基于2μm激光二极管和Herriott多光程吸收池的高灵敏二氧化碳气体传感器（特邀）

为了提高二氧化碳气体检测系统的测量空间分辨率并减小系统体积，设计了一种基于2μm激光二极管和Herriott多光程吸收池的高灵敏二氧化碳气体传感器。设计并加工了有效光程为2.6 m的Herriott池来进行光路折叠。使用中心波长为2μm的激光二极管，覆盖二氧化碳分子在4 989.9 cm^-1处的较强吸收线。采用波长调制技术减小系统的噪声。此外，为系统加载Kalman滤波技术来进一步提高探测灵敏度。实验结果表明，采用该传感器，系统的探测极限在1 s的积分时间下可达到0.18×10^-6，而经过自编程实时Kalman滤波后探测极限可达到0.13×10^-6，提高了27%。采用该传感器对室内二氧化碳浓度进行长达8 h的连续监测，并在暨南大学理工学院楼顶进行了24 h的二氧化碳浓度监测，证明了仪器的稳定性。     

基于离轴腔增强吸收光谱双组分CH4/H2O高灵敏度探测研究

H₂O和CH₄在气候变化过程中起着关键作用,实时在线测量H₂O和CH₄浓度一直都是国内外学者研究的热点问题之一。利用1.653 μm可调谐半导体激光器作光源,结合反射率为99.997 6%的两片高反射镜组成离轴腔增强吸收光谱装置,开展了H₂O和CH₄的高灵敏度测量研究。离轴腔增强系统的有效吸收光程通过吸收面积-浓度关系法来标定,吸收面积-浓度关系法的可行性首先通过已知光程的光学吸收池进行验证,确定有效后用于标定离轴腔增强系统的有效光程。结果表明,基长为21 cm的离轴腔增强系统的有效吸收光程达到了8 626.3 m。当谐振腔内压力为5.06 kPa时,利用7组不同浓度的CH₄标准气体（0.2～1.4 μmol·mol-1）对系统进行了线性响应标定测试,得到了CH₄吸收的积分面积与浓度拟合关系曲线。系统的稳定性、可实现的最小探测灵敏度等信息通过Allan方差进行分析,结果表明系统对探测CH₄的最佳平均时间为100 s,最小可探测浓度极限为7.5 nmol·mol-1;系统对探测H₂O的最佳平均时间为200 s,最小可探测浓度极限为55 μmol·mol-1。对提高系统测量精度的数据处理方法也进行了分析研究,结果表明相比于多次平均方法,Kalman滤波能显著的提高测量精度,而且缩短了系统的响应时间。最后,利用搭建的离轴腔增强实验系统结合Kalman滤波数据处理方法对实际大气中CH₄和H₂O浓度进行了连续两天的测量,CH₄每天平均的浓度分别为2.1和2.08 μmol·mol-1,H₂O每天平均的浓度分别为11 515.6和11 628.6 μmol·mol-1,由此可知建立的离轴腔增强吸收光谱装置能够用于大气CH₄和H₂O的测量,另外建立的系统也可用于相关工业领域的高灵敏度CH₄和H₂O监测。     

1.653 μm处甲烷分子谐波探测技术研究

谐波探测被广泛应用于激光光谱技术中,利用它可以提高探测灵敏度。利用1.653 μm的分布反馈式(DFB)二极管激光器作为光源,建立了一套可调谐半导体激光吸收光谱(TDLAS)甲烷探测装置。该装置利用由2块圆形柱面镜构成的光学多通池增加吸收光程,提高探测灵敏度。吸收池基长为15 cm,在112次反射情况下,有效吸收光程达到16.8 m,实现甲烷0.60×10-6(2 s采样时间)的探测极限,可应用于实际大气甲烷的痕量探测。     

基于差分吸收光谱技术的大气痕量气体二维观测方法

基于差分吸收光谱技术, 对大气痕量气体二维观测方法进行研究. 对常规多轴差分吸收光谱系统进行改进, 使望远镜可指向不同方位角, 获取测量点各方位角上的痕量气体信息, 从而更直观地了解测量点四周污染气体分布及其演变情况. 主要对NO₂浓度分布进行了研究, 同时获取了不同方位角上的O₄斜柱浓度; 采用辐射传输模型模拟计算O₄斜柱浓度并与实测数据对比, 结果表明二者具有高度相关性, 验证了大气中O₄分布的稳定性; 基于实测O₄数据提取光路信息, 结合辐射传输模型对NO₂和O₄因廓线不同造成的散射路径差异进行修正, 将NO₂斜柱浓度进一步转化为体积混合比, 获得了不同方位角上NO₂ 浓度分布图. 将计算结果与长光程差分吸收光谱技术数据进行对比, 结果表明二者具有较好的一致性.     

5.33 μm处磁旋转吸收光谱NO分子探测研究

本文基于直流磁场的磁旋转吸收光谱技术探测研究一氧化氮分子的痕量. 使用5.33 μm连续波量子级联激光器作为探测光源，结合Chernin型光学多通池，在1875.81 cm^-1(²∏_3/2(3/2)，υ=1←0)波长处进行探测. 108 m吸收光程下，实现了1.15 ppbv的探测极限(1s，1σ). 当采样时间延长到15 s，探测极限可提高至0.43 ppbv.     

宽带腔增强吸收光谱法测量大气NO2定标方法研究

非相干宽带腔增强吸收光谱法定量探测大气痕量气体浓度需要准确定标。以定量探测大气NO₂为目的,建立了基于蓝色发光二极管光源的非相干宽带腔增强吸收光谱测量系统,研究了(1)仅使用浓度已知的NO₂吸收光谱、(2)同时使用浓度已知的NO₂和纯氧气中氧气二聚体O₂-O₂吸收光谱、(3)利用纯氮气和纯氦气的瑞利散射消光差异等三种方法,分别获取非相干宽带腔增强吸收光谱在430～490 nm波段的镜片反射率定标曲线。三种方法得到的镜片反射率最大值对应波长均约为460 nm,但这些最大值存在一定差异,分别为0.999 25,0.999 33和0.999 37。利用NO₂样气吸收测量对比了三种定标方法,发现方法(1)与另外两种方法的测量结果不一致性分别约为14%和19%,而后两种方法所测结果的不一致性仅为4%。测量结果表明,NO₂标准气体浓度的不准确性以及壁损耗等因素恶化了方法(1)的定标精度,应尽量避免使用该定标方法。通过对实际大气中NO₂和O₂-O₂在440～485 nm波段内的同时测量,进一步验证了非相干宽带腔增强吸收光谱法的高灵敏度以及所用标定方法的有效性。     

2μm波段高灵敏度离轴积分腔装置实际大气CO2测量

利用分布反馈式(DFB)二极管激光器为光源, 搭建了一套2 μm波段的离轴积分腔输出光谱装置. 利用高纯甲烷气体, 测量了腔镜反射率随腔内气体压力 变化的规律. 当腔内压力为3.59 kPa 时, 标定的镜面反射率为0.99865, 在此条件下, 基长55 cm 的离轴积分腔实现了407.4 m的吸收光程. 选取CO₂ 在4993.7431 cm^-1处的吸收谱线对实际大气中的CO₂浓度进行了测量, 探测限为0.53 ppmv (1σ), 利用小波去噪对光谱信号进行了去噪处理, 信噪比提高了80%, 探测限提高到0.29 ppmv(1σ). 利用搭建的装置在实验室内测量了从上午9时到中午12时实际大气中CO₂的浓度, 并与H₂O/CO₂分析仪进行了同时观测与对比分析, 初步验证了测量装置的可靠性.     

5.33μm处磁旋转吸收光谱NO分子探测研究（英文）

本文基于直流磁场的磁旋转吸收光谱技术探测研究一氧化氮分子的痕量.使用5.33μm连续波量子级联激光器作为探测光源,结合C hernin型光学多通池,在1875.81 cm~(-1)(~2Π_(3/2)(3/2),v=1←0)波长处进行探测.108 m吸收光程下,实现了1.15 ppbv的探测极限(1s,1σ).当采样时间延长到15 s,探测极限可提高至0.43 ppbv.     

新型Sr（NO3）2的水热合成及其晶体结构

本文以Sr（NO₃）₂和水为原料,采用水热法合成了一种新型的Sr（NO₃）₂结构。利用X-射线单晶衍射对其结构进行了测定,结果表明:该晶体属于立方晶系,Pa-3空间群,α=b=c=0.77402（7）nm,α=β=γ=90.00°,V=0.46372（7）nm³,Z=4,Dc=3.031g/cm³,F（000）=400,R_gt（F）=0.0287,wR_ref（F²）=0.0888。     

基于光声光谱技术的NO,NO2气体分析仪研究

NO, NO₂是大气污染源中的常见气体, 对环境具有严重的危害性. 为检测污染源中这两种气体的浓度, 构建了成本较低的基于红外热辐射光源的光声光谱气体检测系统. 分析计算得到了NO, NO₂ 在2500–6667 nm波段吸收谱线. 通过建立光声传输线RLC振荡电路模型和仿真得到品质因数、声压大小与谐振腔长、内腔半径以及调制频率的关系, 据此设计了光声池几何结构. 实验表明该系统所测得的光声信号与气体浓度有很好的线性关系, 并且对NO, NO₂气体极限检测灵敏度分别达到4.01 和1.07 μL. 通过调节激光发射波长和选取滤波片, 该系统还可用于其他微量气体的浓度检测. 关键词： 大气污染 光声光谱 气体检测     

Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Absorptions of the ϱστ, 0.8 μm and a bands of the water vapor

Absorptions of the ?στ, 0.8 μm and a bands of water vapor were measured using a long pathlength, multiple-traversal absorption cell. The band intensities were found to be 842.3, 53.2, and 50.12 cm^-1/g-cm^-2 at 334 K for the ?στ, 0.8 μm and a bands, respectively. The measured equivalent widths gradually exceed calculated values for the Lorentz line profile and the self-broadening coefficients of 5 with increasing absorber amounts. Possible causes of this excess absorption are discussed.     

Cavity-enhanced absorption: detection of nitrogen dioxide and iodine monoxide using a violet laser diode

We present an application of cavity-enhanced absorption spectroscopy with an off-axis alignment of the cavity formed by two spherical mirrors and with time integration of the cavity-output intensity for detection of nitrogen dioxide (NO₂) and iodine monoxide (IO) radicals using a violet laser diode at λ=404.278 nm. A noise-equivalent (1σ≡ root-mean-square variation of the signal) fractional absorption for one optical pass of 4.5×10^-8 was demonstrated with a mirror reflectivity of ∼0.99925, a cavity length of 0.22 m and a lock-in-amplifier time constant of 3 s. Noise-equivalent detection sensitivities towards nitrogen dioxide of 1.8×10¹⁰ molecule cm^-3 and towards the IO radical of 3.3×10⁹ molecule cm^-3 were achieved in flow tubes with an inner diameter of 4 cm for a lock-in-amplifier time constant of 3 s. Alkyl peroxy radicals were detected using chemical titration with excess nitric oxide (RO₂+NO→RO+NO₂). Measurement of oxygen-atom concentrations was accomplished by determining the depletion of NO₂ in the reaction NO₂+O→NO+O₂. Noise-equivalent concentrations of alkyl peroxy radicals and oxygen atoms were 3×10¹⁰ molecule cm^-3 in the discharge-flow-tube experiments. Received: 4 February 2003 / Revised version: 10 March 2003 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +44-1865/275-410, E-mail: vlk@physchem.ox.ac.uk     

Pulsed photothermal laser deflection for low-level smoke and NO2 measurements in engine exhausts

Pulsed Photothermal Laser Deflection (PLD) is developed to make temporally and spatially resolved measurements of NO₂ and smoke. The rapid response PLD signal is produced when a HeNe probe beam is deflected by a thermal lens produced by a pulsed XeCl-excimer laser pumped dye laser. The fast time response (30 ns) and good spatial resolution make the PLD method a candidate for future in situ measurements in turbulent engine exhausts. The PLD signals, measured in a sample cell, exhibit a linear response for NO₂ concentrations from 3 ppm to 208 ppm and for smoke concentrations from 0.3 mg/m³ to 10 mg/m³. With a low pulse energy of 4 mJ, single-shot PLD measurements in a sample cell have accuracies of ± 14 ppm for NO₂ indicating accuracies of ±0.7 mg/m³ for smoke. With increased pulse energy and multi-shot averaging, sensitivities of ± 0.4 ppm of NO₂ or ± 20 µg/m³ of smoke are expected.     

Wavelength modulated cavity enhanced absorption spectroscopy of ammonia at 1994 nm

We describe the sensitive detection of ammonia by wavelength modulated cavity enhanced infrared tunable diode laser absorption spectroscopy at 1994 nm. The spectrometer can measure a fractional absorption of ∼10^-5 for an absorption pathlength of a few kilometers. The spectral resolution and sensitivity are sufficient to measure ammonia isotopomers (¹⁴NH₃, ¹⁵NH₃) in planetary atmospheres. The spectrometer is miniaturisable, so a future multiple-species version will be highly suitable for in situ planetary exploration and life-detection. PACS 42.62.Fi; 33.20.-t; 33.20.Ea     

Chemical and isotopic analysis using diode laser spectroscopy: applications to volcanic gas monitoring

We report on a diode-laser-based spectrometer, operating at a wavelength of 2 μm, which enables for simultaneous measurements of CO₂ and H₂O concentrations in gaseous mixtures with high precision and accuracy. We implemented the very simple approach of a direct measurement of absorption in a multiple reflection cell with a pathlength of 50 m. Gas concentration is simply retrieved from the integrated absorbance, without using calibration cells. The spectrometer is equipped with single-mode optical fibers in order to probe remote environments. The possible application in volcanic areas will be discussed. We also investigated the possibility to measure the isotopic ratio ¹³CO₂/¹²CO₂, which is another relevant parameter for monitoring volcanic activity.     

High-sensitivity detection of NO2 using a 740 nm semiconductor diode laser

 An AlGaAs diode laser was used to detect NO₂ absorption lines belonging to the (0 0 0)–(2 13 1) vibrational band, within the X˜² A ₁ electronic ground state, at 739 nm. A simple absorption spectrometer based on wavelength-modulation spectroscopy with second-harmonic detection was developed. The minimum detectable pressure of pure NO₂ was 0.1 μbar with 2 m absorption path-length, corresponding to an absorbance of 10^-6. High-sensitivity detection of NO₂ was also performed in the presence of N₂ and air at different total pressures: The effects on the detection limit of our apparatus were accurately investigated. The minimum NO₂ concentration at 500 mbar of air was measured to be 2 ppm. Received: 11 June 1996 / Revised version: 11 October 1996     

Simultaneous measurements of atmospheric HONO and NO<Subscript>2</Subscript> via absorption spectroscopy using tunable mid-infrared continuous-wave quantum cascade lasers

Nitrous acid (HONO) is important as a significant source of hydroxyl radical (OH) in the troposphere and as a potent indoor air pollutant. It is thought to be generated in both environments via heterogeneous reactions involving nitrogen dioxide (NO₂). In order to enable fast-response HONO detection suitable for eddy-covariance flux measurements and to provide a direct method that avoids interferences associated with derivatization, we have developed a 2-channel tunable infrared laser differential absorption spectrometer (TILDAS) capable of simultaneous high-frequency measurements of HONO and NO₂. Beams from two mid-infrared continuous-wave mode quantum cascade lasers (cw-QCLs) traverse separate 210 m paths through a multi-pass astigmatic sampling cell at reduced pressure for the direct detection of HONO (1660 cm⁻¹) and NO₂ (1604 cm⁻¹). The resulting one-second detection limits (S/N=3) are 300 and 30 ppt (pmol/mol) for HONO and NO₂, respectively. Our HONO quantification is based on revised line-strengths and peak positions for cis-HONO in the 6-micron spectral region that were derived from laboratory measurements. An essential component of ambient HONO measurements is the inlet system and we demonstrate that heated surfaces and reduced pressure minimize sampling artifacts.     

Growth of high quality non-linear optical crystal zinc germanium phosphide for Mid-infrared optical parametric oscillator

ZnGeP₂ single crystals were grown from Vertical Bridgman method. High-quality near-stoichiometric ZnGeP₂ single crystals were obtained in the diameter of 30 mm and length of 120 mm. The results showed that after thermal annealing of the crystals the optical absorption coefficient was below 0.03 cm^?1 at 2.05 μm, and ～0.02 cm^?1 at 3–8 μm. The low absorption loss ZnGeP₂ samples with dimension of 6 × 6 × 18 mm³ were cut from the annealed ingots for 3–5 μm optical parametric oscillation (OPO) experiments. For OPO experiment, we obtained up to 8.7 W output in the 3–5 μm wavelength range (with signal of 3.80 μm and idler of 4.45 μm, respectively) pumped by a 16.3 W 2.05 μm Tm,Ho:GdVO₄ laser at pulse repetition rate of 10 kHz, which corresponded to a conversion efficiency of 53.4% and slope efficiency of 64.8%, respectively.     

Femto-Fourier transform-cavity enhanced absorption spectroscopy in a supersonic expansion

Proofs of principle spectra of C₂H₄, N₂O and C₂H₂, including H¹²C¹³CH in natural abundance, are reported, recorded in the 1.6?µm range in an Ar supersonic expansion using femto-Fourier transform–cavity enhanced absorption spectroscopy. The effective absorption pathlength in the jet-cooled sample is up to 78?m and the optimal S/N is over 2300. The data processing is detailed. Saturation effects are reported for the C₂H₂ bands.