techniques are compared, and potential future developments are discussed. Received: 1 November 2000 / Revised version: 19 January 2001 / Published online: 20 April 2001     

Fundamental noise sources in a high-sensitivity two-tone frequency modulation spectrometer and detection of CO2 at 1.6 μm and 2 μm

2 , and its sensitivity is 7(2)×10^-8 in a 1-Hz bandwidth. The corresponding minimum detectable concentration of CO₂ in air has been estimated to be 1 ppm · m. This opens the possibility of a detection at ppb levels at 2 μm, where a two orders of magnitude increase in the CO₂ absorption signal is demonstrated. Received: 06 April 1998/Revised version: 02 July 1998